Abstract Book
RHODIUM PORPHYRIN CATALYZED HYDRODEBROMINATION WITH WATER
Yang, W, Chan, K.S.
e-mail: [email protected]
Department of Chemistry, Chinese University of Hong Kong, Shatin, N.T. Hong Kong, China
In the course of exploring the carbon-carbon bond activation of cyclopropane, we have discovered 1,1,dibromo-2-phenylcyclopropane undergoes rhodium porphyrin catalyzed hydrogenation with water as the hydrogenating agent to give 2-bromo-1-phenylpropene with one C-Br undergoing hydrodebromination. We have extended this hydrodebromination with water to other allylic and benzylic bromides and will report the results.
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Synthesis, characterization and DFT evaluation of trinuclear clusters containing isocyanides
Shawkataly, O. B.1, Sirat, S. S.1 and Goh, C. P.1 [email protected]
1Chemical Sciences Programme, School of Distance Education, Universiti Sains Malaysia, Penang, Malaysia
The chemistry of trinuclear carbonyl from Group 8 is dominated by the reactions of Group 15 ligands, particularly tertiary phosphines, phosphites or arsines. These ligands are widely studied in metal cluster chemistry due to their steric and electronic effects that are easily tunable. However, not many mono-, di and tri-substituted clusters containing isocyanide ligands have been structurally characterized. Thus, the structures of Ru3(CO)11[(CNC6H3(CH3)2], Os3(CO)11[(CNC6H3(CH3)2], Ru3(CO)10[(CNC6H3(CH3)2]2 and Os3(CO)9[(CNC6H3(CH3)2]3 had been synthesized and their molecular structures determined using single crystal X-ray crystallography method. Generally, isocyanide ligands coordinates at the axial position on metal cluster, while phosphines and arsine ligands tend to coordinate at equatorial position. However, in this work, it was found that the 2,6-dimethyl isocyanide ligand was coordinated to equatorial position on Ru3(CO)11[(CNC6H3(CH3)2] while in Os3(CO)11[(CNC6H3(CH3)2] it is at the axial position. Such deviation in ligand site preference is cannot be explained purely based on steric hindrance of the isocyanide ligand to the metal cluster. Thus, the geometry structures with the isocyanide ligand located at either equatorial/axial site were simulated. The theoretical studies were conducted in order to investigate whether or not the ligand site preference of these ligands correlates to the electronic effects. The electronic structure details obtained have provided supportive explanation on the deviation of the ligand site selection.
Ru3(CO)11[(CNC6H3(CH3)2]
Os3(CO)11[(CNC6H3(CH3)2]
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11 CO2 adsorption in porous coordination frameworks
Southon, Peter D1, Perkins, Gary2, Kepert, Cameron J1 and Pascali, Giancarlo2
1 School of Chemistry, The University of Sydney, Australia 2 Camperdown Cyclotron Facility, Australian Nuclear Science and Technology Organisation, Sydney, Australia
In this work we report a novel application for CO2 capture materials. A range of porous coordination frameworks (or metal-organic frameworks), already known to selectively 11 adsorb CO2, have been used to capture CO2 generated by a cyclotron. This opens up a means to improve the efficiency of radiopharmaceutical synthesis, and also a potential method to characterise and map CO2 adsorption systems.
Positron Emission Tomography is an important method for non-invasive monitoring of metabolic processes and molecular targets. Imaging agents incorporating 11C are used for cancer diagnosis and drug research, but the half-life of 20 minutes makes the rapid 11 11 separation and use of this isotope imperative. C is generated in a cyclotron as CO2 at ppm concentrations, and is usually separated using a liquid nitrogen trap. We report a series of experiments in which a set of coordination-framework materials are tested for 11 CO2 adsorption at low concentrations: UiO-66, amino-modified UiO-66, Mg(dobdc), ethylendiamine-appended Mg(dobdc), and Fe3[Co(CN)6]2 Prussian Blue, as well as reference materials Carbosphere and Zeolite 4A. Release profiles were measured as the materials were heated and substantial differences between materials were observed, which we relate to their sorption properties. We found that the UiO-66 based materials substantially outperformed the other candidates, with a comparatively high temperature for 11 100% capture and a narrow release profile. We have also shown that capture of CO2 by UiO-66 directly from the cyclotron is feasible. The implications both for improved radiopharmaceutical synthesis and novel methods for characterisation of CO2 capture systems will be discussed. 70 75 Activity in UiO-66 60 MOF Temperature 50
50 25 40 0 30 Activity / TBq / Activity
-25 / C Temperature 20
10 -50
0 -75 0 5 10 15 20 3 Time / min
II II 3D Hofmann Clathrate [M Pt (CN)4]∞ (M = Co, Ni) Synthesized by Postsynthetic Reductive Elimination
Takaishi, S1, Okamura, T1, Iguchi, H1, Breedlove, B, K1, Kosaka, W2, Miyasaka, H2, Yamashita, M1,3
Presenting author’s e-mail: [email protected]
1 Graduate School of Science, Tohoku University, Sendai, Japan 2 Institute for Materials Research, Tohoku University, Sendai, Japan 3 Advanced Institute for Materials Research, Tohoku University, Sendai, Japan
Metal-organic frameworks (MOFs) have been attracted much attention because they can be potentially used in a wide range of applications, such as gas storage, gas separation, chemical sensing, and chemical catalysis. Among them, cyano-bridged MOFs have been extensively studied because of their striking magnetic, photomagnetic, electrochemical, and adsorption properties. Especially, MOFs based on the square planar divalent II 2– tetracyanometalate [M (CN)4] (M = Ni, Pd and Pt) assemble with divalent transition metal ions (M' = Fe, Co, Ni, Cu, Zn and Cd), which are known as two dimensional Hofmann type clathrates ([M'M(CN)4]∞·nH2O.), have been interested in catalytic properties. Although some form 3D frameworks by connecting the 2D layer each other using pillar ligands such as pyrazine, there are no examples of 3D frameworks without using pillar ligands to the best of our knowledge. Furthermore, such a pillared layer structure has a drawback from the viewpoint of catalytic properties because the pillar ligands occupy the axial site of the M', which block the open metal sites. In this presentation, we report novel 3D MOFs II IV [M (H2O)2Pt (CN)4Br2]∞·8/3(H2O) (1: M = Co, 2: M = Ni) with an NbO topology using tetravalent dibromotetracyanoplatinate(IV) ion. Although these MOFs have no accessible pores for gas adsorption, we found that the axial and crystallization water molecules as well as axial Br ions on the Pt ions could be eliminated, accompanied by reduction of the Pt II II II II ions, by heating, affording porous frameworks [Co Pt (CN)4]∞ (1') and [Ni Pt (CN)4]∞ (2'). In this presentation, we report pore formation via post-synthetic reductive elimination and desolvation and the structures of the new MOFs as well as catalytic properties.
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A BIOHYBRID CATALYST USING A HEME-POCKET WITH AN ARTIFICIAL METALLOCOMPLEX
Hayashi, T, Onoda, A, Oohora, K
Osaka University, Suita, Japan
Hemoproteins are well-known and versatile metalloproteins. These proteins have a heme cofactor located within the interior of the protein. One of the heme cofactors, protoheme IX (heme b), is non-covalently bound within the heme pocket. Thus, the heme b-containing hemoproteins can generally be converted into the apo-form under acidic conditions, and the addition of heme b or an appropriate metal complex into a solution of the apoprotein triggers refolding to generate the corresponding reconstituted protein. Our group has focused on this process and devoted our efforts to obtain a series of modified hemoproteins with artificially created cofactors, because it is found that a hemoprotein pocket after the removal of native heme is useful for an attractive scaffold as a metallocomplex-linked site to produce a new biocatalyst. In this presentation, several examples of reconstituted hemoproteins will be presented: (1) Replacement of heme b in myoglobin with manganese porphycene provides a catalytic activity toward the hydroxylation of several inert alkanes via C(sp3)–H bond activation (Oohora 2013). (2) Conjugation of a diiron-carbonyl cluster with apocytochrome c is found to give a new [FeFe]-hydrogenase model which generates H2 in the presence of a Ru complex as a photosensitizer (Onoda 2011). Furthermore, our group also prepares the second generation of the hydrogenase model using aponitrobindin consisting of a -barrel structure with the diiron-carbonyl cluster. (3) Insertion of an organorhodium complex into the cavity of aponitrobindin via covalent linkage provides a polymerization catalyst for phenylacetylene in an aqueous media (Onoda 2014).
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A NEW FUNDAMENTAL TYPE OF CONFORMATIONAL ISOMERISM REVEALED
Canfield, PJ1,2,3, Blake, IM2, Cai, ZL2, Luck, IJ2, Krausz, E4, Kobayashi, R,1,4 Reimers, JR1,5, and Crossley, MJ2
1 Shanghai University, Shanghai, China, 2 The University of Sydney, Australia, 3 OraInnova, Sydney, Australia, 4 The Australian National University, Canberra, Australia, 5 University of Technology Sydney, Australia
The first new fundamental form of conformational isomerism since the discovery of pyrimidal inversion in 1961 is described. A new fundamental form of conformational isomerism based on bond-angle inversion is revealed through synthesis of four resolved stereoisomers 2a, 2b, 3a,and 3b of a transoid (BF)O(BF) quinoxalino[2,3- b’]porphyrin. These manifest structural relationships not describable within existing IUPAC nomenclature and terminology. The term “akamptisomerisation” is proposed to describe observed thermal diastereomeric interconversion processes, occurring in this case over a barrier of 104 2 kJ mol-1. We also introduce the new stereodescriptors parvo and amplo to describe the two coordinated atoms (here borons) with respect to their non-local environment (here a low- symmetry porphyrin). Density-functional theory calculations map out interconversion processes between conceivable synthesis products and reaction intermediates, with all 37 considered species successfully named using our new notation. Based on an extended polytope formalism of molecular structure and stereoisomerisation, bond-angle inversion is shown to be the final simple fundamental type of conformational isomerisation.
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A selection of polyoxometalate inorganic-organic hybrids and their properties
Ritchie, C., Xu, J., Karoui, H., and Spillane, S.
The University of Melbourne, Melbourne, Australia
Polyoxometalates (POMs) are anionic molecular fragments of early transition metal oxides that can be isolated through the condensation of simple oxyanions to yield oligomeric structures with somewhat predictable structural features and nuclearities.1 Control of the synthetic conditions within well understood pH and concentration domains can be exploited to yield molecules suitable for further derivatization by incorporation of heteroatoms, organometallic complexes or grafting of organic ligands to the surface of the molecular metal oxide.2
Herein, we discuss our recent progress regarding the preparation of new molecular species through a variety of approaches, with an emphasis on the utility of microwave-assisted synthesis.3 The compounds discussed have value as molecular precursors for incorporation in advanced materials as well as well as photoactivity resulting in single crystal to single crystal transformations and modulation of the electronic structure in both the solid and solution state.
[1] M. T. Pope, Polyoxometalate Molecular Science, Springer Netherlands, Dordrecht, 2003.
[2] D.-L. Long, E. Burkholder, L. Cronin, Chem. Soc. Rev. 2007, 36, 105–121.
[3] S. Spillane, R. Sharma, A. Zavras, R. Mulder, C. A. Ohlin, L. Goerigk, R. A. J. O’Hair, C. Ritchie, Angew. Chem. Int. Ed. 2017, DOI: 10.1002/anie.201608589
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A Spin Crossover Framework That Does It All
1 1 1 1 Zenere, K. A. , Neville, S. M. , D’Alessandro, D. M. and Kepert, C. J.
1The University of Sydney, Sydney, Australia
Spin crossover (SCO) is an electronic phenomenon where a 3d4–7 metal ion can reversibly switch between a high spin (HS) and low spin (LS) state upon an external perturbation (such as temperature, pressure, light irradiation, or guest exchange). One of the most exciting behaviours observed in these materials is the possibility of bistability, in which the material can exist in both spin states under the same conditions. For example, some materials have exhibited spin state switching at a single temperature using light of specific wavelengths, the application of increased pressure can induce a HS to LS transition, and guest exchange has been demonstrated to dramatically influence SCO behaviour within the one host material (particularly in porous systems). Notably, cooperative SCO behaviour in solid state systems arises through elastic interactions between the SCO sites, which propagate communication of spin state throughout the material, typically resulting in hysteretic and room temperature spin transitions. Such SCO behaviour has particular promise for applications such as data storage and molecular sensing devices.
Our research group focuses on incorporating 1,2,4-triazole functionalised ligands into 2D Hofmann-type framework materials, many examples of which have displayed interesting SCO behaviours. This work will explore one such material that exhibits a diverse range of SCO behaviours with temperature variation, pressure application, light irradiation, and guest manipulation. Through exploring the structural and magnetic consequences of spin state switching under these conditions, we have developed a greater fundamental understanding of the synergy between SCO and structural properties.
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AB INITIO LIGAND FIELD MOLECULAR MECHANICS APPLIED TO FE(II) SPIN CROSSOVER COMPLEXES
Deeth, R. J.1
1 University of Bath, Bath, UK
ABSTRACT Ligand Field Molecular Mechanics (LFMM) is an efficient tool for computer modelling of coordination complexes. It merges a d-electron energy term derived from the Angular Overlap Model (AOM) with a conventional force field to generate a method which explicitly accounts for the stereochemical activity of open d shells such as the Jahn-Teller effect. However, deriving realistic AOM parameters can be problematic in the absence of suitable experimental data. Here we exploit the recently-developed Complete Active Space Self Consistent Field/n-Electron Valence State Perturbation Theory (CASSCF/NEVPT2) ‘ab initio ligand field theory’ method developed by Neese and Anatasov to generate d orbital energy levels from first principles. The latter can then be used in a conventional AOM parameter fit suitable for use in LFMM simulations. The power of the approach is 2+ demonstrated using the Fe(II) spin crossover system [Fe(bpp)2] (bpp = 2,6-di(pyrazol-1- yl)pyridine). A new LFMM force field is generated which accurately describes both low spin and high spin structures, and their energy difference, with a single set of parameters. The potential for using the method to explore the intermolecular interactions responsible for hysteretic effects will be described.
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ACTIVATION AND FUNCTIONALIZATION OF SMALL MOLECULES USING IRIDIUM COMPLEXES BEARING PINCER LIGANDS
Balaji R. Jagirdar*, A. Ramaraj
e-mail: [email protected]
Department of Inorganic & Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India
ABSTRACT TEXT The partial oxidation of methane in natural gas to a liquid fuel, for example, methanol under relatively mild conditions using homogeneous organometallic compounds as catalysts, is a holy grail in the field of catalysis. Our research activities toward this goal have been concentrated at investigating the activation of unreactive chemical bonds in small molecules such as H2, silanes, borane-Lewis base adducts, and methane. As a first step towards this, rather challenging goal, it is imperative to study and understand the binding of these strong and inert H–X (X = H, SiR3, BH2·NR3, CH3) sigma bonds to transition metal centers and their unusual reactivity patterns relevant to activation and functionalization. Interaction of these bonds with metal centers is rather weak and studying them is rather challenging. In this talk, some of our efforts toward understanding these aspects using certain novel iridium pincer complexes will be discussed as shown in the scheme below.
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ADAPTIVE COMPLEXES IN MATERIALS COORDINATION CHEMISTRY
Hor, T. S. A.
The University of Hong Kong, Pokfulam, Hong Kong SAR
ABSTRACT TEXT Adaptive complexes are coordination systems that can respond to environmental changes or stimuli. Responses are commonly conformational, electronic, and physical, but could also be chemical and structural, etc. Different forms of stimulus are possible, from chemical to catalytic, from physical to photolytic, and from electro- to mechanical. Systems assembled from hybrid ligands with responsive complexes are typical examples of adaptive materials that are emerging in contemporary coordination chemistry. In this presentation, we shall describe our recent attempts and successes in the synthesis of adaptive complexes and assembly of dynamic materials from hybrid ligands. The multifunctional roles played by the functional ligands will be examined. We shall also explore future opportunities and possibilities in this growing field.
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Adsorption and sensing property of metal-organic frameworks with mixed ligands
Sun, Wei-Yin
e-mail: [email protected]
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
In recent years, metal-organic frameworks (MOFs) have attracted remarkable interests not only because of their intriguing framework structures, but also due to their interesting properties and potential applications in adsorption, storage and separation, heterogeneous catalysis, chemical sensing and drug delivery. We focus our attention on syntheses and properties of MOFs with mixed multicarboxylate and imidazole-containing ligands. In this presentation, we will report porous MOFs with selective adsorption and sensing properties. For example, two new MOFs [Co4(biimb)3(DSBPDC)2(H2O)3]·9H2O (1) and [Cd2(biimb)2(DSBPDC)(H2O)]·DMF·5.5H2O (2) (DMF = N,N-dimethylformamide) were successfully obtained by reactions of corresponding metal salts with imidazol-containing ligand 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (biimb) and 3,3'- disulfobiphenyl-4,4'-dicarboxylic acid (H4DSBPDC) under solvothermal conditions. Interestingly, 1 and 2 were found to show ability to selectively adsorb CO2 over N2, indicating their potential applications in separation. Furthermore, 2 can selectively sensing acetone molecule via the fluorescence quenching. On the other hand, reactions of 1,3,5- tris(1-imidazolyl)benzene (tib) and 4,4′,4″-benzene-1,3,5-triyl-tribenzoic acid (H3BTB) with Cd(II) salt give rise to two novel MOFs [Cd3(tib)2(BTB)2]·3DEF·4.5H2O (3) and [Cd3(tib)2(BTB)2(DMA)2(H2O)2]·2DMA·8H2O (4) (DEF = N,N-diethylformamide, DMA = N,N- dimethyl acetamide) with 3D framework structures. It is fascinating that 3 and 4 not only show unique selectivity for detection of acetone through fluorescence quenching mechanism but also exhibit selective adsorption of gas and dye molecules.
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Alkylamine-based Coordination Polymers Batten, SR1, Hawes, CS1, Hicks, J1, Emerson, AJ1, Hamilton, SE1, Beeching, LJ1, Knowles, GP1, Chaffee, AL1, Turner, DR1
Presenting author’s e-mail: [email protected]
1 Monash University, Melbourne, Australia
We have been investigating the use of alkylamine ligands in the synthesis of porous coordination polymers. The amine groups form part of the ligand backbones, and are designed to improve the selectivity of carbon dioxide capture over other gases. More than 50 new ligands have been made, and more than a dozen porous frameworks identified and tested. The ligands investigated fall into three different categories: (i) azamacrocycles, (ii) piperazines, and (iii) linear alkyl amines. Good carbon dioxide capacities and selectivities have been observed, as well as unusual structural transformations and interesting structural features. Related work has also looked at the use of these materials for the separation of complex aromatic hydrocarbon mixtures, and the incorporation of metal carbonyl species into the ligand backbones, with a view to creating new heterogeneous catalysts.
Figure 1. Example alkylamine ligands and porous coordination polymer.
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AMINE SYNTHESIS BY CATALYTIC REDUCTION OF NITROCOMPOUNDS USING MOLYBDENUM CLUSTERS
Llusar, R1, Pedrajas, E1, Sorribes, I1,2, Junge, K,3 Beller, M3 Presenting author’s e-mail: [email protected]
1 Universitat Jaume I, Castelló, Spain 2 ITQ-Universitat Politècnica de Valencia-CSIC, Valencia, Spain 3 Leibniz-Institute für Katalyse-University of Rostock, Rostock, Germany
Amines represent a key building block in academic research laboratories as well as for the preparation of fine and bulk chemicals, agrochemicals and pharmaceutical products.1 In recent years, molybdenum sulfide clusters have emerged as an alternative to noble metals for the catalytic reduction of organic substrates, in particular nitroarenes.2 Herein we present the synthesis of cuboidal homo and heterometallic diamino and diimino trimetallic molybdenum cluster sulfides, represented in Figure 1, emphasizing relevant reactivity aspects related to their catalytic applications.
Figure 1. Structures of diamino and diimino Mo3S4 and Mo3PtS4 cluster complexes
The activity and selectivity of these new cluster complexes in the catalytic hydrogenation of nitrocompounds directed toward the production of primary amines will be presented.
Tandem catalytic processes mediated by Mo3S4 and Mo3PtS4 clusters directed towards the chemoselective preparation of a variety of secondary and tertiary amines will be discussed. Tentative reaction mechanisms will be proposed.
1. A. Ricci, Amino Group Chemistry: From Synthesis to the Life Sciences 2008, ed. Wiley-VCH, Weinheim. 2. (a) I. Sorribes, G. Wienhöfer, C. Vicent, K. Junge, R. Llusar, M. Beller Angew. Chem. Int. Engl. Ed.. 2012, 51, 7794. (b) E. Pedrajas, I. Sorribes, K. Junge, M. Beller, R. Llusar ChemCatChem, 2015, 7, 2675. 14
AN IRON-BASED CATALYST THAT MIMICS FUNCTION OF THE OXYGEN-EVOLVING COMPLEX
Okamura, M1,2, Kuga, R1, Kawata, S3, Kondo, M1,4, Masaoka, S1,2
Presenting author’s e-mail: [email protected]
1 Institute for Molecular Science, Okazaki, Japan 2 Nagoya University, Nagoya, Japan 3 Fukuoka University, Fukuoka, Japan 4 JST ACT-C, Saitama, Japan
In natural photosynthesis, oxygen-evolving complex (OEC) catalyses water oxidation with high catalytic activity (TOF = 400 s-1). The development of an artificial catalyst that mimics function of the OEC has attracted extensive attention due to the urgent need to solve the energy and environmental problems. 1 Here, we report an iron-based molecular complex showing a high catalytic activity for water oxidation by mimicking key features of the OEC. 2 We employed an iron complex with multinuclear structures for enhancing four-electron transfer and with two water-activation sites separated by an appropriate distance for promoting intramolecular O–O bond formation. O2 evolution from water was confirmed by a controlled potential electrolysis. The TOF was electrochemically calculated to be 1,900 s-1, which is greater than that of the OEC. Interestingly, the estimated catalytic cycle is similar to the Kok cycle. The multiple iron centres contribute to the accumulation of four oxidizing equivalents through five oxidation intermediates from S0 to S4 and water activation occurs from the most oxidized state (S4). Quantum chemistry calculations indicate O–O bond formation proceeds smoothly between terminal iron-oxo units at adjacent sites to produce peroxo species. The details of the water oxidation catalysis and recent progress regarding the iron based systems will be discussed in this presentation.
(1) M. Okamura S. Masaoka, Chem. Asian J., 2015, 10, 306. (2) M. Okamura, M. Kondo, R. Kuga, Y. Kurashige, T. Yanai, S. Hayami, V. K. K. Praneeth, M. Yoshida, K. Yoneda, S. Kawata, S. Masaoka, Nature, 2016, 530, 465.
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Anaerobic Oxidation of Alcohols by Cu(I) Systems under Mild Conditions
Liu, Zhenzhen1, Zhan, Guangli1, Zhong, Wei2, Zhang, Ning1, Liu, Xiaoming2
Presenting author’s e-mail: [email protected]
1 Nanchang University, Nanchang, China 2 Jiaxing University, Jiaxing, China
Conversion of alcohols into aldehydes through anaerobic oxidation under mild conditions is of particular importance in chemical industry. Galactose oxidase (GOase) is a copper- containing enzyme which catalyses anaerobic oxidation of an alcohol into an aldehyde under physiological conditions. The structure of its metal centre revealed that the copper is five-coordinated, Figure 1.1 Mimicking the coordination environment around the metal centre has been one of the intensively studied areas in bioinorganic chemistry via ligand design.2 Another approach is functionally mimicking the enzymatic catalysis by using a bidentate ligand such as 2,2’-bipyridine and TEMPO radical. It is interesting to note that almost all the catalytic systems use N-methyl imidazole (NMI) as an additive. A curious question arises, what is the role of this small organic compound, the residual group of histidine, a base or a ligand, or both? Bearing this in mind, we attempted to explore the chemistry behind the catalytic systems. A recent report 3 and our preliminary results do confirm that imidazole itself, TEMPO and Cu(I) salt catalyse anaerobic oxidation of a variety of alcohols. The ratio of NMI over Cu(I) affects severely the catalytic activity and 2 to 1 ratio turns out the best. The reaction does not need a base and in fact, a base can jeopardise the catalysis. Now, it is certain that the coordination chemistry between Cu and NMI play an essential role. The ratio is in agreement with the observation that a bidentate ligand such as tetramethylethylene-diamine can nicely catalyse the oxidation with the help of TEMPO. That CuI can be replaced by [Cu(NCMe)4] indicates that both the mono and bidentate ligand dictate the coordination chemistry in the catalysis. The systems can convert nearly and quantitatively 1-octanol into 1-octanal using air as the oxidant under ambient temperature. The catalysis is investigated using a variety of techniques such as electrochemistry, UV-vis and FTIR spectroscopies.
Figure 1 Structural view of the metal centre of GOase (left) and the Cu(I) catalytic systems (right).
References 1. Ito, N, Phillips, SEV, Stevens, C, Ogel, ZB, McPherson, MJ, Keen, JN, Yadav, KD, Knowles, PF, Nature, 1991, 350, 8790. 2. Lyons, CT, Stack, TD, Coord. Chem. Rev., 2013, 257, 528540.
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3. Steves, JE, Preger, Y, Martinelli, JR, Welch, CJ, Root, TW, Hawkins, JM, Stahl, SS, Org. Process Res. Dev., 2015, 19, 1548−1553.
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Anion/solvent influences on Ag(I) architectures containing flexible asymmetric ligands
Marina Roxburgh, David A. McMorran and Lyall R. Hanton
University of Otago, Dunedin, New Zealand
The use of flexible ligands in coordination polymer chemistry gives rise to a diverse range of interesting and novel architectures with highly variable networks. The unpredictable nature of these structures is further exacerbated when they are formed using ligands that are also unsymmetrical. Previous research involving flexible dipyridyl ligands has shown the formation of a wide range of structural motifs, in part due to the ability of the rings to rotate. X-ray crystallography has shown a range of differing architectures that can be formed by altering the counter ion, solvent or metal cation.
The use of the unsymmetrical flexible ligand 3,4-dipyridyl methanol in the formation of a range of architectures when coordinated to varying Ag(I) salts will be described. The strength of the interaction between the Ag(I) cation and the counter ion affected the formation and packing of 1-D polymer chains, which ranged from helices, double helices - - - - and meso-helices. Both non-coordinating and binding anions (PF6 , BF4 , ClO4 , CF3SO3 - and NO3 ) generated 1-D helical chains, where the nature of the interaction between the anion and Ag(I) cation determined if the helices interacted to form sheets or double helices.
Of note was the formation of both a discrete hexameric macrocycle and 2-D sheet - comprised of helices formed with the CF3CO2 anion. The two structures are devoid of solvent and have the same asymmetric unit. The difference appears to arise from the - templating influence of different solvents. The CF3CF2CF2CO2 anion also formed a - discrete hexameric macrocycle while the CF3CF2CO2 anion formed 2-D sheet comprised of helices.
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Anticancer Organometallic Compounds of Anti-inflammatory Oxicams: Bioanalytical Studies and Cytotoxicity
Hanif, M1, Aman, F2, Ashraf, A,2 Siddiqui, W. A,2 Söhnel, T,1 Jamieson, S. M. F,3 Hartinger, C. G1
Presenting author’s e-mail: [email protected]
1 School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1142, New Zealand 2 Department of Chemistry, University of Sargodha, Sargodha 40100, Pakistan 3 Auckland Cancer Society Research Centre University of Auckland, Private Bag 92019, Auckland 1142, New Zealand
ABSTRACT
The nitrogen- and sulfur-containing 1,2-benzothiazines meloxicam and piroxicam are widely used as non-steroidal anti-inflammatory drugs for the treatment of a variety of inflammatory and rheumatic diseases in humans.1 Intrigued by the presence of multiple donor atoms and therefore a potentially rich coordination chemistry, we prepared a series of organo-Ru and -Os compounds with meloxicam and piroxicam featuring either as mono- or bidentate ligand systems. The choice of the solvent and the pH value was identified as the critical parameter to achieve selectively mono- or bidentate coordination.2 The coordination modes were confirmed experimentally by NMR spectroscopy and single crystal X-ray diffraction analysis of a wide variety of derivatives. Using DFT calculations, it was established that complexes where meloxicam acts as a bidentate N,O donor are energetically more favorable than coordination as O,O and S,O donor systems. Since meloxicam and piroxicam derivatives have shown anticancer activity, the complexes were evaluated on their in vitro anticancer activity.3 In this presentation, synthetic strategies, the versatile coordination chemistry of oxicams and the biological activity of their metal complexes will be discussed.
References 1. Cuzick, J.; Otto, F.; Baron, J. A.; Brown, P. H.; Burn, J.; Greenwald, P.; Jankowski, J.; La Vecchia, C.; Meyskens, F.; Senn, H. J.; Thun, M. Lancet Oncol. 2009, 10, 501. 2. F. Aman, M. Hanif, A. Ashraf, W. A. Siddiqui, M. Kubanik, T. Söhnel, S. M. F. Jamieson, C. G. Hartinger;; Chemistry – A European Journal (2017), DOI: 10.1002/chem.201700263. 3. Aman, F.; Hanif, M.; Siddiqui, W. A.; Ashraf, A.; Filak, L. K.; Reynisson, J.; Söhnel, T.;
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Jamieson, S. M. F.; Hartinger, C. G. Organometallics. 2014, 33, 5546.
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Artificial Photosynthesis by Light Absorption, Charge Separation, and Photoredox Catalysis
Ng, Y. Y.1, Wang, J.1, Ho, X. L.1,2, Lim, J. H.1, Gazi, S.1, Dokic, M.1, Soo, H. S.1,2,3
Presenting author’s e-mail: [email protected]
1 Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, Singapore, Singapore 2 Solar Fuels Laboratory, Nanyang Technological University, Singapore, Singapore 3 Singapore-Berkeley Research Initiative in Sustainable Energy, Singapore, Singapore
ABSTRACT TEXT Artificial photosynthesis has been recognized as a sustainable approach to utilize solar energy for chemical reactions and energy storage. The critical functions of artificial photosynthetic systems include light absorption, charge separation, and multi-electron catalysis. In this presentation, I will summarize my team’s early contributions to each of these elementary components. I will describe our efforts in the preparation of Cu(I) photosensitizers supported by bis(arylimino)acenaphthene ligands. The diamagnetic, homoleptic Cu(I) complexes exhibit panchromatic light absorption extending to the near infrared region. The transient absorption spectroscopic and photoluminescence measurements of some of the new Cu(I) complexes will be reported.1 For the multi-electron reductive half-reaction, my team has recently reported new salicylaldimine nickel complexes bearing ether pendant arms that perform as hydrogen evolution electrocatalysts, even in seawater.2 Regarding the multi-electron oxidative half-reaction, we have discovered a new selective, photoredox C-C activation reaction catalyzed by vanadium complexes, which occurs under ambient, atmospheric conditions using visible light as the energy source.3 We have prepared a library of over 10 vanadium catalysts and performed kinetics and mechanistic studies to identify the most active variant. In another example, we have utilized nanosecond time-resolved optical spectroscopy and density functional theory calculations to elucidate the mechanism of an anthraquinone photocatalyzed aliphatic C-H bond fluorination reaction. In addition, I will briefly discuss how our team has shown that high valent iron complexes can be accessed by outer sphere photooxidation processes.
[1] Inorg. Chem. Front. 2017, 3, 651. [2] Chem. Commun. 2016, 52, 2948. [3] Chem. Sci. 2015, 6, 7130.
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Assembly of Metal-organic Architectures and Enzymatic Simulation
Chunying Duan1, Yang Jiao 2
Presenting author’s e-mail: [email protected]
1 State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023 (P. R. China). 2 College of Chemistry, Dalian University of Technology, Dalian, 116023 (P. R. China). Humans are urged to learn from how nature obtains energy and materials through a sustainable approach called artificial enzymatic simulation. Metal-organic supramolecular systems, which constructed through the coordination of metal ions and organic linkers, represent a unique species of functional molecular containers that display interesting recognition properties and fascinating reactivity reminiscent of the natural enzymes. These architectures generating well-defined cavities provided functional interaction sites and well- defined inner void spaces for selective bonding of a specific guest molecules and catalysing related reactions. Owing to their promising functionalities as artificial metalized host platforms, it is possible for these molecular hosts to mimic protein receptors or enzymes for their abilities to effectively bind substrates, stabilize reactive intermediates, and catalyse chemical transformations. Through incorporating amide-containing multidentate chelators within the ligand backbone, herein we reported the synthesis and catalytic properties of several metal-organic hosts to investigate the possibility in the application of enzymatic simulation. These metal-organic architectures could capsule guest molecular through specific inner spaces and bonding sites and realize natural enzymes simulation.
Scheme 1. Schematic diagram of metal-organic architectures
References 1. L. Zeng, T. Liu, C. He, D. Y. Shi, F. L. Zhang and C. Y. Duan, J. Am. Chem. Soc. 2016, 138, 3958. 2. Z. Zhou, C. He, L. Yang, Y. F. Wang, T. Liu, and C. Y. Duan, ACS Catal. 2017, 7, 2248. 3. X. Z. Li, J. G. Wu, C. He. R. Zhang and C. Y. Duan, Chem. Commun. 2016, 52, 5104. 4. X. Z. Li, J. G. Wu, L. Y. Chen, X. M. Zhong, C. He. R. Zhang and C. Y. Duan, Chem. Commun. 2016, 52, 9628. 22
B−H···π Interaction: A New Type of Nonclassical Hydrogen-Bonding
Yan, H
Nanjing University, Nanjing, China
ABSTRACT TEXT
Nonclassical hydrogen bonds (H-bond) between an X−H donor and the π face of an aromatic ring (X−H···π bonding, X = C, N, O) have been verified by both experimental and computational methods. They are of tremendous importance in structural biology and supramolecular self-assembly. The potential interaction between a B−H bond as H-donor and the π face of an aromatic moiety in the sense of B−H···π interaction has not been observed before our work because the electropositive character of boron (B) makes B a poor H-donor. Herein we describe the nonclassical H-bonding involving a B−H···π interaction by utilizing both quantum chemical predictions and experimental realization. Ir- dimercapto-carborane complexes [Cp*Ir(S2C2B10H10)] are designed to react with phosphines PR3 to give [Cp*Ir(PR3)S2C2B10H10] for an investigation of B−H···π interactions at ambient temperature. X-ray diffraction studies reveal that the interaction between the carborane BH bonds and the phosphine aryl substituents involves a BH···π H-bond (H···π distance: 2.40−2.76 Å). 1H NMR experiments reveal that B−H···π interactions exist in solution according to the measured 1H{11B} signals in the range 0.0 ≤ δ ≤ 0.3 ppm. They are high-field shifted by more than 1.5 ppm relative to the 1H{11B} signals obtained for the PMe3 analog without B−H···π bonding. Quantum chemical calculations suggest that the interaction is electrostatic.[1]
Fig.1 Evidences of B−H···π interaction both in solid (left) and in solution (right).
REFERENCES
23
[1] Zhang, X, Dai, H, Yan, H, Zou, W, Cremer, D, J. Am. Chem. Soc. 2016, 138, 4334.
24
Bioinspired Catalytic Reactions Using Vitamin B12 Derivative
Hisaeda, Y
Kyushu University, Fukuoka, Japan
As part of a study directed toward design of artificial enzymes based upon a hydrophobic vitamin B12, we report preparation of various nanomaterials with the vitamin B12 derivative and photosensitizers. We have been interested in vitamin B12-dependent enzymes, involving the cobalt species as a catalytic center, and dealing with a hydrophobic vitamin B12, heptamethyl cobyrinate perchlorate, which has ester groups in place of the peripheral amide moieties of the naturally occurring vitamin B12. In order to construct a good catalytic system, we prepared various nanomaterials with vitamin B12 activities. Examples include a vitamin B12-Rose Bengal combined system, a vitamin B12-titanium dioxide hybrid catalyst, a vitamin B12-Ru complex combined system, and vitamin B12-hyperbranched polymers. These bioinspired materials have potential as catalytic systems for degradation of organic halide pollutants and for molecular transformations via radical intermediates under irradiation with UV or visible light, and offer scope for applications that are of great interest in terms of green chemistry. Recently, we applied trifluoromethylation reactions catalyzed by hydrophobic vitamin B12 using electrochemical and photochemical activation. This catalytic system can apply to perfluoroalkylation reactions.
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Bio-inspired Efficient Electrocatalysts for the Oxygen Reduction Reaction in Fuel Cells
Liu, Jin-Gang*, Wei, Ping-Jie, Yu, Guo-Qiang, Wang, Fei-Fei, Zhao, Ye-Min
e-mail: [email protected]
School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, P. R. China
The oxygen reduction reaction (ORR) has been regarded as a major bottleneck that limits fuel cell performance due to the sluggish reaction kinetics and diverse reaction pathways. To explore an alternative to the dominant noble metal Pt-based ORR electrocatalysts in current use, a large variety of nonprecious metal catalysts have been explored, which were generally prepared by pyrolysis of suitable transition metal ions and nitrogen containing precursors with or without a carbon matrix at high temperatures. However, uncertainties remain in controllable catalyst preparation and elusive active sites for the ORR. On the other hand, ORR catalysts prepared in a non-pyrolyzed manner offer the feasibility to tune the catalytic activity via controllable variation of the catalyst structure with defined reaction active sites. Based on our biomimetic mechanistic studies on the binding/activating of O2 by metalloenzymes such as heme-containing enzymes, we developed a new class of high performance catalysts for the ORR, wherein structure- defined biomimetic catalysts including iron porphyrins and copper complexes were covalently grafted onto the surface of carbon-based supports.1 In this presentation, we will show our efforts to improve the ORR catalyst's activity and stability via rational catalyst design from a bio-inspired approach, and demonstrate their applications to low temperature fuel cells.
References: 1．J.-G. Liu*, et al. Angew. Chem. Int. Ed. 2014, 53, 6659; RSC Adv. 2015, 5, 66487; Chem. Commun. 2015, 51, 7455; Chem. Eur. J. 2016, 22, 382; Chem. Commun. 2017, 53, 1514.
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Bismuth Vs. Bacteria: Compounds for Antibacterial Materials
Werrett, M.V1, Andrews, P.C1, Brammananth, R1, Crellin, P1, Garusinghe, U1, Batchelor, W1, Herdman, M1, Kidner, E1
1 Monash University, Melbourne, Australia
Antimicrobial resistance is causing an alarming number of deaths in hospitals and healthcare facilities. Bacteria which were once easily treatable are now resistant to last line antibiotics.1 High-contact surfaces often harvest biofilms which are a common source for the transfer of infection.2 To overcome this crisis, it is important to incorporate antibacterial properties into these high-touch surfaces to ensure a reduced spread of infection.3-4 We have synthesised a series of bismuth(III) complexes; with varying lepticity. The complexes are either of the type BiL3, with three ligands surrounding the bismuth centre, or BiPhL2, where the bismuth contains one phenyl group and two ligands. Interestingly, depending on the type of ligand, the lepticity plays a direct role in the activity of the overall complex.
We have incorporated some of the active bismuth(III) complexes into a range of polymer supports including; agar, cellulose, polyethylene and nylon. The bismuth-containing materials tested appear to have comparable activity to some silver-based antibacterial additives (Figure 1).
Figure 1: Zone of inhibition test against VRE, using bismuth paper. Bismuth complex loaded at 0, 0.1, 0.5, 1 and 5 wt%. Ag: silver sulfadiazine at 0.5 wt%.
References 1. World Health Organization, (2014), 1–232. 2. P. L. Russo; A. C. Cheng; M. Richards; N. Graves and L. Hall, Aust. Heal. Rev. 2015, 39, 37 3. M. Cruickshank and J. Ferguson, Reducing harm to patients from health care associated infection: the role of surveillance, Australian Commission on Safety and Quality in Health Care. 2008. 4. W.W. Metcalf; W.A. van der Donk, Annu. Rev. Biochem. 2009, 78, 65.
27
The nature of bonding in nickel(0) complexes: an X-ray spectroscopic perspective
Pierre Kennepohl
The University of British Columbia, Department of Chemistry, Vancouver, Canada
Transition metal -complexes play an important role in inorganic and organometallic catalytic processes. They often serve either as useful precursors or as putative intermediates in a number of important transformations. Spectroscopic and computational studies on the nature of certain olefin complexes have revealed that such systems are often more complex than typically envisaged. We have undertaken a systematic evaluation of a series of nickel -complexes formed from nickel(0) precursors to explore the importance of -backbonding in these systems. A combination of spectroscopic and computational methods are used to evaluate the electronic structure of these systems and to develop a better understanding of the factors that control the reactivity of such systems.
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CERIUM(IV) OXO COMPLEXES AND CLUSTERS WITH A TRIPODAL OXYGEN LIGAND
Leung, W.-H, So, Y.-M., Au-Yeung K.-C. Presenting author’s e-mail: [email protected]
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
ABSTRACT
Metal-oxo complexes are of importance due to their involvement as active intermediates in metal-catalyzed oxidations. Although transition metal and actinide oxo complexes are well documented, lanthanide complexes with terminal oxo ligands are very rare owing to the high polarity of the lanthanide-oxo bond. Supported a sterically bulky, -donating tripodal - - oxygen ligand, [CpCo{P(O)(OEt)2}3] (LOEt ), a stable Ce(IV) terminal oxo complex, [(LOEt)2Ce=O(H2O)]Me2CONH2 (1), which contains a short [1.857(3) Å] and polarized Ce=O multiple bond has been isolated recently. Complex 1 exhibits nucleophilic reactivity and can be reduced to a Ce(III) species by CO.1 In hexanes containing water, 1 is readily 2 converted to a tetranuclear Ce(IV) oxo cluster, [(LOEtCe)4(O)5(OH)2] (2). Herein, we describe the reactivity of 1 and 2 toward electrophiles and Brønsted acids, and their redox behaviour.
References 1. So, Y.-M.; Wang, G.-C.; Li, Y.; Sung, H. H.-Y.; Williams, I. D.; Lin, Z.; Leung, W.-H. Angew. Chem., Int. Ed. 2014, 53, 1626. 2. So, Y.-M.; Li, Y.; Au-Yeung, K.-C.; Wang, G.-C.; Wong, K.-L.; Sung, H. H. Y.; Arnold, P. L.; Williams, I. D.; Lin, Z.; Leung, W.-H. Inorg. Chem. 2016, 55, 10003.
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CHARGE TRANSFER INTERACTIONS FOR MOLECULAR MAGNETISM
Hiroki Oshio
University of Tsukuba, Tsukuba, Japan
Metal ions are assembled into a molecule, which may exhibit interesting chemical and physical properties, characteristic of its structure and electronic state. In particular, mixed valence molecules show specific properties such as enhanced magnetic interactions and state conversion, which are essentially due to their charge transfer (CT) interactions. Mixed valence species can be classified into three groups depending upon delocalization of the valence electrons and it is important to control CT interactions by tuning redox potentials and the orientation of frontier orbitals. CT interactions have been used for constructing high-spin molecules and electron transfer (ET) systems which result in quantum magnetism and multi-bistability. Specifically, we focus on the CT interactions and the ET for molecular magnetism, including: ferromagnetic interaction due to orthogonal orbital arrangement, state conversions by spin crossover and electron transfer, and solid to solution chemistry.
References [1] H. Oshio, T. Watanabe, A. Ohto, T. Ito, Angew. Chem., Int. Ed. Engl. 1994, 33, 670- 671. [2] G. N. Newton, K. Mitsumoto, R. -J. Wei, F. Iijima, T. Shiga, H. Nishikawa, H. Oshio, Angew. Chem. Int. Ed. 2014, 53, 2941-2944. [3] T. Matsumoto, G. N. Newton, T. Shiga, S. Hayami, Y. Matsui, H. Okamoto, R. Kumai, Y. Murakami, H. Oshio, Nat. Commun., 2014, 5, 3865/1-3865/8. [4] M. Nihei, Y. Yanai, I.-J, Hsu, Y. Sekine, H. Oshio, Angew. Chem. Int. Ed. 2017, 56, 591- 594.
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Chemical Property of Elemental Substituents of Heme Thiolate Complex
Shirakawa, Y, Niwa Y, Umezawa, N, Kato, N, Higuchi, T
e-mail : [email protected]
Graduate School of Pharmaceutical Sciences, Nagoya City University, Nagoya, Japan
ABSTRACT TEXT Cytochrome P450 plays a central role in drug metabolism and steroid biosynthesis. Among heme enzymes, cytochrome P450 and NO synthase (NOS) have strong oxidizing ability and unusual structure, in that their heme iron has thiolate coordination. We previously succeeded in synthesizing the first synthetic heme thiolate (SR complex)1 which retains thiolate coordination during catalytic oxidation and found several remarkable axial ligand effects on catalytic oxidation. However, alcoholate and selenolate ligand, which are belonged to chalcogen group same as thiolate, have not ever been examined for researching such relative effect of axial ligand by us and other investigators. Now we prepared the first isolable heme alcoholate 1, heme selenolate 2 and manganese heme thiolate 3 in order to investigate the effect of elemental substitution on SR complex on spectroscopic and catalytic properties. We obtained UV-Vis spectra, FT-IR and EPR spectra of these complexes. The N-O stretching mode of complex 1-NO was 60 cm-1 higher than that of SR-NO and 38 cm-1 lower than that of an alcohol-ligated heme2. Complex 1 had 0.2 V higher E1/2 (Fe(II)/Fe(III)) than that of SR complex. These two results indicate that electron donative ability of alcoholate is much less than that of thiolate. Catalytic activity of 1 was much lower than that of SR on the oxidation of 2,4,6-tri-tert- butylphenol with perphenylacetic acid. On the other hand, catalytic activity of complex 3 was comparable to that of SR.
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CONSTRUCTION AND STRUCTRUAL CHEMISTRY OF TP*-COORDINATED MOLYBDENUM(TUNGSTEN)-SULFUR- COPPER CLUSTERS
Lang, J. P.
E-mail: [email protected]
Soochow University, Suzhou, China
ABSTRACT In the past decades, we have investigated assembly reactions of the metal sulfide 2- - synthons [MS4] and [Cp*MS3] (M = Mo, W; Cp* = 1,2,3,4,5-pentamethylcyclo- 2- pentadienyl) with Cu(I) salts or some preformed clusters like [MS4Cu4X6] and - [Cp*MS3Cu3X3] via different N-donor ligands. The as-prepared Mo(W)/Cu/S clusters showed rich structural chemistry and good third-order NLO responses.[1a,b] This presentation will demonstrate our recent progress in exploring assembly reactions of the synthons ([Et4N][Tp*WS3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) and [1c] [Et4N][TpMoS(S4)] (Tp = hydridotris(pyrazol-1-yl)borate) with Cu(I) salts or the [Tp*MS3Cux]-based precursors via bridging ligands. To date, several dozens of Tp*- coordinated Mo(W)/Cu/S clusters and coordination polymers have been separated, which [2] exhibit many interesting [Tp*WS3Cux]-based topological architectures. Some tetrahedral- cage clusters like [(Tp*WS3Cu3)(4,4'-bipy)]4(BF4)8 (4,4'-bipy = 4,4'-bipyridine), hma@{[Tp*WS3Cu3][Cu(CN)3]}4 (hma = hexamethylenetetramine), [(Tp*WS3Cu3)4(µ- CN)6](SO4) and square-like cluster like [(Tp*WS3Cu3)4(µ-CN)2(µ-Cl)4(µ4-Cl)2] are even 2- - unparalleled in the chemistry of [MS4] and [Cp*MS3] , and their NLO performances could be improved relative to those of their synthons and the cluster precursors.
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Controlling of Ligand Field Splitting in Four- and Five-Coordinated Complexes
Ishii, T1, Tsuneda, D1, Tsutsumi, Y1, Nakano, M1, Iwakura, M1, Sakane, G2, Ogasawara, K3
1 Kagawa University, Takamatsu, Japan 2 Okayama University of Science, Okayama, Japan 3 Kwansei Gakuin University, Sanda, Japan
ABSTRACT We have investigated a new way to obtain a novel spin crossover (SCO) compound in a four- and five-coordinated metal complexes by distorting a shape of the molecule from tetrahedral (Td), square planar (D4h), trigonal bi-pyramidal (D3h), and square pyramidal (C4v) symmetries. In order to obtain the novel metal complex having a SCO phenomenon, it is required to adjust the value of the ligand field splitting to the boundary between high and low spin states. However, the boundary should be varied depending on the combination of the central metal ion with a ligand molecule. There is no way to investigate by an experimental how much is the boundary of the ligand field splitting. Therefore, in order to design efficiently a novel metal complex having SCO phenomenon, not by a conventional trial and error method, but a create a novel type of the Tanabe-Sugano diagram, for investigating the size of the boundary between a high and a low spin states. Few researches of SCOs in the cases of four- and five-coordinated metal complexes have been investigated. The ligand field splitting in four- and five-coordinated metal complexes are smaller than that in the case of an octahedral (Oh) symmetry. Researches of the basic spectrochemical series and the Tanabe-Sugano diagram in four- and five-coordinated compounds are quite rare. In this study, we introduce a method to control the ligand field splitting in four- and five-coordinated metal complexes.
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Coordination Assembly of Metal-Organic Materials ---Metal-Organic Containers (MOCs) and Applications
Cheng-Yong Su, Mei Pan, Kang Li, Sha Chen, Kai Wu, Ya-Jun Hou
School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China
ABSTRACT TEXT
The use of metal-ligand interactions as driving forces to assemble metal-organic container (MOC) structures of varied shapes and sizes is emerging as one important supramolecular approach towards well-defined and ordered architectures containing internal cavities. Such systems have attracted considerable attention owing to their potentials in molecular storage, recognition, delivery, catalysis, as well as nanoreactors.
We have long been involving in the design and synthesis of cyclic, tubular or cage-like MOCs through various rigid, semi-rigid or flexible ligands, with specific interest in coordination containers installing redox- and photoactive functional sites and groups. This lecture will focus on the design and assembly of some MOCs from our group.
References [1]. Kai Wu, Kang Li, Ya-Jun Hou, Mei Pan, Lu-Yin Zhang, Ling Chen and Cheng-Yong Su, Nat. Commun. 2016, 7:10487. [2]. Li, K.; Zhang, L.-Y.; Yan, C.; Wei, S.-C.; Pan, M.; Zhang, L.; Su, C.-Y. J. Am. Chem. Soc., 2014, 136, 4456−4459. [3]. He, Q.-T.; Li, X.-P.; Liu, Y.; Yu, Z.-Q.; Wang, W.; Su, C.-Y. Angew. Chem. Int. Ed., 2009, 48, 6156−6159. [4]. Chen, C.-L.; Zhang, J.-Y.; Su, C.-Y. Eur. J. Inorg. Chem., 2007, 2997−3010. [5]. Su, C.-Y.; Cai, Y.-P.; Chen, C.-L.; Smith, M. D.; Kaim, W.; zur Loye, H.-C. J. Am. Chem. Soc., 2003, 125, 8595−8613.
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COORDINATION CHEMISTRY OF METALLODRUGS AND METAL SENSORS
Guo, Z.J.
Nanjing University, Nanjing, China
ABSTRACT Molecular design of metal-based anticancer drugs and sensors for biological inorganic species are two active research areas in coordination chemistry. In this context, our lab has been focusing on the following two research subjects: 1) design and delivery of platinum- based antitumor complexes; 2) molecular sensing and imaging of bio-medicinal inorganic species. In this lecture, I will summarize our recent works in these two topics, and illustrate the close links between their coordination chemistry and bio-medical applications. In the search for novel sensors of bio-metals and inorganic signalling species, we have been concentrating on the design of fluorescent probes that can be excited by visible light and have ratiometric potential. The targeting properties to specific sub-cellular compartments such mitochondria or lysosomes are also desirable. On the other hand, the biological and pharmacological properties of metallodrugs can be finely tuned by rationale design of the coordination sphere of metal centres, or by conjugating the drug molecules with additional targeting vehicles.
References: 1) Wang X.Y., Wang X.H., Guo Z.J. Acc. Chem. Res. 2015, 48, 2622−2631. 2) Chen Y.C.; Bai Y., Han Z., He W.J., Guo Z.J. Chem. Soc. Rev., 2015, 44, 4517-4546. 3) Muhammad N., Guo Z.J. Curr. Opin. Chem. Biol., 2014, 19, 144-153.
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Coordination Controllable Single-Molecule Magnets with Enhanced Anisotropic Energy Barrier
Ding, Y.-S.1 and Zheng, Y.-Z.1
Presenting author’s e-mail: [email protected]
1 Frontier Institute of Science and Technology (FIST), Xi’an Jiaotong University, Xi’an 710054, P. R. China.
Single-molecule magnets (SMMs) have received much attention due to their potential applications in high-density information storage, carriers of spin qubits and molecular spintronics. However, up to date, typical SMM behaviors are only realized at very low temperatures. How to enhance the energy barrier to magnetic reversal (Ueff) and so as the blocking temperature needs a deeper understanding of the magneto-structural correlation of specific metal centers. With this purpose, we chose some complexes in which the metal centers are low-coordinated and synthetically easily to control to investigate their magneto- structural correlations.1-3
Upon this effort we recently designed and realized a monometallic dysprosium t 4 complex, [Dy(O Bu)2(py)5][BPh4] 1, in which the Dy(III) ion locates in a near-perfect pentagonal bipyramid geometry with strong bis-trans-disposed t-butoxide ligands coordinated in the axial position and five pyridine donors weakly surrounded in the equatorial plane (Figure 1). This complex fits perfectly to the pseudo-two-coordinate model and thus shows a record Ueff (1815 K) and for the first time, observable magnetic relaxations above liquid nitrogen temperature. The blocking temperature of this complex is 14 K, defined by zero-field-cooled magnetisation experiments, and is the highest for any monometallic complex.
t + Figure 1, (a) Crystal structure of the [Dy(O Bu)2(py)5] cation in complex 1. (b) plot of magnetic relaxation times of 1, the solid line is the best fitting.
1) Deng et al. Chem. Commun., 2015, 51, 17688. 2) Deng et al. Chem-Eur J, 2016, 22, 14821. 3) Yu et al. Inorg. Chem. Front., 2016, 3 , 798. 4) Ding et al Angew. Chem. Int. Ed., 2016, 55 , 16071. 37
Coordination Exchange for Activation of Open Metal Sites in MOFs
Jeong, N. C.
Presenting author’s e-mail: [email protected]
DGIST, Daegu, Korea
ABSTRACT TEXT (Arial, 12 font, left aligned, maximum 250 words) Open coordination site (OCS) on intersectional transition metal ion has shown considerable potential in its role for the applications in i.e., high ion transport and efficient gas adsorption. Thus, the activation of MOFs, the removal of precoordinated solvent molecules at the OCSs, has been thought as a prerequisite process prior to use of the MOFs for those applications. To date, several strategies for activating MOFs have been suggested. Among them, the thermal activation, which is normally performed by applying heat and vacuum, has been a unique way to remove the OCS-coordinated solvent molecules. Given that high temperature can lead to structural damage to MOFs, conceivable low-temperature process will be a promising way, compared to the cumbersome, pricey heat-and-vacuum technique. In this presentation, we will discuss how to control the activation condition for maintaining structural integrity during the activation process. Particularly, a new activation method, “chemical activation” which is operated by the coordination-scissoring function of dichloromethane (DCM), will be presented. While DCM treatment is surely a known method for replacing pore-filling solvent prior to thermal activation process, the role of the DCM for dissociating the metal-solvent coordination has never been demonstrated. We observed that the chemical activation by DCM arises via (i) exchange of pre-coordinating solvent with the coordination of DCM and (ii) subsequent spontaneous decoordination of DCM with low activation energy at room temperature. Meanwhile, although this chemical activation is an effective method, strongly coordinated solvents such as N,N-dimethylformamid (DMF), N,N-diethylformamid (DEF), and dimthylsulfoxide (DMSO) cannot be applied to this method because their coordination strength is too high to be replaced by DCM. To exceed this limit, we designed an advanced chemical activation method, “multistep chemical activation”. This process includes an intermediate coordination exchange step with moderate strength coordination. More concretely, the process consists of (i) initial coordination exchange of strongly precoordinating DMF molecules by other solvent molecules with moderate coordination strength such as methanol, ethanol, or acetonitrile, (ii) the exchange of the coordinated solvents by DCM, and (iii) lastly, spontaneous decoordination of the MC molecule. With this strategy, we could completely remove the strongly coordinating molecules at OCSs without structural damage.
38
Coordination Polymers from Amine-Based Ligands
Emerson, A. J.,1 Batten, S. R.,1 Turner, D. R.1
Email: [email protected]
1 Monash University, Clayton, Australia
[1] Amines are known to favourably interact with CO2 due to the polar C···N interaction, with direct incorporation of amine functionality into the PCP has shown to improve the adsorption of CO2 over the unfunctionalised PCP.[2] Common synthetic approaches towards the inclusion of amine functionality into PCPs is to post-synthetically modify the PCP via a chemical transformation once the parent framework has formed.[3] The direct incorporation of amine functionality into ligands is relatively unexplored compared to the post-synthetic modification of polymers, with some examples including ligands derived from the small polyamine ethylenediamine.[4] Starting from small polyamines such as diethylenetriamine and 1,4-bis(aminomethyl)benzene to synthesise a new family of ligands containing secondary and tertiary amines within ligand core, with one example being N,Nʺ-(4-carboxybenzyl)-N,N′,Nʺ-(carboxymethyl)-diethylenetriamine (H5L1). The three-dimensional framework poly-[Cd3(L1)(OH2)]·2H2O contains one-dimensional, square-shaped solvent channels with 23 % 3 void volume, with a CO2 uptake of 66 cm /g at 273 K. An interesting property of this material is that it maintains crystallinity when exposed to boiling water and steam, which is critical if PCPs are going to be implemented as CO2 sequestration materials. Another example is the ligand N,N′-di(4-carboxybenzyl)-1,4- bis(aminomethyl)benzene (H4L2), with the framework poly-[Cd2(L2)(OH2)] containing large one- dimensional, hexagonal-shaped solvent channels with 37 % void volume. By using small polyamines as a basis of new series of ligands, there is a large scope for customisation in the positioning of various functional groups. This allows for a study on the influence of the positioning of functionality within the ligand has on the resulting compounds that are formed, which will allow for greater design in the future.
Figure 1: The three-dimensional frameworks poly-[Cd3(L1)(OH2)]·2H2O (left) and poly-[Cd2(L2)(OH2)] (right), displaying the one-dimensional solvent channels of 23 % and 37 % respectively. References [1] G. F. Versteeg, L. A. J. Van Dijck, W. P. M. Van Swaaij, Chem. Eng. Commun. 1996, 144, 113-158. [2] K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. Bloch, Z. R. Herm, T.-H. Bae, J. R. Long, Chem. Rev. 2011, 112, 724- 781. [3] K. K. Tanabe, S. M. Cohen, Chem. Soc. Rev. 2011, 40, 498-519. [4] C. S. Hawes, G. P. Knowles, A. L. Chaffee, D. R. Turner, S. R. Batten, Cryst. Growth. Des. 2015, 15, 3417-3425
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COPPER POLYAMINES AS ATOM TRANSFER CATALYSTS
Zerk TJ, Bernhardt PV
e-mail: [email protected]
School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, Australia
Once of academic interest only, Cu complexes of polyamine ligands have reemerged as central catalysts in atom transfer radical polymerization (ATRP) reactions.1,2 The role of the Cu complex is in converting an alkyl halide into a radical via a coupled electron and atom transfer reaction (see Scheme below for the tertiary tetraamine Cu complex of Me6tren). A wide spectrum of activity (quantified by the activation equilibrium constant KATRP =kact/kdeact) covering several orders of magnitude has been reported for a range of different polyamines and the factors that result in an increase in activity are still being understood.
We have investigated this interesting reaction using a variety of spectroscopic and electrochemical methods and have found that accurate values of the forward and back reaction rate constants (kact/kdeact in the Scheme) can be measured by simulation of experimental cyclic voltammetry data.3-5 In most recent results we have discovered some unusual features that are important in defining effective ATRP catalysts including some side reactions that lead to unexpected organocopper complexes.
References 1. K. Matyjaszewski, J. Xia, Chem. Rev. 2001, 101, 2921-2990. 2. A.J.D. Magenau, N.C. Strandwitz, A. Gennaro, K. Matyjaszewski, Science 2011, 332, 81-84. 3. C.A. Bell, P.V Bernhardt, M.J. Monteiro, J. Am. Chem. Soc. 2011, 133, 11944– 11947. 4. T.J. Zerk, P.V. Bernhardt, Dalton Trans. 2013, 42, 11683-11694. 5. T.J. Zerk, P.V. Bernhardt, Inorg. Chem. 2014, 53, 11351-11353
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COPPER(I) COMPLEXES: INTRAMOLECULAR AND INTERMOLECULAR ARENE-C– H···π(QUASI-CHELATE RING) INTERACTIONS
Yeo, C. I. 1, Zukerman-Schpector, J. 2, Ferreira, M. A. B. 2, Tiekink, E. R. T. 1
1 Sunway University, Bandar Sunway, Malaysia 2 Universidade Federal de São Carlos, São Carlos, Brazil
ABSTRACT TEXT
A series of bis(phosphane)copper(I) thiocarbamates, namely (Ph3P)2Cu[ROC(=S)N(H)Ph]Cl, were prepared in response to the promising biological properties exhibited by the related phosphanegold(I) analogues. The presence of an intramolecular N-H···Cl hydrogen bond in the title compounds, was found leading to the formation of a six-membered quasi-chelate ring, {CuCl···HNCS}. Following ring closure, unanticipated C–H···π(quasi-chelate ring) interactions were evidenced in one-third of related copper(I) complexes capable of forming similar quasi-chelate rings. Computational chemistry calculations revealed that these interactions when occurring intramolecularly, afforded energies of attraction approximating 3.5 kcal mol-1. In a subsequent review of analogous copper(I) complexes, intermolecular C–H…π(quasi-chelate) interactions imparted stabilisation to the crystal structures, leading to zero-, one-, two- and even three- dimensional architectures.
41
CRYSTAL DESIGN FOR FUNCTIONAL METAL COMPLEXES
Nakamura, T, Oshima Y, Kubo, K, Noro, S
e-mail: [email protected]
Hokkaido University, Sapporo, Japan
We are developing novel functional materials utilizing supramolecular units exhibiting dynamic features such as large amplitude molecular motions and proton transfers in the crystalline state. We already reported a ferroelectric based on molecular rotation in a crystal. By introducing dipole moments perpendicular to the rotational axis, inversion of the dipoles occurs by the molecular rotation. The crystal of (m- fluoroanilinium)(dibenzo[18]crown-6)[Ni(dmit)2] showed a ferroelectric transition arising from the dipole-moment flip with the flip of the aryl ring by applying outer electric field. Molecules tend to pack densely in the crystal. Therefore, appropriate design of molecular assemblies is indispensable. In this study, we utilized symmetries of molecules as well as crystals (point groups and space groups) in addition to intermolecular interactions to regulate molecular-assembly structures. For example, trans-syn-trans- dicycrohexano[18]crown-6 exhibits a planer conformation, since the oxygen atoms substitute cyclohexane rings from equatorial positions. The C2h symmetry of the molecule - induced a columner structure with anilinium cation derivatives in the crystal of [Ni(dmit)2] having the space group of P-1. The trans-syn-trans-dicycrohexano[18]crown-6 also utilized for developing a proton transfer system, in which the conformational change of the crown ether may assist the proton transfer. Flexible supramolecular cations induced chiral space groups of the crystals. The II III - [Mn Cr (ox)3] anions form a honeycomb structure, whose single crystals showed ferromagnetic phase transition at aroung 5 K. We introduced molecular rotator structures II III - as a countor cation for the [Mn Cr (ox)3] . The (m-fluoroanilinium)(trans-syn-trans- II III dicycrohexano[18]crown-6)[Mn Cr (ox)3] had a chiral space group, whose magnetic and dielectric properties of the chiral crystal will be discussed.
42
DECOUPLING OF SPIN CROSSOVER AND CYSTALLOGRAPHIC PHASE CHANGE
Boonprab, T1, Harding, P1, Murray, KS2, Phonsri, W2, Telfer, SG3, Alkaş, A3 and Harding, DJ1
Email: [email protected]
1Functional Materials and Nanotechnology Centre of Excellence, Walailak University, Thasala, Nakhon Si Thammarat, 80160, Thailand 2School of Chemistry, Monash University, Clayton, Melbourne, Victoria, 3800 Australia 3MacDiarmid Institute for Advanced Materials and Nanotechnology, Institute of Fundamental Sciences, Massey University, Palmerston North, New Zealand
ABSTRACT Spin crossover materials are attractive targets in the development of new technologies. Being molecular they are highly tunable and readily processable. In seeking more immediately applicable devices we have designed a new ligand, HnaphEen (1-{[2- (Ethylamino)ethylimino]methyl}-2-naphthol) which incorporates H-bonding and aryl supramolecular connectivity. Reaction of the ligand with a variety of iron(III) salts in a 2:1 ratio gives [Fe(naphEen)2]Y (Y = F 1, Cl 2, Br 3, I 4, BF4 5, PF6 6, ClO4 7) as dark green or purple solids.
+ Crystallographic studies show layers of [Fe(naphEen)2] cations held together by C-HO, C-H and - interactions with strong H-bonds between the N-H groups and the anions. This results in strong cooperativity with the anions trapped in between these cationic sheets. In 3 the compound undergoes a phase change around room temperature tripling the unit cell but remarkably does not show any change in spin state at the Fe(III) centres. SQUID magnetometry reveals gradual and incomplete spin crossover which is anion dependent. Moreover, the fluoride complex appears to exhibit a different spin state in + solution to the other compounds allowing [Fe(naphEen)2] to act a simple naked eye sensor.
43
DEHYDROGENATION OF FORMIC ACID UNDER HIGH-PRESSURE CONDITIONS BY Cp*Ir CATALYST
Kawanami, H1, Iguchi, M1, Himeda, Y2
Presenting author’s e-mail: [email protected]
1 National Institute for Advanced Industrial Science and Technology, Sendai, Japan 2 National Institute for Advanced Industrial Science and Technology, Tsukuba, Japan
ABSTRACT TEXT We have developed a simple and continuous high-pressure hydrogen gas (over 120 MPa) production system from formic acid (FA) catalyzed by the Ir catalyst ([Cp*Ir(4DHBP)(H2O)][SO4], 4DHBP = 4,4’-dihydroxy-2,2’-bipyridine) without any compressor. The system can generate the high-pressure gas (H2 : CO2 = 1:1) continuously with a high rate (TOF = 1900 - 2500 h-1 at 30 MPa) even at a mild temperature of 80oC. However, Ir-4DHBP has the ability to generate high-pressure gas from FA aqueous solution effectively, but it is not suitable for the development of a high-pressure H2 evolution system for practical, because of the decomposition of Ir-4DHBP catalyst under high-pressure conditions. To overcome this problem, we have developed an Ir catalyst bearing the 1,10-phenanthroline-4,7-diol ligand (Ir-PHDP), which can be used for the generation of high-pressure hydrogen from FA with an obtained highest TON value of 5,000,000 for 3.5 months!! It can be successfully recycled over 10 times without losing any catalytic activity. The developed Ir-PHDP has comparable activity with Ir-4DHBP with the advantage that after the reaction, it can be easily separated due to its pH-dependent solubility properties. This work will be extended to develop a high-pressure H2 evolution system from highly-concentrated FA and to confirm the practical application of FA as a H2 storage material. In our presentation, we also discuss the decomposition mechanism of Ir- 4DHBP under high-pressure condition comparing that under atmospheric conditions.
44
A desferrioxamine B squaramide ester for the incorporation of zirconium-89 into antibodies
Rudd, S. E1., Roselt, P2., Cullinane, C2,3., Hicks, R. J3,4., and Donnelly, P. S1.
1 School of Chemistry, University of Melbourne and Bio21 Molecular Science and Biotechnology Institute 2 Research Division, Peter MacCallum Cancer Centre 3The Sir Peter MacCallum Department of Oncology, University of Melbourne 4Centre for Cancer Imaging, Peter MacCallum Cancer Centre
Attaching positron-emitting radioisotopes to antibodies allows for targeted positron emission tomography (PET) imaging. The half-life of 89Zr (78 hours) is sufficient timing to enable imaging with antibodies that take several days to reach the target site in vivo. Desferrioxamine B (DFO) is commonly used as a chelator for Zr, and in recent years several DFO-based ligands for Zr have been reported. These bifunctional chelators incorporate a reactive functional group for bioconjugation to an antibody, however the stability of these conjugates must be extremely high for the imaging agents to progress to the clinic. The most popular 89Zr chelator, p-isothiocyanatobenzyl-desferrioxamine, results in a thiourea linkage after bioconjugation which is susceptible to cleavage through radiolysis. Furthermore, the coordination sphere of ZrIV is not saturated by most hexadentate DFO- based chelators, suggesting the stability of the complex may be improved by ligand modification. In order to address these issues, we have synthesised a novel DFO-based bifunctional chelator for Zr using an alternative squaramide linkage (DFOSq). The squaramide acts as both a stable bioconjugation method as well as providing additional donor atoms for the conversion of DFO to an octadentate ligand. DFOSq was conjugated to the monoclonal antibody trastuzumab for the diagnostic imaging of human breast cancer tumours. The synthesis, stability studies and small animal PET imaging results (Figure 1) will be presented, as well as recent advances showing the versatility of DFOSq in labelling other antibodies and tumour targeting peptides.
Figure 1. PET image following administration of 89ZrDFOSq-trastuzumab into a BT474- xenograft tumour-bearing mouse. S. E. Rudd, P. Roselt, C. Cullinane, R. J. Hicks and P. S. Donnelly, Chem. Comm., 2016, 52, 11889-11892
45
DESIGN OF CHIRAL METAL-ORGANIC FRAMEWORKS FOR ASYMMETRIC HETEROGENEOUS CATALYSIS
Chen, X, Jiang, H, Han, X, Liu, Y, Cui, Y
e-mail: [email protected]
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China
The incorporation of catalytically active chiral molecules like metallosalen and BINOLate complexes into MOFs has been recognized as an efficient strategy for heterogeneous asymmetric catalyst design and synthesis with considerable impact. Besides crystalline structures and high catalyst loadings, spatial control of reactive sites engendered by frameworks could often dramatically enhance reactivity by precluding self-quenching or facilitating coorperativity in confined space, thus offering advantages over other immobilized catalyst systems. However, the heterogenized catalysts are typically less effective than their homogeneous analogs, and success examples of chiral MOF catalysts especially those for asymmetric catalysis and framework confinement effect on incorporated molecular catalysts are still scarce. Given their intrinsic features and excellent asymmetric catalytic behavior, metallosalen and biphenol are expected to be ideal functional struts in chiral functional MOFs. We report here the assembly of chiral MOFs and COFs from metallosalen or biphenol complexes and show that they are efficient heterogeneous catalysts for asymmetric organic transformations.
46
Design of Targeted Platinum Anticancer Complexes
Wang, XY
Presenting author’s e-mail: [email protected]
State Key Laboratory of Pharmaceutical Biotechnology, School of Life Sciences, Nanjing University, Nanjing, P. R. China.
Platinum anticancer drugs play a crucial role in the treatment of various tumours. However, the e cacy and application of platinum drugs are largely restricted by severe systemic toxicities and drug resistance because of poor specificity. Di erent strategies have been developed to prevent the shortcomings of platinum drugs. For instance, inert platinum(IV) complexes can be reduced to cytotoxic platinum(II) complexes with the loss of axial ligands under hypoxic conditions in the tumour tissue and thus act as prodrugs; targeting groups can be attached to platinum complexes so as to improve the selective accumulation of platinum drugs in tumour tissues. Recently, we designed and synthesized a series of targeted platinum complexes, including bisphosphonates (BPs)-modified platinum(II) complexes for osteosarcoma and biotin-modified platinum(IV) complexes for breast cancer. Biological tests indicate that the complexes with BP targeting groups display significant selectivity to osteosarcoma U2Os cell line and can effectively inhibit the tumor cells; the complexes with biotin targeting group remarkably increase the cellular uptake in breast cancer cells as compared to that in normal breast epithelial cells. In brief, targeted platinum complexes demonstrate better therapeutic efficacy than the corresponding non-targeted complexes.
47
Design, Synthesis and Application of Hard Metal Ion Affinity Adsorbents.
Gabriel S. A. L. Gillner, Chunfang Zhang, Eva M. Campi, Tamsin R. Sawford, Ute Kreher, Rachel Daly, Leone Spiccia and Milton T. W. Hearn Department of Chemistry, Monash University, Clayton, Victoria, Australia 3800
Immobilised metal ion affinity chromatography (IMAC) for the purification of recombinant and wild-type proteins using hard metal ions, such as Ca2+ or Fe3+, as the chelated metal ion is a very attractive option due to their lower toxicities compared to the traditionally employed borderline metal ions, such as Ni2+, Cu2+ or Co2+. In addition, different separation selectivities might be achieved with such systems. Despite extensive efforts, however, the significant affinity of numerous biological molecules towards Ca2+ or Fe3+ has not been adequately exploited. This is due in part to the inability to find low molecular weight chemical ligands that can match or exceed the affinity of Ca2+- or Fe3+-binding proteins for the metal ion and thus prevent desorption of the metal ion from the ligand during the procedure. This challenge has now been solved with the development of specific functionalised macrocyclic ligands that can be readily immobilised onto benign support materials and the development of specific peptide tags that replicate the binding motif for the metal ion within the native protein. These peptide tags can be readily incorporated into a heterologous target protein through established recombinant DNA procedures and subsequently removed to generate the mature native protein should that be required for biological or higher order structural studies. In this presentation, the design methods, synthetic approaches and experimental approaches will be illustrated using several exemplars related to commercially important industrial enzymes, and the scope of this approach explored as a new platform for the purification of recombinant proteins in general.
48
DESIGNING ROOM TEMPERATURE SPIN CROSSOVER MATERIALS
Harding, DJ1, Harding, P1, Phukkaphan, N1, Cruickshank, D2, Murray, KS3, Phonsri, W3
Presenting author’s e-mail: [email protected]
1 Functional Materials and Nanotechnology Centre of Excellence, Walailak University, Thasala, Nakhon Si Thammarat, 80160, Thailand 2 Rigaku Oxford Diffraction, Kemsing, Sevenoaks, TN15 6QY, United Kingdom 3 Monash University, Clayton, Melbourne, Victoria, 3800, Australia
ABSTRACT Molecular switches represent attractive targets in the development of functional nanomaterials. In this context spin crossover compounds are of particular interest as the switching between the high spin and low spin states may be achieved by changes in temperature and pressure or by the application of light. Moreover, as the physical properties of the compounds change upon spin crossover the switch is addressable in multiple ways.
In this presentation we report our recent efforts in the discovery of robust iron(III) spin crossover materials based on halogen substituted quinolylsalicylaldiminate (qsal-X) ligands. We show how careful control of the type of anion and the qsal-X ligand employed can lead to spin crossover systems with abrupt spin crossover and a wide hysteresis near room temperature.
49
DEVELOPMENT OF FUNCTIONALIZED IRIDIUM COMPLEXES FOR BIOLOGICAL AND MATERIAL SCIENCES
Aoki, S.1
1 Tokyo University of Science, Noda, Japan,
Cyclometalated iridium(III) (Ir) complexes such as fac-Ir(tpy)3 (tpy = 2-(4’-tolylpyridine) play central roles as triplet emitters not only in the production of organic light-emitting diodes (OLED) but also as chemosensors and bioimaging agents, because of their excellent photophysical properties and stability even in aqueous solutions.1 Besides, the cyclometalated Ir complexes possess C3-symmetric structure and hence could be useful platform to mimic biomolecules that have the C3-symmetric homotrimeric structures. In this paper, we present design and synthesis of functionalized cyclometalated Ir complexes based on the regioselective substitution reactions and subsequent conversions to a variety of functional groups.2 Moreover, the selective degradation reactions of tris- cyclometalated Ir complexes promoted by zinc(II) has been discovered.3 These reactions have allowed us to access various analogues such as blue, red, and white-emitting phosphorescent compounds, pH sensors, and singlet oxygen sensitizers.2-4 It has also been found that the amphiphilic Ir complex-peptide hybrids are capable of inducing cell death of the cancer cells, possibly via interaction with calcium complex of calmodulin.5,6 These results may provide useful information for theranostics, a combination of diagnosis and therapy of diseases.
1) (a) Flamigni, L., et al. Top. Curr. Chem. 2007, 281, 143. (b) Lo, K. K.-W., et al. Coord. Chem. Rev. 2010, 254, 2603. 2) (a) Aoki, S., et al. Inorg. Chem. 2011, 50, 806. (b) Hisamatsu, Y., et al. Eur. J. Inorg. Chem. 2011, 5360. (c) Moromizato, S., et al. Inorg. Chem. 2012, 51, 12697. (d) Nakagawa, A., et al. Inorg. Chem. 2014, 53, 409. (e) Kando, A., et al. Inorg. Chem. 2014, 53, 409. (f) Hisamatsu, Y., et al. Inorg. Chem. 2017, 56, 886 3) Tamura, Y., et al. Inorg. Chem. 2017, 56, 812. 4) Kumar, S., et al. Inorg. Chem. 2016, 55, 3829. 5) (a) Hisamatsu, Y., et al. Bioconjugate Chem. 2015, 26, 857. (b) Hisamatsu, Y., et al. Bioconjugate Chem. 2017, 28, 507. 6) Masum, A.-A., et al. Manuscript in preparation.
50
Dinuclear Tantalum Complexes as a Model for Alkyne Cyclotrimerization
Yamamoto, K., Tsurugi, H., and Mashima, K.
e-mail: [email protected]
Osaka University, Osaka, Japan
A dinuclear tantalum complex Ta2Cl6(-C4Et4) bearing a tantallacyclopentadiene moiety was synthesized by reaction of ( -EtC≡CEt)TaCl3(DME) with AlCl3. Such the dinuclear complex served as an active catalyst for cyclotrimerization of internal alkynes. During the catalytic reaction, we isolated a dinuclear complex bearing -hexaethylbenzene and a -3-hexyne ligands as a product of the intermolecular [4+2] cycloaddition between the metallacyclopentadiene moiety and 3-hexyne rather than the other possible insertion/cyclization mechanism. Such the complex had a unique sandwich structure where the dinuclear tantalum center was sandwiched by a two–electron reduced hexaethylbenzene ligand and a -3-hexyne ligand. We disclose synthesis and reactivity of related mixed metal complexes including tantalum/iridium and tantalum/rhodium.
Path A: Diels-Alder Type Cyclization
Et Et n Et n Et Pr Et Pr Et Et Et Et nPr Et Et Cl nPr nPr nPr Et Cl Cl Cl Cl Ta Ta Ta Ta Ta Ta Cl Cl Cl Cl Cl Cl Cl
C Me3Si SiMe3 Me3Si SiMe3 Me3Si SiMe3 S 7
C6D6, 60 ºC
Path B: Insertion / Cyclization Et Et Et Et nPr Et Et Et n n Pr Et nPr nPr Pr Cl Cl nPr Cl Ta Ta Ta Ta Cl Cl Cl Cl Cl Me Si SiMe C Me3Si SiMe3 3 3 1
References: 1. Keishi Yamamoto, Hayato Tsurugi, Kazushi Mashima, Chem. Eur. J., 2015, 21, 11369-11377. 2. Keishi Yamamoto, Haruki Nagae, Hayato Tsurugi, Kazushi Mashima, Dalton Trans. 2016, 45 (43), 17072-17081. 3. Keishi Yamamoto, Hayato Tsurugi, Kazushi Mashima, Organometallics 2016, 35 (10), 1573-1581. 4. Keishi Yamamoto, Kosuke Higashida, Haruki Nagae, Hayato Tsurugi, Kazushi Mashima, Helv. Chim. Acta 2016, 99 (11), 848-858.
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Dipyridylpyrrolato anion analogues of terpyridine metal complexes
McPherson J,1 Bhadbhade M,2 Colbran S1
1 School of Chemistry, University of New South Wales (UNSW), Sydney, Australia 2 Mark Wainwright Analytical Centre, UNSW, Sydney, Australia
Metal complexes of the 2,2ʹ:6ʹ,2ʺ-terpyridine (terpy) family of ligands are ubiquitous. The photophysical and redox properties of metal-terpy complexes are well understood and, for example, these functional units are now extensively exploited within supramolecular devices. 2,5-Di(2-pyridyl)pyrrolato (dpp-) ligands are wide bite angle analogues of the terpyridine ligand and are available by deprotonation of the 2,5-di(2-pyridyl)pyrrole (dppH) precursor. They are, however, little known or used.
The chemistry of dpp- ligands is underdeveloped, perhaps because the previously reported synthetic routes are difficult, multistep protocols. We recently reported1 a one-pot synthesis of a range of dppH derivatives, which allows quick, direct access to ligands with functional groups installed at the C3/4-position of the central pyrrole core while also tolerating modification of the pyridyl motifs.2
Novel organometallic, rare-earth and transition metal-dpp- complexes will be presented such as those shown below. These new complexes demonstrate reactivities induced through the different electronics and chelate strain associated with the pyrrolic core which are different from their terpy analogues.
2 Figure 1: Piano-stool organometallic [Cp*Rh(κ -dpp)Cl] (left), homoleptic [Ru(dpp)2] (centre) and [La(dpp)3] (right) complexes from the single crystal X-ray structures (with Hatoms and lattice solvent molecules omitted for clarity). The red lines in the view of [La(dpp)3] highlight its tricapped trigonal prismatic cooordination geometry.
References 1. McSkimming et al. Chem. Eur. J. 2014, 20, 11445 2. McSkimming et al. Chem. Asian J. 2014, 9, 136 52
Dual Properties of the Metal-Metal Quintuple Bonds in Catalysis
Tsai, Y.-C.
National Tsing Hua University, Hsinchu, Taiwan ROC
We have demonstrated that the amidinate-stabilized quintuply bonded dinuclear group VI complexes show an interesting resemblance to alkynes in terms of their reactivity. For example, they undergo [2+2+2] cycloaddition reactions with two equivalents of terminal alkynes under catalyst-free condictions,1 and the Friedel-Crafts haloacylation with acyl halides without Lewis acids.2 Moreover, the Mo-Mo quintuple bond is utilized as a ligand to stabilize the group 10 “metals” and form the unprecedented δ complexes, in which bonding between the “metals” and the M-M quintuple bond complies with the Dewar-Chatt bonding model.3 One very important factor to make these reactions possible is the M-M quintuple bonds showing dual properties; the M-M bonds are nucleophilic and the metal centers remain acidic. In this presentation, we will show that this character can be exploited to catalyze the [2+2+2] cyclotrimerization of alkynes with excellent regioselectivity. It is interesting to note that the quintuply bonded dichromium and dimolybdenum amidinates are effective catalysts, but they proceed through two very different mechanisms.
References: (1) Chen, H.-Z.; Liu, S.-C.; Yen, C.-H.; Yu, J.-S. K. Shieh, Y.-J.; Kuo, T.-S.; Tsai, Y.-C. Angew. Chem. Int. Ed. 2012, 51, 10342-10346. (2) Chen, H.-G.; Hsueh, H.-W.; Kuo, T.-S.; Tsai, Y.-C. Angew. Chem. Int. Ed. 2013, 52, 10256-10260. (3) Lu, D.-Y.; Chen, P. P.-Y.; Kuo, T.-S.; Tsai, Y.-C. Angew. Chem. Int. Ed. 2015, 54, 9106- 9110.
53
DUAL-LOCKING FLUORESCENT MOLECULAR ASSEMBLY OF AN ION-SENSING QUINOXALINONE DERIVARIVE
Akutagawa, T1, Nakane, Y1, Sakai, K2
Presenting author’s e-mail: [email protected]
1 Tohoku University, Sendai, Japan 2 Chitose Institute of Science and Technology, Chitose, Japan
An [18]crown-6 unit was introduced into a cation–anion dual-ion-sensing quinoxalinone derivative (1) as a new fluorescent molecule for successive cation (K+) and anion (F− and − [1] CH3COO ) sensing in CH3CN. The lactam (–NH) and lactim (=N) tautomerization of 1 in CH3CN was biased in favor of the major tautomer of lactam form, exhibiting an efficient fluorescence band at 490 nm with a typical Stokes shift of 5600 cm−1. High anion-sensing abilities for F− and AcO− were observed at the hydrogen-bonded acidic N–H proton of the positively charged K+-capturing 1 at the [18]crown-6 site due to electrostatic cation–anion interactions. On the other hand, the acidic N–H proton of lactam tautomer 1 strongly recognized basic AcO− or F− anions via N–H•••AcO− or F− hydrogen-bonding interactions, and further AcO− or F− additions facilitated the deprotonation reaction, forming anionic 1−. The molecular structures of cationic K+•1 and anionic 1− were confirmed by single-crystal X-ray structural analyses. Anionic 1− showed a much higher K+-sensing ability at the [18]crown-6 site than neutral 1 through effective cation–anion electrostatic interactions. Interestingly, the electrostatically stabilized zwitterionic K+•1− formed fluorescent organogels in CH3CN, acetone, and THF; the organogels underwent reversible transformation between a blue fluorescent organogel and green fluorescent sol by the addition of trifluoroacetic acid (gel → sol) and trimethylamine (sol → gel). Both K+ and AcO− (or F−) ions acted as the key ions in the fluorescent organogel formation.
Reference [1] Nakane, Y, Akutagawa, T. et al., J. Phys. Chem. A 2015, 119, 6223–6231.
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Dynamic Metal–Organic Frameworks: Design and Properties Xian-He Bu* TKL of Metal- and Molecule-Based Material Chemistry, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China
Flexible metal-organic frameworks (FMOFs) have received much attention due to their attractive properties that originate from their flexibility and dynamic behavior, and show great potential applications in many fields.“Dynamic behavior” has been used to describe the transformation process between the multistable states of flexible MOFs. Also, though strategies and methods for the design and investigation of the properties of MOFs have been well developed during the wide exploration, the rational construction of flexible MOFs is still a great challenge. This should be due to the fact that the successful introduction of flexible factors into a MOF and the realization of the anticipated dynamic properties are somewhat random.1 We herein report some of our new results in the construction of flexible metal-organic frameworks and investigation of their properties, some other related results in our group will also be reported [1-10]。
Some Recent References: 3. Z. Chang, D. H. Yang, J. Xu, T. L. Hu, and X. H. Bu*, Adv. Mater. 2015, 27, 5432. 1. Y. Q. Chen, G. R. Li, Z. Chang, Y. K. Qu, Y. H. Zhang, and X. H. Bu*, Chem. Sci. 2013, 4, 3678. 2. Q. Chen, Z. Chang, W. C. Song, H. Song, H. B. Song, T. L. Hu, and X. H. Bu*, Angew. Chem. Int. Ed. 2013, 52, 11550. 3. D. Tian, Q. Chen, Y. Li, Y. H. Zhang, Z. Chang, and X. H. Bu*, Angew. Chem. Int. Ed. 2014, 53, 837. 4. H. Wang, J. Xu, D. S. Zhang, Q. Chen, R. M. Wen, Z. Chang, and X. H. Bu*, Angew. Chem. Int. Ed. 2015, 54， 5966. 5. S. D. Han, J. P. Zhao, S. J. Liu, and X. H. Bu*, Coord. Chem. Rev. 2015, 289‐290, 32. 6. D. Tian, J. Xu, Z. J. Xie, Z. Q. Yao, D. L. Fu, Z. Zhou, and X. H. Bu*, Adv. Sci. 2016, 3, 1500283. 7. Q. Gao, J. Xu, D‐P. Cao, Z. Chang, and X.‐H. Bu*, Angew. Chem. Int. Ed. 2016, 55, 15027. 8. B. Zhao, N. Li, X. Wang, Z. Chang, and X. H. Bu*, ACS Applied Maters & Interfaces, 2017, 3, 2662. 9. J. P. Zhao, J. Xu, S. D. Han, Q. L. Wang, and X. H. Bu*, Adv. Maters. 2017, accepted.
55
ELECTRICALLY CONDUCTIVE MOFs
Kitagawa, H
Kyoto University, Kyoto, Japan
Recent studies on metal–organic frameworks (MOFs) have shown that their designable framework architectures and specific pore surfaces are of potential interest to chemists studying various functionalities of solid-state materials, such as selective gas sorption, heterogeneous catalysis, magnetism, and electrical conductivity. Electron or proton conductivity is now regarded as a new functionality of the porous MOFs, and has attracted much interest, not only for scientific studies, such as biological systems, but also for practical investigation. MOFs can provide well-designed pores for electron- or proton- conducting pathways and include various conducting media, such as frameworks and/or water molecules in the pores. To date, we have studied the introduction of acid molecules and water molecules into the pores as proton carriers and conducting media, respectively, and have succeeded in synthesizing highly proton-conductive MOFs. We have also investigated on the MOF electron conductors including conductive tubular and surface MOFs. [1-4] We demonstrate a bottom-up approach for the fabrication of well-defined dimensional- crossover nano-architectures with high tunability using metal ions and or¬ganic molecules as building blocks. We succeeded in rationally constructing an assembly of square prism- shaped metal-organic nanotubes with aside of 2 nm. A uniform 1D channel is fabricated inside the tube, and H2O and alcohol can be selectively adsorbed. Its optical gap is about 0.76 eV of semiconductive region, and X-ray and theoretical studies revealed its unique electronic structure of CDW quartets. In addition, its electronic states can be successively controlled by exchanges of structural components and guest molecules. The results presented here demonstrate a rational route to the creation of nanotubes with high tunabilities of structures and electronic states, and might also offer valuable insights into multifunctional nanomaterials.
1. T. Yamada, K. Otsubo, R. Makiura, H. Kitagawa, Chemical Society Reviews, 42,6655-69 (2013). 2. K. Otsubo, Y. Wakabayashi, J. Ohara, S. Yamamoto, H. Matsuzaki, H. Okamoto, K. Nitta, T. Uruga, H. Kitagawa, Nature Materials, 10, 291-295 (2011). 3. S. Sakaida, K. Otsubo, O. Sakata, C. Song, A. Fujiwara, M. Takata, H. Kitagawa, Nature Chemistry, 8, 377-383 (2016). 4. K. Otake, K. Otsubo, K. Sugimoto, A. Fujiwara, H. Kitagawa, Angew. Chem. Int. Ed., 55, 6448-6451 (2016).
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Electronic Structure Contributions to Reactivity in High Valent Iron Model Complexes
Shengfa Ye,1 Bhaskar Mondal,1 Eckhard Bill,1 Lawrence Que Jr.,2 Franc Meyer,3 Frank Neese1
Presenting author’s e-mail: [email protected]
1Max-Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, D45470, Mülheim an der Ruhr, Germany 2Department of Chemistry, Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, USA. 3Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstr. 4, D- 37077 Göttingen, Germany
ABSTRACT High-valent iron-oxo species have been postulated as key intermediates in various pivotal biological processes. To rationalize their diverse reactivity, one has to analyze their electronic structures in detail, because electronic structures and reactivity are intimately linked. The talk will present our recent work on the correlation of electronic structures with reactivity for two oxo-iron(IV) model complexes. The majority of S = 1 ferryl model complexes feature an electron configuration of σ(O- 2 2 2 2 0 0 pz) π(O-px,y) δ(dxy) π*(dxz,yz) σ*(dx2-y2) σ*(dz2) , for which complex 1 serves as a representative example. When macrocyclic tetracarbene was employed as the supporting ligand, our detailed electronic structure study by using magnetic circular dichorism spectroscopy and ab initio calculations prove that complex 2 has a distinct electron 2 2 2 2 0 0 configuration of σ(O-pz) π(O-px,y) δ(dxy) π*(dxz,yz) σ*(dz2) σ*(dx2-y2) with the dz2 orbital (MO) lying higher in energy than dx2-y2. As a result of the different electronic structures, complex 1 invokes a two-state reactivity scenario for H atom transfer, whereas complex 2 follows a mechanism of single-state reactivity.
57
Emergence of Conductivity by Chemical Reduction in Cu-Naphthalenediimide-Based Coordination Polymer
Authors (Arial, 12 font, Surname, Initials. Presenting author to be in bold and italics. Iguchi, H, Miyata, M, Takaishi, S, Yamashita, M
Presenting author’s e-mail: [email protected]
Tohoku University, Sendai, Japan
ABSTRACT Metal-organic frameworks (MOFs) have attracted much attentions due to their unique properties such as gas adsorption, separation and catalysis derived from their robust framework and molecular-sized pores. The electrical conduction in MOFs enables various applications such as capacitors and electrode materials. However, electron-conductive MOFs have rarely been reported because of the difficulty in designing conduction path.
In this work, we synthesized coordination polymer containing infinite-stacked column structure and to reduce it so that carriers are introduced into the -stacked column to realize electrical conduction.
We chose naphthalenediimide (NDI) as the -conjugated moiety of the ligand, because NDI has large -conjugated plain, low LUMO level for stable radical, and ease of modification in the imide position. Most NDI-based ligand used in MOFs to date have rigid coordination moiety such as pyridyl group in the imide position. It is not suitable for realizing -stacked column because the framework structure is mostly affected by coordination bond, whose energy is stronger than that of - stacking. Therefore, we introduced flexible ethylene spacer between NDI and pyridyl group to realize infinite - stacked column in coordination polymers.
The slow liquid-liquid diffusion of N,N'-bis(2-(4-pyridyl)ethyl)naphthalenediimide (NDI-enpy) and Cu(NO3)2 solutions gave one-dimensional coordination polymer with square unit, 2+ + [Cu(NDI-enpy)2(NO3)2]•2CHCl3 (1). The reaction with hydrazine reduced Cu to Cu and neutral NDI-enpy to its radical anion. Moreover, 1 changed from insulator to semiconductor (10–7 S cm–1 at room temperature) by the chemical reduction. The strategy used in this work can be the rational method to design electron-conductive MOFs.
58
ENDOHEDRAL CLUSTERS OF THE TRANSITION METALS: A COORDINATION CHEMISTRY PERSPECTIVE
McGrady, J.E., Arcisauskaite, V.
[email protected] Department of Chemistry, University of Oxford, United Kingdom
The structures and electronic properties of metal ions trapped inside endohedral clusters of the tetrel elements (Si, Ge, Sn, Pb), are of great interest to both the physics and chemistry communities. To a physicist, clusters such as M@Sin represent the smallest conceivable models for metal impurities in bulk silicon, and designing systems which retain the characteristic magnetic properties of the encapsulated metal is an important target. From a chemical perspective, the Wade-Mingos rules provide an important framework for understanding the structure of clusters, although the emphasis is firmly on the bonding within the cluster rather than between the cluster and the metal. A coordination chemist might, in contrast, regard the cluster as a pseudo ligand, donating and potentially accepting electron density from the metal. In this presentation I will review our recent attempts to understand the structural diversity of these systems in the context of the available structural, magnetic and spectroscopic data.i,ii The complex structural chemistry can be understood if the cluster is viewed as an electron deficient ligand, withdrawing -electron density from the metal. Most remarkably, we also present evidence that in combination with first row transition elements (notably Mn), the cluster can itself exhibit radical character, mirroring the behaviour of redox non-innocent ligands like bipy.
59
Enhanced luminescence of gold(I) complexes with a fluorescent radical ligand
Kusamoto, T, Hattori, Y, Ogino, Y, Nishihara, H
The University of Tokyo, Tokyo, Japan
ABSTRACT: The luminescence of radicals with a doublet ground state has attracted growing interest owing to its unique characteristics such as long emission wavelength and high efficiency in electroluminescent devices, based on the unusual spin-multiplicity. So far, doublet luminescence has been investigated much less than singlet- and triplet-mediated luminescence because of its relative rarity and the low chemical stability. We developed a highly photostable pyridyl-containing organic radical PyBTM that exhibited fluorescence in CH2Cl2 with an emission peak wavelength (em) of 585 nm with a quantum yield (em) of 0.02.[1] Here we show our two developments to enhance the emission properties of PyBTM. (i) The coordination to gold(I) and the introduction of the fluorine atom to the pyridyl ring synergistically contributed to yield ten-times increase of em (0.02 → 0.20) in I [2] [Au (F2PyBTM)PPh3](BF4). The chemical stability in the photoexcited state was also I improved. (ii) A novel gold(I) complex Au (C6F5)(PyBTM) displayed em of 0.23 in CCl4 while [3] em was 0.01-0.04 in the other halogenated solvents. The formation of an interligand charge transfer excited state suggested in CCl4 would be a key for achieving highly emissive radicals.
[1] Hattori, Y.; Kusamoto, T.; Nishihara, H. Angew. Chem., Int. Ed. 2014, 53, 11845. [2] Hattori, Y.; Kusamoto, T.; Sato, T.; Nishihara, H. Chem. Commun. 2016, 52, 13393. [3] Ogino, Y,; Kusamoto, T.; Hattori, Y.; Shimada, M.; Tsuchiya, M.; Yamanoi, Y.; Nishibori, E.; Sugimoto, K.; Nishihara, H. Inorg. Chem. 2017, in press.
60
Enhanced Optical Nonlinearities of Porphyrin Covalently Functionalized Graphene and Carbon Nanotube Nanohybrids
Zhang C1, Wang A J1, Fu L L1, Song Y L2
Tongji University, Shanghai, P.R. China Harbin Institute of Technology, Harbin, P.R. China
A growing number of nanomaterials, including graphene, carbon nanotubes and their derivatives have been shown to possess remarkable nonlinear optical properties, which promotes the design and fabrication of nano-scale optoelectronic and photonic materials. It is thus of critical importance to explore innovative NLO materials required for the practical applications. Porphyrin covalently functionalized graphene and multi-walled carbon nanotube (MWCNT) nanohybrids have been synthesized via various facile approaches for potential NLO materials. The axial ligands dihydroxotin(IV) tetraphenylporphyrin and the phosphorus-cored porphyrin were covalently linked to the surface of graphene oxide, resulting in the enhanced optical limiting. The fabrication of MWCNT-porphyrin conjugates by using 1,3-dipolar cycloaddition reactions was investigated, which significantly improves the solubility and dispersion stability of MWCNT-based materials in organic solvents; while the porphyrin covalently functionalized reduced-GO was also prepared through 1,3- dipolar cycloaddition for the first time. The conjugated polymers with porphyrin units were introduced onto the surface of MWCNTs through radical polymerization, which may help to improve the solubility of the nanotubes in various solvents. All these nanohybrids exhibit enhanced optical nonlinearities compared to their precursors and the physical blended systems, due to a combination of different nonlinear mechanisms, such as nonlinear scattering, excited-state absorption and photoinduced energy/electron transfer. Porphyrin covalently functionalized graphene and MWCNTs represent a key branch in the field of nano-scale materials and devices for nonlinear optics. Particularly, it is being attached significant importance to electron/energy transfer from porphyrin moieties to graphene or MWCNTs, which is considered to play an important role in improving optical limiting effect.
61
EXPLORING C-H···METALLOAROMATIC INTERACTIONS
Tan, Y. S.1, Halim, S. N. A.2, Otero-de-la-Roza A.3, Tiekink, E. R. T.1
1 Sunway University, Bandar Sunway, Malaysia 2 University of Malaya, Kuala Lumpur, Malaysia 3 National Research Council of Canada, Edmonton, Canada
ABSTRACT TEXT The C-H···metalloaromatic interaction is an of intermolecular contact which is less explored compared to the common secondary interactions such as hydrogen bonding and π··· π stacking. A series of 12 palladium(II) xanthate complexes was prepared by varying the xanthate side group from one carbon to six carbons, i.e. primary, secondary and tertiary hydrocarbons. All 12 complexes were crystallised and the intermolecular interactions present in each system were delineated. Among the series, 11 out of 12 palladium(II) xanthates showed at least one pair of the anticipated C-H···metalloaromatic π interaction, and up to a maximum of six pairs as identified in Pd[S2CO(neo-hexyl)]2. Further, the C- H···metalloaromatic π interactions led to the formation of zero, one and even two dimensional motifs in the respective crystals. From a computational chemistry study performed on Pd[S2CO(n-propyl)]2, it is revealed that a C-H···metalloaromatic π interaction is of similar strength as intermolecular Pd···S secondary bonding which led to the dimerisation of palladium(II) xanthate in the condensed phase.
62
FACILE C-H METALLATION OF NITRILES AND CATALYTIC C-C BOND FORMATIONS
Wierenga, TS,1 Ariafard, A,1 Bissember, AC,1 Gardiner, MG1
Presenting author’s e-mail: [email protected]
1 School of Physical Sciences (Chemistry), University of Tasmania, Hobart, Australia
We have been continuing mechanistic studies on the formation of a novel dipalladium(I) hydride species [{-CH2(MesIm)2}2Pd2H][PF6] II by base-assisted reduction (NaOMe/MeOH) of a chelating bis(NHC) palladium(II) precursor I.1 While examining the dual roles of the base (hydride formation and reduction) we discovered that alkoxide ligands lacking -hydrogens deprotonate acetonitrile rapidly under mild conditions, allowing isolation of monomeric and dimeric derivatives III and IV. Given the common usage of acetonitrile as solvent under basic conditions, the grounds for this infrequently reported outcome was investigated by synthetic and DFT-based mechanistic studies.
A survey of recent breakthroughs in a range of catalytic reactions involving C-C bond formations with deprotonated nitriles will be presented, including the catalysed formation of -hydroxynitriles under base-free conditions that has important functional group tolerance advantages.2 The findings of our DFT studies establishing the mechanism of this reaction will be summarised,3 which highlighted the desirable supporting ligand design features of the Ni-PCP pincer catalyst. Our preliminary efforts to develop alternative CNC- and CCC- pincer catalysts based on NHC ligands for a range of related C-C bond formation reactions will be described.
1. P.D.W. Boyd, A.J. Edwards, M.G. Gardiner, C.C. Ho, M.-H. Lemée-Cailleau, D.S. McGuinness, A. Riapanitra, J.W. Steed, D.N. Stringer, B.F. Yates, Angew. Chem. Int. Ed. 2010, 49, 6315. 2. S. Chakraborty, Y.J. Patel, J.A. Krause, H. Guan, Angew. Chem. Int. Ed. 2013, 52, 7523. 3. A. Ariafard, H. Ghari, Y. Khaledi, A. Hossein Bagi, T.S. Wierenga, M.G. Gardiner, A.J. Canty, ACS Catalysis 2016, 6, 60.
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Fine-controlled Subano-metal Particles in a Dendrimer Reactor
Yamamoto K.
e-mail: [email protected]
Tokyo Institute of Technology, Yokohama, Japan
ABSTRACT We show that tinchlorides, SnCl2 and FeCl3 complexes to the imines groups of a spherical polyphenylazomethine dendrimer in a stepwise fashion according to an electron gradient, with complexation in a more peripheral generation proceeding only after complexation in generations closer to the core has been completed. The metal-assembly in a discrete molecule can be converted to a size-regulated metal cluster with a size smaller than 1 nm as a molecular reactor. Due to the well-defined number of metal clusters in the subnanometer size region, its property is much different from that of bulk or general metal nanoparticles. Dendrimers are highly branched organic macromolecules with successive layers or “generations” of branch units surrounding a central core. Organic inorganic hybrid versions have also been produced, by trapping metal ions or metal clusters within the voids of the dendrimers. Their unusual, tree-like topology endows these nanometresized macromolecules with a gradient in branch density from the interior to the exterior, which can be exploited to direct the transfer of charge and energy from the dendrimer periphery to its core. Here we show that tin ions, Sn2+, complex to the imines groups of a spherical polyphenylazomethine dendrimer in a stepwise fashion according to an electron gradient, with complexation in a more peripheral generation proceeding only after complexation in generations closer to the core has been completed. By attaching an electron-withdrawing group to the dendrimer core, we are able to change the complexation pattern, so that the core imines are complexed last. By further extending this strategy, it should be possible to control the number and location of metal ions incorporated into dendrimer structures, which might and uses as tailored catalysts, building blocks, or fine-controlled clusters for advanced materials.
1. K. Albrecht, Y. Hirabayashi, M. Otake, S. Mendori, Y. Tobari, Y. Azuma, Y. Majima, K. Yamamoto, Science Advances 2016, 2, e1601414.. 2. T. Kambe, A. Watanabe, T. Imaoka, K. Yamamoto, Angew. Chem. Int. Ed. 2016, 55, 13151. 3. K. Albrecht, K. Matsuoka, K. Fujita, K. Yamamoto, Angew. Chem. Int. Ed. 2015, 54, 5677. 4. K. Yamamoto, T. Imaoka, Acc. Chem. Res. 2014, 47, 1127. 5. T. Imaoka, Y. Kawana, T. Kurokawa, K. Yamamoto, Nature Commun. 2013, 4, 2581. 6. T. Imaoka, H. Kitazawa, W. Chun, S. Omura, K. Albrecht, K. Yamamoto, J. Am. Chem. Soc. 2013, 135, 13089-13095. 7. K. Yamamoto, T. Imaoka, W.-J. Chun, O. Enoki, H. Katoh, M. Takenaga, A. Sonoi, Nature Chemistry 2009, 1, 397. 8. N Satoh, T. Nakashima, K. Kamikura, K. Yamamoto, Nature Nanotechnology 2008, 3, 106. 9. K. Yamamoto, M. Higuchi, S. Shiki, M. Tsuruta, and H. Chiba, Nature 2002, 415, 50
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65
FORMATION OF ELECTROACTIVE GIANT MOLECULAR CAPSULES
Abe, M1, Nakagawa, T1, Tomoda, M2, Inatomi, A2, Ono, T2, Hisaeda, Y2
Presenting author’s e-mail: [email protected]
1 University of Hyogo, Hyogo, Japan 2 Kyushu University, Fukuoka, Japan
Recent development of metallosupramolecular chemistry has afforded a series of interesting high-molecular-weight discrete complexes with distinct structures, electronic properties, and chemical functions.1-3) Molecular capsules are one of such supramolecular compounds that provide a unique feature for molecular recognition by incorporating guest molecules into the cavity. In this presentation, we report that a new, remarkably large molecular cavity can be prepared by employing a pyridyl-appended porphyrin and trimetallic clusters as molecular building blocks. New molecular capsules have been structurally identified by single-crystal X-ray diffraction analysis. The compounds contain two cofacially-oriented porphyrin motifs which are supported by four triangular Ru3O clusters through the Ru–pyridyl bonds. A Zn-metallated capsule has shown highly selective guest-binding ability for long alkyl-chain diamine molecules onfirmed by UV-vis titration experiments. VT-NMR and DOSY studies have further addressed the guest-binding structures of the giant capsules in solution. References: 1) M. Abe, A. Inatomi, Y. Hisaeda, Dalton Trans., 2011, 40, 2289. 2) R. Matsuse, M. Abe, Y. Tomiyasu, A. Inatomi, H. Yonemura, S. Yamada,Y. Hisaeda, J. Inorg. Organomet. Polym., 2013, 23, 136. 3) A. Ikegami, M. Abe, Y. Hisaeda, Chem. Lett., 2014, 43, 456.
66
FROM DISCRETE METAL-LIGAND MOTIFS TO SUPRAMOLECULAR ASSEMBLY, NANOSTRUCTURES AND FUNCTIONS
Yam, VWW 1
e-mail: [email protected]
1 Institute of Molecular Functional Materials† and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, PR China
Recent works in our laboratory have shown that novel classes of light-absorbing and luminescent metal-containing molecular materials could be assembled through the use of various metal-ligand chromophoric building blocks. In this presentation, various design and synthetic strategies will be described. A number of these metal-ligand chromophoric complexes have been shown to display rich optical and luminescence behavior. Correlations of the chromophoric and luminescence behavior with the electronic and structural effects of the metal complexes have been made to elucidate their spectroscopic origins. These simple discrete metal complexes are found to undergo supramolecular assembly to give a variety of nanostructures and morphologies. By understanding the spectroscopic origin and the structure-property relationships, different approaches and assembly motifs have been employed to tune their electronic absorption and emission characteristics. Subtle changes in the microenvironment and nanostructured morphologies have led to drastic changes in both the electronic absorption and emission properties of these supramolecular assemblies. Explorations into the underlying factors that determine their spectroscopic properties and morphologies as well as their assembly mechanisms have provided new insights into the understanding of the interplay of the various intermolecular forces and interactions for the directed assembly of novel classes of metal- containing soft materials and hybrids. The exploration into the potential applications and functions of these metal-ligand chromophores and luminophores will also be described.
† UGC Areas of Excellence Scheme, University Grants Committee (Hong Kong)
67
FROM NANOGRAPHENES TO PHENATHROLINES: TUNING METAL-CENTRES THROUGH N-COORINDATED LIGANDS 1 1 1 1 Draper, S. M , Lu, Y , Wang J , Conway-Kenny R
Presenting author’s e-mail: [email protected]
1 Trinity College Dublin, University of Dublin, Dublin 2, Ireland, Adelaide, Australia
ABSTRACT TEXT
It is now well-documented that the incorporation of heteroatoms such as N, P, S, or B into the core of polycyclic aromatic hydrocarbon (PAH) derivatives fundamentally affects their electronic and optical properties.1 It is one means by which to tailor the HOMO-LUMO gap in nanographenes and to confer upon them either p- or n-type semiconducting properties as required in organic field-effect transistors and organic light emitting diodes.
Depending on the position of the heteroatom (periphery or core), such substituents can also provide ligand or coordination functionality to PAH-based molecules and imbibe them properties that can be mediated by a coordinated metal centre. This paper will detail the headway made by the Draper team in modifying and devising new synthetic strategies to planar and twisted chromophores. These have linear or laterally extended conjugation and exhibit unusual and desirable solid-state and optical properties curtesy of their aromaticity and resultant low-lying LUMO. To date the Draper team have been able demonstrate molecular complexes with a wide range of applications as triplet photosensitisers (for Triplet-triplet annihilation upconversion,2 singlet oxygen quenching,3 photodynamic therapy4 and hydrogen generation). This paper will give an insight into the emergent structure/property relationships.5
6 7 8 Figure 1: (a) [Rh(COD)(HBC)]BArF4; (b) (dppe)Pt(II) ethynylHBC; (c) Ferrocenyl-HBC; and (d) Ru(N- 2+ 5 HSB)(bpy)2] [1] Stępie et al., Chem. Rev., 2017, 117 (4), 3479–3716; [2] Lu et al., Chem.-Eur. J., 2016, 22 (32), 1521- 3765; [3] Lu et al., Angew. Chem. Int. Ed. 2016, 55, 14688; [4] Wang et al., J. Mater. Chem. C., 2016, 4, 6131-6139; [5] Draper et al., J. Am. Chem. Soc., 2004, 126, 8694-8701 ; [6] Woolf et al., Eur. J. Inorg. Chem., 2011, 1614-1625; [7] Nolan et al., Eur. J. Inorg. Chem., 2011, 3248-3256; [8] Roberts et al., Dalton Trans., 2012, 41, 8850-8860.
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From Nanoporous Inorganic Topologies to Novel Hybrid Framework Materials
Sue-Lein Wang
Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan
ABSTRACT In the last two decades, the research field of porous solids has grown rapidly, established varied chemical systems with extraordinarily novel structures and versatile functions. It has progressively expanded from the traditional inorganic framework systems of aluminosilicate zeolites, zeotypic metal phosphates/phosphite systems (MPOs) to more recently the organic-inorganic hybrid systems of organic frameworks (MOFs). These porous structures hold the key to versatile and powerful potential for novel applications. Especially, the explosive discoveries of novel MOF materials have stimulated intense search for their application science. But due to certain unstable attributes of MOF structures, it is no feasible to put them in real applications. On the other hand, the inorganic MPO systems, although less developed in the aspect of pore innovation and functional properties, have been observed to possess higher stability than the hybrid MOF structures. To increase the likelihood of stability in hybrid frameworks, we have constructed a new hybrid system where the inorganic units are entirely MPO sublattice. In this talk, I will present our new findings in MPO-based porous solids, from which emerged unique and superior functional properties not observed in existing inorganic and hybrid frameworks. Importantly, the MPO- based materials are capable of withstanding harsh conditions, having a promising prospect for real applications. The presentation will focus on breakthroughs in rational synthesis and advances of novel pore topologies, interesting properties and functionality discovered in MPO-based porous solids.
69
Frustrated Lewis pairs like reactivity of rare-earth metal complexes
Xu, P1, Chang, K1, Xu, X1 Presenting author’s e-mail: [email protected]
1 Soochow University, Suzhou, P. R. China
ABSTRACT TEXT Frustrated Lewis pairs (FLPs) have flourished into one of the most promising fields at interdiscipline of organic and inorganic chemistry during last decade. There is currently an emerging tendency to search for Lewis acid components in FLPs other than boron-based systems e.g. transition-metal (TM). These TM-based FLPs, providing their delicately- tunable Lewis acidity in contrast with the boron-based FLPs, are promising for novel and tunable stoichiometric and catalytic reactivity. Rare-earth metals, on the other hand, have been widely recognized as strong Lewis acids and the unique strong Lewis acidity is the corner stone of their widespread applications in organic synthesis. However, in FLP chemistry, Lewis acidic rare-earth metals were scarcely used. We have develped several systems that contain intra/inter-molecular combination of neutral/cationic rare-earth Lewis acids with phosphine Lewis bases, which exhibited typical and intriguing FLP-type reactivity towards a variety of unsaturated small molecules. Furthermore, they were also found to be effective catalysts for polymerization of polar alkenes initiated by novel FLP- type additions. Herein, we will present our recent research related to this topic.
70
FUNCTIONAL METAL-BASED NANOMATERIALS FROM MOLECULAR PRECURSORS
Wong, Wai-Yeung1,2
Presenting author’s e-mail: [email protected]
1 Department of Applied Biology & Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong, P.R. China 2 Institute of Molecular Functional Materials and Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong, P.R. China
Organometallic polymers represent an important research field due to their combination of unique and intriguing redox, electronic, magnetic, optical, and catalytic properties and their ability to be easily processed and fabricated into thin films, fibers, and other forms. Modern technology depends on fast, reliable data processing and storage. Hard ferromagnetic (L10-phase) FePt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are considered to be one of the most promising candidates for the next generation of ultrahigh-density data storage systems. The question of how to generate ordered patterns of L10-FePt NPs and how to transform the technology to the practical application is challenging. As these metallopolymers can be readily shaped and patterned using various lithographic techniques, they offer a convenient synthetic access to patterned arrays of metal NPs with control of their composition and density per unit area. However, many of the most desirable properties are exhibited by metal alloy NPs rather than single- component metal NPs. In this talk, the recent advances in developing new functional organometallic polymers as precursors to magnetic metal alloy NPs and their lithographic patterning studies will be presented. These metallated polymers are promising as building blocks in high-density magnetic data storage media where the convenient and rapid patterning of magnetic NPs is highly desirable. In a related context, the synthesis and characterization of new bottom-up photofunctional metal complex nanosheets will also be presented.
71
Functions Integration in Flexible MOFs for Selective Gate Opening Adsorption
Matsuda, R1,2, Ma, Y1, Hori, A1.
1Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan 2PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi 332- 0012, Japan
The discovery of a new nanoporous compound that has unique porous properties is scientifically and technologically important. Flexible MOFs show unique abrupt guest adsorption/desorption (so-called gate opening adsorption) based on their structural change in response to the adsorption of specific guest molecules or external stimuli such as light[1], leading to high selectivity for guest inclusion [2,3]. Dynamic effects can arise either from flexible ligands and/or flexibility of the coordination geometry of the metal ions, or from the global cooperative movement of the framework on a periodic scale. Here, we will report flexible MOFs that show gate opening adsorption for specific gas molecules such as hydrocarbons, carbon monoxide (CO), carbon dioxide (CO2), acetylene (C2H2), etc, realizing highly selective gas adsorption. Such selective gate opening behaviors were achieved by synergistic functions integration in MOFs, e.g. synergistic correlation between local interaction sites such as open metal sites and global flexible motion of crystalline lattice. As an example of such functions integration in a MOF, we will present a flexible MOF [Mn(bdc)(dpe)] (H2bdc= 1,4- benzenedicarboxylic acid, dpe= 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores showed an adsorbate discriminatory gate effect[4]. The compound shows gate opening type abrupt adsorption for C2H2 but not for CO2, leading to an appreciable selective adsorption of CO2 over
C2H2 at near ambient temperature (273 K) (Figure 1).
References [1] H. Sato, R. Matsuda, K. Sugimoto, M. Takata, S. Kitagawa, Nature Mater. 9 (2010) 661. [2] H. Sato, W. Kosaka, R. Matsuda, A. Hori, Y. Hijikata, R. V. Belosludov, S. Sakaki, M. Takata, S. Kitagawa, Science, 343 (2014) 167. [3] M. L. Foo, R. Matsuda, Y. Hijikata, R. Krishna, H. Sato, S. Horike, A. Hori, J. Duan, Y. Sato, Y. Kubota, M. Takata, S. Kitagawa, J. Am. Chem. Soc. 138 (2016) 3022. [4] Y. Ma, R. Matsuda, H. Sato, Y. Hijikata, L. Li, S. Kusaka, M. Foo, F. Xue, G. Akiyama, R. Yuan, S. Kitagawa, J. Am. Chem. Soc. 137 (2015) 15825.
Figure1. Adsorption isotherms for CO2 (left) and C2H2 (right) at various temperatures (left).
72
Graphene oxide hybrids with SCO complexes
Hayami, S, Kobayashi, F, Sekimoto, Y, Ohtani, R
e-mail: [email protected]
Kumamoto University, Kumamoto, Japan
The van der Waals interactions in pores of micro-porous materials generate a confinement effect for guest species. Confinement effects, in particular pseudo-pressure effects, are of importance to developments of characteristic states and unique phases of materials in pores under mild conditions. Recently, it has been reported that stacking structures of two- dimensional (2D) nano-sheets of graphene also act as a field to produce the confinement effects. Although there are many types of porous materials, tunable confinement effects arising from pore size tuning in one material remain unexplored. In most cases, the different size pores should be prepared one by one to obtain required pseudopressure effects. Materials exhibiting tunable confinement effects will produce a useful platform for the precise control of physical properties of nanomaterials confined in the pores. Accordingly, we have focused on the structural transformation from graphene oxide (GO) to reduced graphene oxide (rGO) for the development of tunable confinement effects. The tunable pressure effects associated with interlayer distances of twodimensional graphene oxide (GO) and reduced GO (rGO) layers are demonstrated by monitoring the changes of spincrossover (SCO) temperatures (T1/2) of [Fe(Htrz)2(trz)](BF4) nanoparticles (NPs) that are incorporated in space of layers. The interlayer distances of GO-NP composites decrease continuously from 9.00 Å (for GO) to 3.50 Å (for rGO) by increasing temperatures of thermal treatments for GO-NP composites. At the same time, T1/2 increases from 351 K to 362 K. This T1/2 increment of 11 K is in accord with what observed in [Fe(Htrz)2(trz)](BF4) pristine NPs under a hydrostatic pressure of 38 MPa. The influence of the stacking structures of layers on the resulting pseudopressure effects has been probed by investigating differences in T1/2 of [Fe(Htrz)2(trz)](BF4) using larger bulk particles instead of the NPs.
73
GUEST-INDUCED ASSEMBLY OF BIS(THIOSEMICARBAZONATO) ZINC(II) COORDINATION NANOTUBES
Paterson, B. M1, White, K. F1, White, J. M1, Abrahams, B. F1, Donnelly, P. S1
Presenting author’s e-mail: [email protected]
1 University of Melbourne, Melbourne, Australia
ABSTRACT TEXT
The directional and reversible nature of coordination bonds permits supramolecular transformations as a function of stimuli such as solvent, concentration, counterion, or guest. Template molecules serving as guests within a cavity can induce product formation and stabilization in what has been termed “guest-induced assembly”. Guest molecules can also shift the equilibrium from the self-assembled product to an otherwise entropically unfavorable product. The host-guest chemistry of “nanotubes” with one-dimensional hollow channels has potential for applications in molecular separation, gas sorption and storage, or as reaction vessels.
The rotational flexibility demonstrated by thiosemicarbazone (tsc) and bis(thiosemicarbazone) (btsc) ligands allows them to exist in different configurations as either monodentate or polydentate ligands and with multiple binding modes that can lead to diverse and elaborate supramolecular structures from identical metal-ligand combinations.
The flexible dianionic tetradentate ligand formed by deprotonation of glyoxal-bis(4-phenyl- 3-thiosemicarbazone) (H2gtsp) and zinc(II) forms a charge-neutral trinuclear triangular prism. In the presence of linear templating molecules CO2, CS2 or CH3CN charge-neutral tetranuclear square coordination nanotubes form with the templating agent included as a guest and an approximate length of 2 nm. The template can be removed from the inclusion complex while maintaining a porous material capable of adsorbing roughly two molecules -1 of CO2 per nanotube with an isosteric enthalpy of sorption of 28 kJ mol at low loading.
74
Harnessing Electroactivity in Nanoporous Coordination Frameworks
D’Alessandro, D.M.1
Presenting author’s e-mail: [email protected]
1 The University of Sydney, Sydney, Australia
Electroactive coordination frameworks (aka Metal-Organic Frameworks (MOFs)) offer a fundamental platform to explore electron transfer phenomena within 3-dimensional coordination space. At the applied level, these materials have enormous potential as the basis for electrochromic devices, electrocatalysts, porous conductors, batteries and solar energy harvesting systems, amongst numerous other potential applications.
This presentation will detail our latest results in the design and synthesis of electroactive MOFs that integrate molecular components for electron transfer including radical ligands and mixed-valence metal centres. Key to our investigations have been solid-state AC/DC electrochemical methods in addition to solid-state near-IR/Vis, EPR and Raman spectroelectrochemical (SEC) techniques which have been developed in our laboratory, providing powerful in situ probes for the optical and electron transfer characteristics of MOFs. These methods are potentially relevant to exploring electroactivity and fundamental charge transfer phenomena in a wide range of other materials (e.g., supramolecular systems, battery materials, etc). Our work on the DFT computational modelling of the electronic and optical properties of these systems will also be described, providing an important link between experiment and theory.
75
Highly Effective Synthesis of Polyoxometalates Clusters / Coordination Polymers by Using Continuous Flow Chemistry
Zhang, J.1, Chang, S.2, Suryanto, B. H.3, Zhao, C.3, Zeng, Q.2, Xie, J.1
Presenting author’s e-mail: [email protected] (Dr. Jingli Xie)
1 Jiaxing University, Jiaxing, P. R. China 2 National Center for Nanoscience and Technology, Beijing, P. R. China 3 University of New South Wales, Sydney, Australia
Continuous flow chemistry has been developed dramatically in the fields of organic and pharmaceutical synthesis, while its application in preparative inorganic chemistry has been exploited to a lesser extent [1]. Recently, our group reported the dinuclear iridium(III)- containing polyoxotungstate cluster K12Na2H2[Ir2Cl8P2W20O72]·37H2O could be successfully synthesized with a reasonable yield ~ 13% [2]. Compared with the previous report about no diiridium-substituted product could be obtained under batch-type reaction (C. Hill et al, Inorg. Chem., 2009, 48, 5596-5598), the efficient synthesis of dinuclear Ir-POMs product could attribute to the employed flow-type reactor.
To further explore the great potential of flow chemistry for synthesizing coordination polymers, we recently reported that the coordination polymer [Co2L4(2H2O)]n could be obtained with very high yield by using commercial Asia flow synthesis system (chip reactor) [3].
Figure (left) Use the chip reactor to synthesize coordination polymer; (right) top: The synthetic protocol of POMs cluster 1 by using tube reactor; bottom: STM image of the 2D self-assembled structure of 1 / TCDB adsorbed on the HOPG surface.
References：
[1] J. Zhang, C. Gong, X. Zeng, J. Xie, "Continuous Flow Chemistry: New Strategies for Preparative Inorganic Chemistry" Coord. Chem. Rev., 2016, 324, 39-53. [2] J. Zhang, S. Chang, B. H. R. Suryanto, C. Gong, X. Zeng, C. Zhao, Q. Zeng, J. Xie "Efficient Synthesis of Ir-Polyoxometalate Cluster Using a Continuous Flow Apparatus and STM Investigation of Its Coassembly Behaviour on HOPG Surface" Inorg. Chem., 2016, 55, 5585-5591. [3] C. Gong, J. Zhang, X. Zeng, J. Xie, "Highly Effective Synthesis of a cobalt(II) Metal- Organic Coordination Polymer by Using Continuous Flow Chemistry" Dalton Trans., 2017, 46, 25-28 (inside back cover). 76
HOW DOES THE MAGNETIC SUSCEPTIBILITY TENSOR AFFECT NMR PSEUDOCONTACT SHIFT?
Parker, D 1 ; Frawley, AT 1 ; Mason, K 1 ; Suturina, E 2 ; Kuprov, I 2 ; Chilton, N 3 ; Vonci, M 3 ; McInnes, EJ 3
1 Department of Chemistry, Durham University, Durham, UK 2 Department of Chemistry, University of Southampton, Southampton UK 3 School of Chemistry, University of Manchester, Manchester, UK
Paramagnetic lanthanide (III) complexes have found widespread use as shift reagents in NMR, as relaxation agents in MRI and as protein structural probes in solution analysis. Understanding the determinants of the pseudocontact shift (PCS) is essential to understand the scope and limitations of these applications. Old theories relied upon several debatable assumptions, even for coordinatively saturated systems, where no solvent is bound. Thus, it is commonly assumed: that the ligand field splitting is invariant with the lanthanide ion and independent of the solvent medium; that the energy of this splitting is Using variable temperature EPR, magnetic susceptibility, NMR, optical emission methods and CASSCF calculations, several systems have been studied with small or large ligand field splittings. Examples have been defined where the size of the second order crystal field parameter varies with the Ln ion and can even change sign in different solvents. The interaction of the lanthanide multipole with induced dipoles on the solvated ligand may be important here. The orientation of the PCS field is shown to be very sensitive to structural variation in the ligand and to solvent permutation. It is the anisotropy of the magnetic susceptibility tensor and its orientation that is paramount, even in axially symmetric systems. 77 Hydrogenation of Formic acid to methanol by Iridium Catalysts Tsurusaki, A1, Onishi, N1, Laurenczy, G2, Himeda, Y1 Presenting author’s e-mail: [email protected] 1National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan 2École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland ABSTRACT Production of methanol (MeOH) from CO2 using homogenous catalysts has received considerable attention.1 In this presentation, we describe the efficient hydrogenation/disproportionation of formic acid (FA) to MeOH by using iridium catalysts with electronically tuned ligands and by optimizing reaction conditions. We investigated the catalytic activities of the FA hydrogenation using Cp* iridium aqua complexes with various 2,2'-bipyridine ligand.2-4 It was found that an iridium complex with 5,5'-dimethyl-2,2'-bipyridine in FA hydrogenation achieved MeOH selectivity with H2 of up to 47.1% for FA hydrogenation under 4.5 MPa of H2 in the presence of H2SO4. Even under atmospheric pressure, the disproportionation of FA-d2 in D2O produced methanol-d with 15.4% selectivity, probably due to inhibition of the H2 or D2 production by protonation of a deuteride complex as a competitive reaction. These results provide productive information on the catalyst design and the catalytic system of the FA hydrogenation. Ref. 1. Wang, W.-H.; Himeda, Y.; Muckerman, J. T.; Manbeck, G. F.; Fujita, E. Chem. Rev. 2015, 115, 12936-12973. 2. Sordakis, K.; Tsurusaki, A.; Iguchi, M.; Kawanami, H.; Himeda, Y.; Laurenczy, G. Chem. Eur. J. 2016, 22, 15605-15608. 3. Tsurusaki, A.; Murata, K.; Onishi, N.; Sordakis, K.; Laurenczy, G.; Himeda, Y. ACS Catal. 2017, 7, 1123-1131. 4. Sordakis, K.; Tsurusaki, A.; Iguchi, M.; Kawanami, H.; Himeda, Y.; Laurenczy, G. Green Chem. 2017, DOI: 10.1039/C1036GC03359H. 78 INCORPORATION OF TRANSITION METALS INTO SINGLE MOLECULE CONDUCTORS Davidson, R. J.,1 Costa-Milan,2 D. Liang, J.2 Nichols, R. J.,2 Higgins, S. J.,2 Yufit, D. S.,1 Beeby, A.,1 Low, P. J.3 Durham University, Durham, UK University of Liverpool, Liverpool, UK University of Western Australia, Perth, Australia With conventional silicon-based electronics nearing their size and therefore power limits, there has been a drive to develop molecular electronics, whereby individual molecules act as the electronic components. Although it is an active field of research, there still remain a great number of questions about the factors affecting single-molecule conductance. A convenient method for probing this is to incorporate a metal centres into molecular wires (a highly π-conjugated system), allowing the electron properties of the molecule to be modified without significantly altering the geometry. 4-substituted bis-2,2′:6′,2″-terpyridine (tpy) metal complexes provide a distinct advantage existing organometallic systems as the metal, linker and binding site are able to be modified in a modular fashion without requiring significantly different synthetic approaches. In this project we examined a series of mono- and bi-metallic of iron(II), cobalt(II) and ruthenium(II) complexes based on combinations of 2,3,5,6-tetra(pyridine-2-yl)pyrazine and methyl-sulfane or trimethylsilylacetylene substituted 2,2′:6′,2″-terpyridine ligands. Using conductance STM we explored how the single molecule conductance of metal complexes can be significantly affected by the combination of metal and surface binding group, much more so than the their pure organic molecule analogues. 79 Inelastic Neutron Scattering and Linear Spin Wave Theory as a Tool for Molecular Magnetism Mole, R.A.1, Rule K.C.1, Stride, J.A.2, Wood, P.T.3 Presenting author’s e-mail: [email protected] Affiliations (Arial, 12 font Italics, Organisation, City, Country) e.g. 1 Australian Nuclear Science and Technology Organsiation, Lucas Heights, Australia 2 University of New South Wales, Sydney, Australia 3 University of Cambridge, Cambridge, UK The use of SQUID magnetometers to obtain susceptibility data is ubiquitous throughout the field of molecular magnetism. This is due to the low cost and ready availability of the instrumentation. The high sample throughput makes them ideal for use in the discovery of new magnetic networks and frameworks. The primary aim of much of this work is to parameterise a microscopic Hamiltonian for any new material and from this to be able to determine structure property relationships. The main disadvantage of this technique is the relatively low information density associated with this data. In this contribution I will discuss the combined use of inelastic neutron scattering (INS) and linear spin wave theory; although these techniques are not new, they have often been seen as specialist. Using the example of Mn3(1,2,4-(O2C)3C6H3)2, a coordination polymer with a distorted kagomé, lattice I will highlight some of the misconceptions about these techniques. The work involves the use of a modest quantity of material with no effort made to deuterate the ligand. The space group is monoclinic highlighting that the calculations are not restricted to high symmetry unit cells. Modern software programs for the calculation of spin waves easily allow the powder average to be determined and work with arbitrary symmetry and the most general possible Hamiltonian including both anisotropic exchange and single ion anisotropy. As the neutron scattering data span both energy and reciprocal space it is possible to correlate excitations with specific length scales and thus aid in the determination of structure/property relationships. 80 Investigations into Alkali Metallated Imines: Additions vs Deprotonations and Their Applications in Synthesis Border, E1, Blair, V1, Andrews, P1 1Monash University, Melbourne, Australia Imines play an important role in synthetic chemistry as building blocks for more complex molecules. There has been significant focus on chiral secondary and tertiary amines, especially those derived from (S)-N-α-methylbenzylamine and their metallations with alkali metals. This has generated numerous examples of facile metal hydride eliminations leading to anion changes from amines to 2-aza-allyl complexes and rearrangements to 1- aza-allyl and aza-enolate complexes.1 An alternative route to these aza-allylic species is via imines, allowing a more direct synthesis and not relying on decomposition of the metal complex. However, when an imine is reacted with a metal the outcome is dependent on the substitution of the imine and subsequently the ability of the imine bond to “aza-enolise” or become “aza-allylic”.2 There are limited studies of metal mediated anionic rearrangements of imino complexes compared with the amine counterparts with very little evidence on imines of the form RN=C(H)R being reacted with alkali metals. Here we present our findings of deprotonations vs additions and cyclisation reactions of [(4-Methoxyphenyl)methylidine]aniline where the result is highly dependent on the alkali metal source (Figure 1). This has opened up new avenues of imine chemistry including the synthesis of isoindolines and investigations into possible carbene alternatives. Figure 1. Addition (left) vs Deprotonation (right) resulting from two different sodium sources. References: 1. (a) Andrews, P. C., Blair, V. L., Border, E. C., Peatt, A. C., MacLellan, J. G., Thompson, C. D., Organometallics, 2013, 32, 7509. (b) Andrews, P. C., Koutsaplis, M., Robertson, E. G., Organometallics, 2009, 28, 1697. 81 2. Andrews, P. C., Armstrong, D. R., Raston, C. L., Roberts, B. A., Skelton, B. W., White, A. H., J. Chem. Soc., Dalton Trans., 2001, 996. 82 -Expansive Iridium and Ruthenium Complexes as Reverse Saturable Absorbers and In Vitro Theranostic PDT Agents Sun, W.,1,2* Wang, L.,1 Wang, C.,1 Yin, H.,3 Hetu, M.,3 Monro, S.,3 Cameron, C. G.,4 McFarland, S. A.3,4 1Department of Chemistry and Biochemistry, North Dakota State University, Fargo, ND 58108-6050, USA 2College of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin, P.R. China 3Department of Chemistry, Acadia University, Wolfville, NS B4P 2R6, Canada 4Department of Chemistry and Biochemistry, University of North Carolina at Greensboro, Greensboro, NC 27402-6170, USA Iridium(III) and ruthenium(II) complexes with absorption in the visible to the near-infrared region, long-lived triplet excited states, high quantum yield for triplet excited state formation, strong excited-state absorption, and near-IR emission are promising agents for reverse saturable absorption (RSA) and photodynamic therapy (PDT) and bioimaging. The synthesis, photophysics, RSA, and in vitro PDT effect and bioimaging of two series of cationic biscyclometalated Ir(III) complexes and one series of Ru(II) complexes with extended -conjugation on the diimine and/or the cyclometalating ligands are reported. Most of the complexes possess moderate to strong charge-transfer absorption bands between 400 and 600 nm; and these bands are extended to 800 nm when the - conjugation of the diimine or cyclometalating ligands increases. They are all emissive in the red to the NIR region. The natures and energies of the lowest singlet and emitting triplet excited states are primarily influenced by the -conjugation of the ancillary diimine or cyclometalating ligands. However, the lowest-energy triplet excited states for complexes that contain the benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (dppn) ligand are the long-lived dppn-localized 3,* state. Most of the complexes exhibit strong RSA at 532 nm for ns laser pulses, and can generate singlet oxygen efficiently. Thus, those complexes exhibit a PDT effect upon visible or red light activation, with one of the complexes possessing the largest phototherapeutic index reported to date (> 400) for Ir(III) complexes upon white light activation. These complexes also produce strong intracellular luminescence that highlights their potential as theranostic PDT agents. 83 Iron(IV) Imido and Alkylidene Species with NHC and Amido Ligation Deng, L1, Liu, J1, Wang, L1 1 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 20003, People’s Republic of China ABSTRACT TEXT: Transition-metal imido and alkylidene species are implicated as key intermediates in many important transition-metal catalysed transformations, and have thus intrigued great research interests.[1] Among the least understood is the high-valent late 3d metal imido and alkylidene complexes due to their higher activity and the consequent synthetic challenge.[2] In this presentation, we’d like present our studies on iron(IV) imido and alkylidene speices with N-heterocylic carbene (NHC) and amido-phosphine-amido as ancillary ligand, respectively. These ligands have proved effective to stabilize formal iron(IV) species that show diversified group-transfer reactivity.[3,4] The correlation of the electronic structure of the metal-ligand multiple bond species with their group-transfer reactivity will be discussed. References: [1] W. A. Nugent, J. M. Mayer, Metal-Ligand Multiple Bonds, The Chemistry of Transition Metal Complexes Containing Oxo, Nitrido, Imido, Alkylidyne Ligands; Wiley: New York, 1988. [2] C. T. Saouma, J. C. Peters, Coord. Chem. Rev. 2011, 255, 920. [3] L. Wang, L. Hu, H. Zhang, H. Chen, L. Deng, J. Am. Chem. Soc, 2015, 137, 14196. [4] J. Liu, L. Hu, L. Wang, H. Chen, L. Deng, J. Am. Chem. Soc, 2017, DOI: 10.1021/jacs.7b00484. 84 Is Vanadium an Essential Trace Element? Lay, P A1 Presenting author’s e-mail: [email protected] 1 School of Chemistry, Australian Institute of Nanoscale Science and Technology (AINST), Marie Bashir Institute, and Vibrational Spectroscopy Core Facility, The University of Sydney, Sydney, Australia ABSTRACT There has been a long debate as to whether vanadium is an essential trace element for humans? Herein we will discuss a range of roles of vanadium in human biology, all of which can be influenced by selective gene expression and selective protein activation (phosphorylation) of proteins by vanadium. In addition, certain cells have mechanisms to collect vanadium even in V-deficient medium. Taken together, we will present a range of results that indicate that vanadium may well be an essential trace element for humans. 85 ISOLATION AND PRELIMINARY METAL BINDING STUDY OF RICE METALLOTHIONEIN OsMT2b NEO, K.-E1, TAN, Z.-L1, WONG, H. L1, KUMAR, D2, BEH, W. L1, LOH, P. C1 and NG, C.- H3 Presenting author’s e-mail: [email protected] 1 Universiti Tunku Abdul Rahman, Kampar, Malaysia 2 Ton Duc Thang University, Ho Chi Minh City, Vietnam 3 International Medical University, Kuala Lumpur, Malaysia ABSTRACT Metallothionein is a cysteine-rich protein with a molecular weight below 10 kDa. This protein is known to bind a wide range of metals, including arsenic, cadmium, copper, mercury, silver, and zinc. Experimental data suggest metallothionein plays a role in biological processes, such as metal homeostasis, metal detoxification and radical oxygen species scavenging. Plant metallothioneins, which are not well studied as their animal counterparts, have recently received much attention in bioinorganic chemistry research. In this presentation, we describes our preliminary study on a rice metallothionein that is encoded the OsMT2b gene. OsMT2b protein contains two cysteine-rich metal-binding domains separated by a spacer region. We cloned the full-length OsMT2b and separately cloned its two cysteine-rich metal-binding domains. The clones were translationally fused to the glutathione S-transferase (GST) tag. Here we report the isolation, purification and preliminary metal binding study of the full-length OsMT2b and its metal binding domains. This study may provide insights into the metal-binding characteristics and the role of metallothionein in regulating metal ion homeostasis in rice. 86 Isomorphic and Isofunctional Fluorescent Nucleosides Tor, Y Presenting author’s e-mail: [email protected] University of California, San Diego, La Jolla, California, USA Nucleic acids experience a variety of perturbations. These may include hybridization and dissociation, strand cleavage and ligation, local conformational changes, base flipping, excision and modification, as well as perturbations induced upon protein and low MW ligand binding. Additionally, nucleic acids attract increasing attention as drug targets (e.g., bacterial rRNA as a target for antibiotics) and as potential drugs (e.g., siRNA for disease- specific gene silencing). Furthermore, nucleosides and nucleotides derivatives are involved in numerous metabolic and regulatory processes. Isomorphic fluorescent nucleoside analogs, which can serve as faithful surrogates and are sensitive to their local environment, can be powerful probes for investigating such diverse processes. The lecture will present the design, synthesis and photophysical properties of new fluorescent isomorphic nucleobase analogs as well as their oligonucleotide incorporation (by solid-phase and enzymatic reactions) and utilization for the fabrication of "real-time" fluorescence-based discovery and biophysical assays. The overlap of our program with Professor Leone Spiccia’s interests will be highlighted. 87 Kinetic Assembly of Porous Coordination Networks Kawano, Masaki e-mail: [email protected] Tokyo Institute of Technology, Tokyo, Japan Because of the presence of intermolecular interactions during self-assembly, there are many metastable structures before reaching the thermally most stable structure. By controlling the weak intermolecular interactions, we can trap various metastable coordination networks which will not be obtained by conventional thermodynamic control like solvothermal synthesis. In sharp contrast to the thermodynamic synthesis of coordination networks, kinetically trapped metastable networks were not paid much attention, because firstly it is very difficult to analyse crystal structures. Recently we have demonstrated that it is possible to perform ab initio powder structure determination of porous coordination networks using low resolution data.1-3 In addition, we elucidated that totally different coordination networks can be selectively prepared using the same starting materials by thermodynamic and kinetic control.4,5 In this talk, we will introduce selective preparation of metastable porous networks by kinetic control, the chemistry of porous networks, their unique sorption properties, redox properties, and X-ray snapshots of chemical transformation in a pore.6,7 References [1] Martí-Rujas J. and Kawano M. Acc. Chem. Res., 2013, 46, 493. [2] Yakiyama, et al Chem. Commun., 2015, 51, 6828. [3] Ohtsu, H. and Kawano, M. Dalton Trans., 2016, 45, 489. [4] Ohtsu H., et al J. Am. Chem. Soc., 2013, 135, 11449. [5] Kitagawa H., et al Angew. Chem. Int. Ed., 2013, 125, 12621. [6] Koo, J.Y., et al J. Am. Chem. Soc. 2016, 138, 1776. [7] Kitagawa, H., et al IUCrJ，2016, 3, 232. 88 LANTHANOID SINGLE-MOLECULE MAGNETS: INELASTIC NEUTRON SCATTERING AND AB INITIO STUDIES Vonci, M1, Murray, KS2, Mole, R3, Soncini, A1, Boskovic, C1 1 University of Melbourne, Parkville, Australia 2 Monash University, Clayton, Australia 3 Australian Nuclear Science and Technology Organisation, Australia Lanthanoid single-molecule magnets (SMMs) are of interest for future applications in quantum computing and molecular spintronics. The structural rigidity and large negative charge of polyoxometalates (POMs) confer on lanthanoid ions with POM ligands a different local coordination environment to that available with organic ligands. The resulting crystal field governs the key SMM features of slow magnetic relaxation and magnetisation quantum tunnelling. The study of POM-supported lanthanoid-single molecule magnets (SMMs) can thus afford new insights into the effect of lanthanoid coordination environment on SMM properties (Vonci 2014). We have applied a concerted experimental and theoretical approach to investigate the 9- [Ln(W5O18)2] family of SMMs (AlDamen 2008). Inelastic neutron scattering (INS), magnetochemical and ab initio studies have allowed elucidation of the relationship between the lanthanoid crystal field splitting and the measured magnetic and spectroscopic properties (Vonci 2016, Vonci 2017). Inelastic neutron scattering has also proved to be a powerful tool for benchmarking the computational efforts. References: M. Vonci, C. Boskovic, Aust. J. Chem. 2014, 67, 1542-1552. M. A. AlDamen, J. M. Clemente-Juan, E. Coronado, C. Martí-Gastaldo, A. Gaita Ariño, J. Am. Chem. Soc. 2008, 130, 8874-8875. M. Vonci, M. J. Giansiracusa, R. W. Gable, W. Van den Heuvel, K. Latham, B. Moubaraki, K. S. Murray, D. Yu, R. Mole, A. Soncini, C. Boskovic, Chem. Commun. 2016, 52, 2091- 2094 M. Vonci, M. Giansiracusa, W. Van den Heuvel, R. Gable, B. Moubaraki, K. Murray, D.Yu, Dehong, R. Mole, A. Soncini, C. Boskovic, Inorg. Chem. 2017, 56, 378–394. 89 Leone Spiccia's Influence in Geochemistry Casey, W. H.1 Presenting author’s e-mail: [email protected] 1Department of Chemistry, Department of Earth and Planetary Sciences, University of California, Davis, CA, 95616 USA Leone Spiccia's early work on aqueous oxide clusters[1] played a key role in the development of molecular views in aqueous geochemistry. Twenty five years ago, geochemists were starting to explore synchrotron-based methods to establish the structure of metal-oxide features on minerals. Without experimental models, the results were interpreted using electronic-structure calculations only, and this was an ugly business. Their goal was a molecular understanding of mineral oxide surface chemistry, including the Brønsted acid-base chemistry, the steps in dissociation of metal-oxide polymers, and the dissolution/growth of minerals. Until Leone's work was discovered, it was assumed that no experimental models could be found for the complex structures. Leone showed that one could separate by column chromatography (left) oxide clusters of several metals that closely resemble fragments of common metal- (hydr)oxide minerals. The connection was explicit. One could use his information to develop a rich and accurate understanding of oxide polymers of geochemical interest. His detailing of the stepwise reactions in Rh(III) trimeric molecules remains unparalleled in the field, leading to a proud legacy in Geochemistry[2-3]. [1] L. Spiccia, Inorganica Chimica Acta 2004, 357, 2799‐2817. [2] L. Spiccia, W. H. Casey, Geochimica et Cosmochimica Acta 2007, 71, 5590‐5604. [3] R. K. Hocking, R. Brimblecombe, S. L. Y. Chang, A. Singh, M. H. Cheah, C. Glover, W. H. Casey, L. Spiccia, Nature Chemistry 2011, 3, 461‐466. 90 LIGHTING UP SUGARS: LINKING BODIPY TO SUGARS THROUGH BORON Bowen Liu,1 Nina Novikova,1 Martijn Wildervanck,1 Miriana Horacek,1 M. Cather Simpson,1,2 Bridget L. Stocker,3 Tilo Soehnel,1 Mattie S. Timmer,3 David C. Ware,1 Penelope J. Brothers1,2* Presenting author’s e-mail: [email protected] 1University of Auckland, Auckland, New Zealand. 2The MacDiarmid Institute for Advanced Materials and Nanotechnology, NZ 3Victoria University of Wellington, Wellington, New Zealand. F-BODIPY dyes (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) are a well-known group of fluorescent molecules which comprise a dipyrrin framework with a BF core and exhibit sharp fluorescence emissions with high quantum yields. F-BODIPYs are used as probes for a wide variety of biomolecules, typically linked to the target analyte via a tether appended to the to dipyrrin backbone. Although BODIPYs are widely used as fluorescent labels and chemosensors, chemical modifications, including the link to the tether, have been almost exclusively confined to the dipyrrin carbon framework, leaving the BF core intact. Various reports in the literature have described strategies for the synthesis of boron- functionalised BODIPYs by substitution of the F-BODIPY fluoride atoms, including methods for producing BODIPYs bearing 4,4-alkoxide or 4,4-aryloxide substituents (O-BODIPY). Many important biomolecules bear oxygen-containing functional groups, which suggested to us the possibility of directly linking an O-BODIPY fluorophore to a target biomolecule through the O-BODIPY oxygen atoms. The new chemistry we have recently developed towards this aim will be described. In particular, we have explored the direct connection of O-BODIPY to carbohydrates through B-O-C links and have produced examples of 1:1 and 2:1 BODIPY saccharide complexes, characterised through a range of spectroscopic techniques, X-ray crystallography and absorption and emission spectroscopy. 91 Liposome Composites Hierarchically Integrated Functional Metal Complexes Ohba, M, Koshiyama, T Kyushu University, Fukuoka, Japan Hierarchical integration of various functional components, such as cofactors and enzymes, is achieved using biomembrane and protein assemblies in nature, leading to coupling of different chemical reactions. Artificially creating such multifunctional reaction systems is one of the most considerable topics in current chemistry. Although various chemical reactors consisting of polymers and proteins have been studied, it is still difficult to construct reaction systems in which different chemical reactions occur simultaneously. We focus on liposome, which is an artificially-prepared spherical vesicle composed of a lipid bilayer of phospholipids, as a chemical reaction space. It is expected that different functional molecules co-exist in or on one liposome hierarchically, because a liposome provides four different regions, namely - hydrophilic inner water phase, hydrophobic lipid bilayer, and inner and outer surfaces. To construct novel functional composites, we integrated metal complexes (e.g., catalyst, photoreceptor, luminant, electron mediator, and molecular storage and separator) into the liposome space site-specifically. In the presentation, I will introduce the functionalization of liposome surface with lipophilic metal complexes such as the coordination polymer1, the water oxidation catalyst2 and the photoinduced release of nitric oxide3, and the ion-channel driven direct synthesis of coordination polymers in the inner aqueous phase. References [1] Ohtani, R, Kitagawa, S, Ohba, M et al., Angew. Chem. Int. Ed., 54, 1139 (2015). [2] Koshiyama, T, Kanda, N, Ohba, M et al., Dalton Trans., 44, 15126 (2015). [3] Nakanishi, K, Koshiyama, T, Iba, S, Ohba, M, Dalton Trans., 44, 14200 (2015). 92 LIQUID-PHASE INTERFACIAL NANOASSEMBLY OF METAL-ORGANIC FRAMEWORKS INTO HIGHLY-CRYSTALLINE NANOSHEETS Makiura, R Department of Materials Science, Osaka Prefecture University, Osaka, Japan Development of rational methods for creating ordered two-dimensional (2D) structures with nanometer scale precision is one of the central issues in the nanoscience and nanotechnology fields because of their intrinsic physical-chemical properties which are seen in comparison with those of their equivalent bulk state. Inclusion of highly-regulated nanopores into the nanosheet structure should further open possible applications such as nanosieves, molecular/ion storage and sensor devices while introduction of guest molecules into the nanopores should tune variedly the sheet properties (electric conduction, nanoheterojunction). Utilizing molecular building units is suitable for creating such porous nanosheets because of the rich variety of design and facile modification of size and shape. Furthermore, various chemical interactions such as covalent, coordination and hydrogen bonding can be employed for assembling molecular-based nanosheets. Here, I present a facile bottom-up synthesis of molecular nanosheets with both positional- and size-regulated nanopores utilizing air/liquid interfaces. By applying liquid interfaces, the growth direction of the object can be well controlled by utilizing self-assembly feature of the molecules under mild conditions. We have succeeded in finely tuning the nanosheet structures by rational modification of molecular building units. In addition, new methodology we developed based on the liquid interface technique resulted in enlarging the nanosheet size. The highly-crystalline structure remains after transferring to a solid substrate from the liquid surface as well as without any support. Notably, such a highly-oriented porous crystalline structure is obtained specifically by applying bottom-up synthesis at air/liquid interfaces, not by exfoliation of bulk crystals. 93 Luminescence Color Change in Trigonal-planar Digold(I) Complexes with Bis(diphenylphosphino)methane Yoshinari, N,1 Igawa, K,1 Okumura, M,1 Ohtsu, H,2 Kawano, M,2 Konno, T1 Presenting author’s e-mail: [email protected] 1 Osaka University, Osaka, Japan 2 Tokyo Institute of Technology, Tokyo, Japan ABSTRACT TEXT Photoluminescent compounds showing emission color changes in response to external stimuli have received considerable attention because of their wide range of applications. These compounds often involve AuI ions as a metal component, in which their photo-luminescence is highly sensitive to the change in intramolecular and intermolecular Au···Au aurophilic interactions. Generally, each AuI center of these compounds has a 2- coordinated linear geometry. This geometry enables them to form an effective Au···Au interaction and to accept another donor that exists as a counter ion or solvent molecule to their vacant coordination sites. In contrast, the chromic behavior has not been reported for those containing three-coordinated, trigonal-planar AuI centers. Herein, we report the photo-luminescent properties of a digold(I) complex, 2+ 2+ [Au2(dppm)3] (dppm = bis(diphenylphosphino)methane, [1] ), in which two trigonal-planar AuI centers are triply bridged by three dppm ligands.[1] In the solid state, Cl– and OTf– salts of [1]2+ exhibit a quite brilliant emission with a quantum yield of >95%. A reversible, two- step emission color change from green to blue via yellow in responding to heating, moisture, and mechanical force is also reported. [1] K. Igawa, N. Yoshinari, M. Okumura, H. Ohtsu, M. Kawano, T. Konno, Sci. Rep. 2016, 6, 26002. 94 Luminescent Ir(III)-Eu(III) Complexes for Applications in Biological Imaging and Electrochemiluminescence Barnard, PJ, Quan, LM, Ramkissoon, P, Stringer, BD, Baxter, AA, Hulett, MD, and Hogan, CF La Trobe University, Melbourne, Australia The luminescent properties of lanthanide (Ln) complexes are ideal for many sensing applications due to their narrow, well separated emission bands and long excited state lifetimes.1 Recently, d–f heteronuclear assemblies, in which a strongly absorbing d-block chromophore excites the Ln-based fluorophore instead of an organic antenna group, have attracted considerable attention.2 We are interested in the development of novel electrochemiluminescent (ECL) complexes3,4 and recently we have prepared a new class of electrochemiluminescent Ir(III)-Ln(III) heterobimetallic complexes (e.g. 1 and 2, Figure 1) in approximately 12 synthetic steps. Spectroscopic studies on these assemblies show efficient sensitization of the coordinated Eu(III) ion by the Ir(III) complex. These complexes display electrochemiluminescence (ECL) where an electrochemically initiated emission is observed from the Eu(III) ion, following energy transfer from the ECL- active Ir(III) donor. Non-optical sensitization of the luminescence from lanthanide ions opens exciting new possibilities for the development of ECL probes that are emissive in the near-infrared (NIR). These heterobimetallic arrays are also of interest for biological imaging applications and fluorescence confocal microscopy studies show that 1 and 2 are readily taken up by HeLa cells. Figure 1. Structures of heterobimetallic complexes 1 and 2. References [1] Bünzli, J.-C.G., Chem. Rev. 2010, 110, 2729–2755. [2] Ward, M.D., Coord. Chem. Rev. 2007, 251, 1663–1677. [3] Barbante, G.J., Francis, P.S. Hogan, C.F., Kheradmand, P.R., Wilson, D.J.D., Barnard, P.J., Inorg. Chem. 2013, 52 (13), 7448-7459 [4] BD Stringer, LM Quan, PJ Barnard, DJD Wilson, CF Hogan Organometallics 2014, 33 (18), 4860-4872 95 Magnetic and photophysical investigation of versatile rare-earth-dioxolene systems Rousset, E.1, Piccardo, M. 1, Gable, R.W.1, Moubaraki, B. 2, Murray, K.2 Massi, M.3, Soncini, A. 1, Sorace, L.4, Boskovic, C.*,1 1 School of Chemistry, University of Melbourne, Parkville, Victoria 3010, Australia 2 School of Chemistry, Monash University, Clayton, Victoria 3010, Australia 3 Department of Chemistry, Curtin University, Bentley, WA 6102, Australia 4 UdR INSTM and Department of Chemistry “U. Schiff″, University of Florence, 50019 Sesto Fiorentino (FI), Italy The lanthanoid metals are of interest for a range of present and future applications, largely due to their unique optical and magnetic properties. Reported lanthanoid complexes are generally supported by oxygen-donor ligands, β-diketonates particularly. However, in comparison, the family of o-dioxolene ligands is relatively unexplored. We report here the synthesis and structural characterisation of a series of mono- and polynuclear lanthanoid complexes incorporating redox-active dioxolene ligands and other ancillary ligands (eg 2,2’ bipyridine, crown ether). Systematic variation of the reaction stoichiometry of ancillary ligands and redox-active ligands affords mono-, di- or trinuclear complexes. The magnetic investigation of these systems will be described as well as their photophysical properties. Ab initio calculations have afforded insights into the magnetic behaviour of the monomeric species. Figure 1. Examples of different families of complexes of different nuclearities obtained from the reaction of lanthanoids salts with halogenated dioxolenes ligands. 96 Magnetocaloric Effect of High-nuclearity 4f and 3d-4f Metal Clusters La-Sheng Long e-mail: [email protected] State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry Xiamen University, Xiamen (361005), China ABSTRACT TEXT Magnetic refrigeration, a cooling technology based on the MCE, has attracted much interest in the field of magnetic materials,1 due to its environmental friendliness and energy efficiency. The challenge in this field is how to obtain the magnetic materials with large magnetic entropy excellent thermal conductivity. In this work, we introduce our research progress in the magnetocaloric effect of high-nuclearity 4f and 3d-4f metal clusters, which includes in, 1) How to efficiently construct high--nuclearity 4f and 3d- 4f metal clusters;2-8 2) How to efficiently understand the magnetic interaction in the system of high--nuclearity 4f and 3d-4f metal clusters;9,10 and 3) how to improve the magnetocaloric effect of the high--nuclearity 4f and 3d-4f metal clusters. References 1. Y. Z. Zheng, G. J. Zhou, Z. P. Zheng, R. E. P. Winpenny, Chem. Soc. Rev., 2014, 43, 1462. 2. X. J. Kong, Y. P. Ren, L. S. Long, Z. P. Zheng, R. B. Huang, L. S. Zheng, J. Am. Chem. Soc. 2007, 129, 7016. 3. X. J. Kong, Y. P. Ren, W. X. Chen, L. S. Long, Z. P. Zheng, R. B. Huang, L. S. Zheng, Angew. Chem. Int. Ed. 2008, 47, 2398. 4. X. J. Kong, L. S. Long, R. B. Huang, L. S. Zheng, T. D. Harris, Z. P. Zheng, Chem. Commun. 2009, 4354. 5. X. J. Kong, L. S. Long, Z. P. Zheng, R. B. Huang, L. S. Zheng, Acc. Chem. Res. 2010, 43, 201 6. J. B. Peng, Y. P. Ren, X. J. Kong, L. S. Long, R. B. Huang, L. S. Zheng, Z. P. Zheng, Angew. Chem. Int. Ed. 2011, 50, 10649. 7. J. B. Peng, Q. C. Zhang, Y. Z. Zheng, X. J. Kong, Y. P. Ren, L. S. Long, R. B. Huang, L. S. Zheng, Z. P. Zheng, J. Am. Chem. Soc. 2012, 134, 3314. 8. J. B. Peng, X. J. Kong, Q. C. Zhang, M. Orendac, J. Prokleska, Y. P. Ren, L. S. Long, Z. P. Zheng, L. S. Zheng, J. Am. Chem. Soc. 2014, 136, 17938. 9. D. P. Liu, X. P. Lin, H. Zhang, X. Y. Zheng, G. L. Zhuang, X. J. Kong, L. S. Long, L. S. Zheng, Angew. Chem. Int. Ed. 2016, 55, 4532. 10. X. Y. Zheng, H. Zhang, Y. Z. Han, M. H. Du, R. J. Wei, X. J. Kong, G. L. Zhuang, L. S. Long, L. S. Zheng, J. Am. Chem. Soc. 2017, revised. 97 Making the transition from amides to phosphines: a comparative metallation study Blair, V1, Stevens, M1, Border, E1, Thompson C.1 1Monash University, Melbourne, Australia Allyl amines and their metallations have been studied in great detail over the last decade, leading to facile anion rearrangements, unusual reaction pathways and addition reactions.1 In contrast, there has been limited research on the equivalent allyl phosphine complexes. Recently, we have shown the importance of the Lewis base choice in lithium mediated metallation and bond cleavage reactions of allyl phosphine and allyl amines.2 Here we extend this study further, reporting the alkali metal and mixed metal reactions of various allyl phosphines including; allyldiphenylphosphine (ADPP), diallylphenylphosphine (DAPP) and methallyldiphenylphosphine (MADPP) with a range of Lewis donors. Both mono- and di-lithiations of theses phosphines have lead to a variety of new species being isolated resulting from anion rearrangements. Where possible the analogous allyl amines have also been investigated with both the contrasting structural and solution state chemistry investigated. Figure 1 Mono‐ and di‐lithiation of two allyl phosphine complexes 1. E. C. Border, M. Koutsaplis, P. C. Andrews, Organometallics, 2016, 35, 303; P. C. Andrews, V. L. Blair, M. Koutsaplis and C. D. Thompson, Organometallics, 2012, 31, 8135–8144; S. G. Davies, A. D. Smith and P. D. Price, Tetrahedron Asymmetry, 2005, 16, 2833–2891; 2. V. L. Blair, M. A. Stevens, C. D. Thompson, Chem Commun., 2016, 52, 8111. 98 Metal Complexes Designed To Assist In Diagnosis Of Alzheimer’s Disease Lachlan E. McInnes, Asif Noor, Benjamin Spyrou and Paul S. Donnelly* Presenting author’s e-mail: [email protected] School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, Melbourne, Victoria, 3010, Australia Alzheimer’s disease is the most common form of neurodegenerative dementia. The disease is associated with the deposition of extracellular amyloid plaques and the formation of intracellular tau-enriched neurofibrillary tangles in the brain. Radioactive isotopes of copper and technetium are of interest in the development of new molecular diagnostic agents. Incorporation of these radioisotopes into appropriately designed coordination complexes can lead to some degree of specificity for diseased tissue to allow non-invasive diagnosis. Our research into the synthesis of specifically designed copper and technetium complexes that bind to amyloid- plaques and neurofibrillary tangles will be presented. Investigations into the use of copper complexes as potential therapeutics for neurodegenerative diseases will also be discussed. 99 METAL-AZOLATE FRAMEWORKS: SELECTIVE ADSORPTION AND SUPRAMOLECULAR INTERACTIONS Jie-Peng Zhang, Pei-Qin Liao, Chun-Ting He, Xiao-Ming Chen e-mail: [email protected] School of Chemistry, MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, Sun Yat-Sen University, Guangzhou 510275, China ABSTRACT TEXT Porous coordination polymers or Metal-organic frameworks (MOFs) have many useful characteristics, such as high crystallinity, high porosity, structural diversity, designable frameworks, framework flexibility, as well as unique and modifiable organic pore surface. Therefore, they exhibit promising potential applications in adsorption/separation, catalysis, and sensors, etc. Compared to other metal-ligand systems, inexpensive transition metal ions and simple azolates (e.g., imidazolates and triazolates) can be used to furnish stable porous metal-azolate frameworks (MAFs), showing interesting properties [1]. In this presentation, a series of MAFs for CO2 capture [2], hydrocarbon separation [3], and methane storage [4] will be presented, demonstrating the importance of supramolecular interactions, particularly weak hydrogen-bonding interactions, in the selective adsorption and separation. This work was supported by a 973 project of MoST and NSCF. References 1. For reviews: Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M. Chem. Rev. 2012, 112, 1001. Liao, P.-Q.; He, C.-T.; Zhou, D.-D.; Zhang, J.-P.; Chen, X.-M.; in Chemistry of Metal-Organic Frameworks, Ch 13, Ed. S. Kaskel, Wiley-VCH, 2016, pp. 309-343. 2. Liao, P.-Q. et. al., J. Am. Chem. Soc. 2012, 134, 17380. Liao, P.-Q.; et. al., Energy Environ. Sci. 2015, 8, 1011. Liao, P.-Q. et. al., Chem. Sci. 2016, 7, 6528. 3. He, C.-T., et. al., J. Am. Chem. Soc. 2015, 137, 7217; Liao, P.-Q. et. al., Nat. Commun. 2015, 6, 6350. Liao, P.-Q. et. al., Nat. Commun. 2015, 6, 8697. 4. Lin, J.-M. et. al., Angew. Chem. Int. Ed. 2016, 55, 4674. 100 Metal-dependent Thermal Stability of DNA Duplexes containing 5-Hydroxyuracil Nucleobases Takezawa, Y1, Nishiyama, K1, Shionoya, M1 Presenting author’s e-mail: [email protected] 1Department of Chemistry, Graduate School of Science, The University of Tokyo, Tokyo, Japan ABSTRACT Artificial metallo-DNA duplexes, which contain metal-mediated base pairs, have attracted increasing attention due to their high potential as DNA-based materials. A metal- mediated base pair is formed through metal coordination bonding between two ligand-type nucleobases and a metal ion. A variety of unnatural nucleobases as well as natural pyrimidine bases (i.e. T and C) have been proven to form metallo-base pairs in DNA duplexes (Chem. Lett. 2017). In this study, we have demonstrated that the 5-hydroxyuracil nucleobase (UOH), one of the oxidized cytosine derivatives, forms a metal-mediated base pair (UOH–M–UOH; M = metal ion) as well as a hydrogen-bonded base pair (UOH–A; A = adenine) (Chem. Eur. J. 2015; Inorg. Chim. Acta 2016). The UOH nucleobase possesses adjacent 4-carbonyl and 5- hydroxyl groups, which serve as a bidentate metal coordination site. When three UOH–UOH pairs were consecutively incorporated into DNA duplexes, the UOH–M–UOH base pairs were quantitatively formed in the presence of three equivalents of lanthanide ions such as GdIII. The metal-mediated base pairing increased the thermal stability of the resulting duplexes. Interestingly, a duplex possessing UOH–A base pairs was destabilized upon addition of GdIII ions. These results showed that the hybridization preference of the UOH-containing strand can be altered by metal coordination. Furthermore, the addition and removal of metal ions allowed reversible DNA strand exchange reactions induced by metal coordination to UOH nucleobases. Thus, the UOH nucleobase with a bifacial base-pairing property holds great promise as a component for metal-responsive DNA materials. 101 Metallation, Anion Exchange and Click Chemistry in a Metal Organic Framework Authors: Huxley, M.T.,1 Burgun, A.,1 Sumby, C.J.,1 Doonan, C.J.1 Presenting author’s e-mail: [email protected] 1 University of Adelaide, Adelaide, Australia ABSTRACT TEXT Metal Organic Frameworks (MOFs) have attracted intense interest as hosts for catalytically active compounds, owing to their crystallinity, porosity and exceedingly high surface areas[1]. Unlike conventional heterogenous catalysts, MOFs are generally highly crystalline and subsequently lend themselves to the precise characterisation of chemical processes occurring within the framework. Of particular interest are frameworks that can be functionalised post-synthesis with chemically active metal centres, a process deemed ‘post-synthetic metallation’ which can impart targeted, desirable chemical activity into existing frameworks[2- 4]. This presentation will outline our recent results involving the post-synthetic metallation of a MOF scaffold with a Manganese carbonyl bromide complex. By housing this N,N-chelated complex within the porous framework we are able to access and crystallographically characterise an unusual charged Mn(I) complex that is not otherwise accessible in the solid state. The porous framework allows the Mn(I) moiety to participate chemical processes including direct anion exchange and subsequent [3+2] cycloaddition azide-alkyne ‘click’ reactions. The framework retains crystallinity throughout, allowing the coordination environment of the Mn(I) complex to be elucidated via X-ray crystallography. References [1] Furukawa, H., Cordova, K.E., O'Keeffe, M. & Yaghi, O.M. Science 2013, 341, 1230444. [2] Bloch, W.M., Burgun, A., Coghlan, C.J., Lee, R., Coote, M.L., Doonan, C.J. & Sumby, C.J. Nat. Chem. 2014, 6, 906-912. [3] Burgun, A., Coghlan, C.J., Huang, D.M., Chen, W., Horike, S., Kitagawa, S., Alvino, J.F., Metha, G.F., Sumby, C.J. & Doonan, C.J. Angew. Chem. Int. Ed. 2017, accepted (doi:10.1002/anie.201611254). [4] Gonzalez, M., Oktawiec, J. & Long, J.R. Faraday Discuss. 2017, accepted (doi:10.1039/c7fd00061h). 102 METAL-ORGANIC FRAMEWORK CATALYSIS: HETEROGENISING HOMOGENEOUS CATALYSTS Burgun, A.,1 Doonan, C.J.,1 Sumby, C.J.1 Presenting author’s e-mail: [email protected] 1 University of Adelaide, Adelaide, Australia ABSTRACT TEXT Metal-organic frameworks (MOFs) are a class of crystalline materials assembled in the solid state from chemically mutable building blocks and possessing large, available surface areas and interconnected pore volumes.[1] These scaffolds facilitate the precise integration of catalytically active centres, facile diffusion of reactant and product, and the development of catalytic MOFs. Of particular interest is the ability to heterogenise known homogenous catalysts. This presentation will highlight our recent work and summarise some of our key findings with respect to MOF catalysis. The synthesis of MOFs possessing key precursors to important catalytic moieties will be discussed, as will approaches to install the active metal centres both pre- and post-MOF synthesis.[2, 3] Examples of heterogeneous catalysis will also be discussed, including hydroboration of CO2[3] and the gas phase carbonylation of alkyl halides.[4] References [1] H. Furukawa, K.E. Cordova, M. O'Keeffe, O.M. Yaghi, Science, 2013, 341, 974. [2] a) D. Rankine, A. Avellaneda, M. R. Hill, C. J. Doonan, C. J. Sumby, Chem. Comm. 2012, 48(83), 10328. b) W. M. Bloch, A. Burgun, C. J. Coghlan, R. Lee, M. L. Coote, C. J. Doonan and C. J. Sumby, Nat. Chem., 2014, 6, 906. [3] A. Burgun, R. S. Crees, M. L. Cole, C. J. Doonan and C. J. Sumby, Chem. Commun., 2014, 50, 11760. [4] A. Burgun, C. J. Coghlan, D. M. Huang, W. Chen, S. Horike, S. Kitagawa, J. F. Alvino, G. F. Metha, C. J. Sumby and C J. Doonan, Angew. Chem. Int. Ed., 2017, accepted 10/01/17. 103 METAL‐OXYGEN INTERMEDIATES in DIOXYGEN ACTIVATION CHEMISTRY Nam, Wonwoo Ewha Womans University, Seoul, Korea Dioxygen is essential in life processes, and enzymes activate dioxygen to carry out a variety of biological reactions. One primary goal in biomimetic research is to elucidate structures of reactive intermediates and mechanistic details of dioxygen activation and oxygenation reactions occurring at the active sites of enzymes, by utilizing synthetic metal- oxygen complexes. A growing class of metal-oxygen complexes, such as metal–superoxo, –peroxo, –hydroperoxo, and –oxo species, have been isolated, characterized spectroscopically, and investigated in various oxygenation reactions. During the past decade, we have been studying the chemical and physical properties of various reactive intermediates in oxygenation reactions, such as high-valent iron(IV)- and manganes(V)-oxo complexes of heme and non-heme ligands in oxo-transfer and C-H activation reactions, non-heme metal-peroxo complexes in nucleophilic reactions, and non-heme metal- superoxo complexes in electrophilic reactions. The effects of supporting and axial ligands on structural and spectroscopic properties and reactivities of metal-oxygen adducts have been extensively investigated as well. In this presentation, I will present our recent results on the synthesis and structural and spectroscopic characterization of mononuclear nonheme metal-dioxygen intermediates as well as their reactivities in electrophilic and nucleophilic oxidation reactions. 104 MIXED-ANION SEMICONDUCTOR PHOTOCATALYSTS FOR VISIBLE LIGHT INDUCED WATER SPLITTING Abe R e-mail: [email protected] 1Kyoto University, Kyoto, Japan ABSTRACT TEXT Photocatalytic water splitting using semiconductors has received much attention recently due to the potential for clean production of H2 from water utilizing solar energy [1]. Because almost half of all incident solar energy at the Earth’s surface falls in the visible region, the efficient utilization of visible light remains indispensable for realizing practical H2 production. We have developed a new type of photocatalytic water splitting system, mimicking the mechanism of photosynthesis in green plants [2-6]. Over a H2-evolving photocatalyst (HEP), photoexcited electrons reduce water to H2 and holes oxidize a reductant (Red) to an oxidant (Ox). The Ox is reduced back to the Red by photoexcited electrons over an O2-evolving photocatalyst (OEP) where the holes oxidize water to O2. This system reduces the energy required to drive each photocatalysis process, allowing visible light to be utilized more efficiently than in conventional systems. We have achieved water splitting using various HEPs, such as cation-doped SrTiO3 [3], tantalum oxynitrides (TaON or BaTaO2N) [4], and organic dyes [5], which are combined with an OEP such as tungsten oxide (WO3) or oxyhalide (Bi4NbO8Cl) [6] in the presence of a redox couple such – – 3+ 3+ as IO3 /I or Fe /Fe . The porous tantalum oxynitrides film electrode prepared on conducting substrates also showed stable O2 evolution with significantly high quantum efficiency in an aqueous solution, after loading of IrO2 or CoOx nanoparticles as a cocatalyst for water oxidation; enabling water splitting into H2 and O2 under visible light with a Pt electrode under low externally applied bias [7]. [1] R. Abe, J. Photochem. Photobiol. C: Photochemistry Reviews 2011, 11, 179. [2] R. Abe, Bull. Chem. Soc. Jpn. (Award account) 2011, 84, 1000. [3] R. Abe, K. Sayama, and H. Sugihara, J. Phys. Chem. B 2005, 109, 16052. [4] a) R. Abe, T. Takata, H. Sugihara, and K. Domen, Chem. Commun. 2005, 3829; b) M. Higashi, R. Abe, T. Takata, and K. Domen, Chem. Mater. 2009, 21, 1543; c) K. Maeda, M. Higashi, D. Lu, R. Abe, and K. Domen, J. Am. Chem. Soc. 2010, 132, 5858; d) R. Abe, M. Higashi, and K. Domen, ChemSusChem 2011, 4, 228. [5] R. Abe, K. Shinmei, N. Koumura, K. Hara, and B. Ohtani, J. Am. Chem. Soc. 2013, 135, 16872. [6] H. Fujito, H. Kunioku, D. Kato, H. Suzuki, M. Higashi, H. Kageyama, and R. Abe, J. Am. Chem. Soc. 2016, 38, 2082. [7] a) R. Abe, M. Higashi, and K. Domen, J. Am. Chem. Soc. 2010, 132, 11828; b) M. Higashi, K. Domen, and R. Abe, Energy Environ. Sci. 2011, 4, 4138; c) M. Higashi, K. Domen, and R. Abe, J. Am. Chem. Soc. 2012, 134, 6968; d) M. Higashi, K. Domen, and R. Abe, J. Am. Chem. Soc. 2013, 135, 10238; e) S. S. Gujral, N. A. Simonov, M. Higashi, X. Y. Fang, R. Abe, L. Spiccia, ACS Catal. 2016, 6, 3404. 105 Modulation of layered structures of metal carboxylate complexes by cations Shankar K1, Baruah, JB1 [email protected] 1Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781 039 Assam, India, Fax: +91-361-2690762; Ph. +91-361-2582311 Present talk will be based on self-assemblies anionic metal complexes with π-decorated ligands studied to control interlayer separation. Series of anionic self-assemblies guided by cations are characterised. These assemblies are utilised for molecular recognition. An example of varties of building blocks for layered structures is given below: NH Direction of 1D coordination polymer NH H2N 2 H2N 2 N NH Coordination polymer Mononuclear H n 2 Where H3C CH3 n = 2 en O H N taea O O O ipa n = 5 dap 2 N O O O N O Cu OH O N n = 8 dao O Cu O O O O O O N N O N O N O H3C CH3 HN N Cu O O O N O Cu O N N O O N O N O O CH3 H3C tmen py 8hqn im Mononuclear O Dinuclear N NH Direction of 1D 2 O coordination polymer NH2 O N H N N N 2 {[H3taea][Cu1.5(23pdc)3]·5H2O}n O dabco 5aqn 4aba 23pdc NH NH2 2 N H2O N N NH2 N O O N O N N H2N NH N Cu 3aba dapt 2 H N O taea ade O O O O dapt Coordination polymer (H2dapt)[Cu(23pdc)2(H2O)]·H2O O O O O N Amine (Am) O O O OH O Cu O N O OH O N O N O Cu O O O O N NH3 Cu (OAc) .H O O H2N O OH 2 2 O Mononuclear N Cu O N {(Am)x[Cu(23pdc)2]·yH2O}n O O Amine (Am) OHO 3aba Am=Hipa x=2, y=2 Am=Hpy x=2, y=5 (H 3aba)[Cu23dpc) (Haba)] ·9H O 2 2 2 2 Am=H2en x=1, y=4 Am=H8hqn x=2, y=2 Am=Hdao, x=1, y=4 Am=H2im, x=2, y=4 Am=H dabco x=2, y=5 ade Am=H2tmen, x=1, y=6 2 Dinuclear O O O O N Cu O N O N O O Am=H5aqn, x=2, y=8 O O Cu O O O O O O N N O O O O Am=H2dap, x=2, y=3 O Cu O O [H ade][CuL ]·2H O N Am=H24aba, x=2, y=4 2 2 2 O [(Am)x[Cu2(23pdc)4]·yH2O]n Interlayer separations layered structures in a systematic manner and utility in synthesis will be presented. References: 1. Krapa Shankar, J. B. Baruah ChemistrySelect (2016) 1, 3038 – 3044. 2.Krapa Shankar, A. Kirillov and J. B. Baruah Dalton Transactions (2015) 44, 14411- 14423. 106 3. Krapa Shankar, B. Das, J. B. Baruah, Eur. J. Inorg. Chem. (2013) 6147-6155. 107 2- Modulation of redox potentials of [Mn(N)(CN)4] in the solid states Ohtani, R1, Yamamoto R1, Hayami, S1 1 Kumamoto University, Kumamoto, Japan V 2- [Mn (N)(CN)4] complex shows redox behavior between Mn(V) and Mn(VI) and has been investigated as an oxidation catalyst. We focused on its flexible structure in which bond angles of NC-Mn-CN were changed depending on counter ions and solvents. Here, we investigated the relationship between its molecular structure and redox potentials through a + supra-molecular approach using [dabco-CnH2n+1] (n=15~18; dabco=1,4- diazabicyclo[2.2.2]octane) cations of which we could change carbon numbers of the alkyl chains systematically. V We synthesized four lipid assemblies, [dabco-CnH2n+1]2[Mn (N)(CN)4(H2O)]xH2O (Mndabco15~18), and carried out structural analyses of their single crystals. From the structural analyses, a water molecule coordinated to the open metal site of Mn ion. Hydrophilic parts consist of water molecules and metal complexes, and hydrophobic parts consist of dense packing of alkyl chains. We found that the coordination angles between the CN groups in the Mn complexes were different depending on the carbon numbers of the alkyl chains. CV measurements for the obtained compounds in the solid states demonstrated that they showed redox behavior between Mn(V) and Mn(VI) with respective potentials. The redox potentials decrease linearly as increasing the coordination angles of the CN ligands. We revealed that the different energies required for the structural transformations associated with the redox reactions underpin the observed correlation V 2- between the structures and their redox potentials for [Mn (N)(CN)4] complex in the solid state. [1] R. Ohtani, Y. Kitamura, Y. Hijikata, M. Nakamura, L. F. Lindoy, S. Hayami, Dalton Trans. 2017, in press. [2] R. Ohtani, M. Inukai, Y. Hijikata, T. Ogawa, M. Takenaka, M. Ohba, S. Kitagawa, Angew. Chem. Int. Ed. 2015, 54, 1139-114 108 Molecular Engineering of Organometallic Luminophores and photochromes Véronique Guerchais 1Institut des Sciences Chimiques de Rennes, UMR CNRS 6226 University of Rennes 1, Campus de Beaulieu, Rennes, France Catalytic C-H bond functionalisation, generally used for the access of fine chemicals, can be applied to the synthesis of phosphorescent and photochromic compounds. We will show that Pd-catalysed reactions allow the functionalization or the synthesis of diarylethenes (DAE) featuring different designs (normal and inverse types).1 Cyclometallated Pt(II) complexes, featuring a N^N^C- or N^C^N-coordinating ligand, are well-known for their luminescence properties. We have designed and synthesized various types of mono- and dinuclear photochromic Pt(II) complexes, where the DAE unit is incorporated on the cyclometallated or alkynyl ligand t DAE Bu normal DAE inverse DAE F tBu F6 6 N C S S N C N Pt N Pt S S Cl DAE The photochromic and optical properties of the DAE-based complexes depends on the design and on the nature of the linker group.2 [1]. K. Yuan, J. Boixel, H. Le Bozec, H. Doucet, V. Guerchais, A. Boucekkine, D. Jacquemin, Chem. Commun. 2013, 49, 7896-7898. K. Yuan, J. Boixel, A. Chantzis, D. Jacquemin, V. Guerchais, H. Doucet, Chem. Eur. J.. 2014, 20,10073-10083. [2] J. Boixel, Y. Zhu, H. Le Bozec, M. A.Benmensour, A. Boucekkine, K. M. C. Wong, A. Colombo, D. Roberto, V. Guerchais, D. Jacquemin, Chem. Commun. 2016, 52, 9833-9836. 109 Molecular Metal Wires: From Homonuclear Metal Strings to Heteronuclear Metal Strings Shie-Ming Peng Department of Chemistry, National Taiwan University, Taipei Taiwan The study of metal string complexes with 1-D transition metal frameworks began in the early 1990s. Since these complexes provide great insight into multiple metal-metal bonds, and may have potential applications as molecular wires, this field of research has grown in the past 20 years. As such, the electronic structure of the simplest trinuclear complexes, the supporting ligand systems, and single molecular conductance of metal string complexes are discussed. This review will introduce the development of this field and summarize some important results in the newly designed heteronuclear metal string complexes (HMSCs). These molecules may be of great interest in studying the nature of heterometallic electronic effects and molecular electronic applications. An Electric Wire and a Miniature Molecular Wire References 1. Ismayilov RH, Wang WZ, Lee GH, Yeh CY, Hua SA, Song Y, Rohmer MM, Bénard M, S-M Peng Angew. Chem. Int. Ed., 2011, 50, 2045-2048. 1. M-C Cheng, C-L Mai, C-Y Yeh, G-H Lee and S-M Peng Chem. Commun. 2013, 49, 7938-7940. 2. M-J Huang, S-A Hua, M-D Fu, G-C Huang, C Yin, C-H Ko, C-K Kuo, C-H Hsu, G-H Lee; K-Y Ho, C-H Wang, Y-W Yang, I-C Chen, S-M Peng, C-h Chen Chemistry-A European Journal 2014, 20(16), 4526-4531. 3. S-A Hua, M-C Cheng, C-h Chen, and S-M Peng European Journal of Inorganic Chemistry 2015, Micro Review, "From Homonuclear Metal String Complexes to Heteronuclear Metal String Complexes" 2015, 15, 2498.(Cover Picture) 4. T-C Ting, L-Y Hsu, M-J Huang, E-C Horng, H-C Lu, C-H Hsu, C-H Jiang, B-Y Jin, S-M Peng and C-h Chen Angew. Chem. Int. Ed. 2015, 54, 15734-15738. 110 MOLECULAR RECOGNITION USING DOME-LIKE DISTORTION OF ZINC(II) QUADRUPLY-FUSED PORPHYRINATO Ishizuka, T1, Saegusa, Y1, Komamura, K1, Kojima, T1 Presenting author’s e-mail: [email protected] 1 University of Tsukuba, Tsukuba, Japan Porphyrin derivatives bearing fused aromatic moieties at the periphery have been revealed to show unique optical and magnetic properties on the basis of co-planarity between the porphyrin core and the fused aromatic moieties and the resultant expansion of - conjugation circuits.1 Recently, we have reported an efficient procedure of the ZnII complex of a quadruply ring-fused porphyrin (ZnIIQFP, 1), having four fused five-membered rings at the periphery.2 Here, we report the effects of the ring fusion of the QFP ligand on the Lewis acidity of the central metal ions and molecular recognition. QFP has a rigid and rhombically distorted structure due to the ring-fusion, which results in the elongation of the bond lengths between the pyrrolic nitrogen atoms and the central metal ions.2 The elongation of the bond lengths in 1 causes remarkable increase of the Lewis acidity of the central metal ions. To confirm the high Lewis acidity, association behavior of the Zn center in 1 with coordinating solvent molecules such as pyridine was investigated by spectroscopic titration.3 As a result of axial coordination of pyridine on the ZnII center of 1, the core structure of the N5 pyridine complex of 1 (1-py) exhibits C132 N2 Zn N4 dome-like distortion.2 Using the concave surface of 1-py, molecular N3 C139 binding of fullerenes, C60 and C70, with C123 1-py as a host molecule was studied spectro-scopically to reveal that two molecules of 1-py formed a 2:1 C148 associated complex with a fullerene molecule.4 The structures of associated complexes were explicitly established by X-ray diffraction analysis (Figure). The fullerenes in the complexes were fully covered by the concave surfaces of 1-py. Figure. An ORTEP drawing for the crystal structure of a 2:1 complex, (1-py)2·C70. 1) M. Stępień, E. Gońka, M. Żyła, N. Sprutta, Chem. Rev. 2017, 117, 3479. 2) T. Ishizuka, Y. Saegusa, Y. Shiota, K. Ohtake, K. Yoshizawa, T. Kojima, Chem. Commun. 2013, 49, 5939. 3) Y. Saegusa, T. Ishizuka, K. Komamura, S. Shimizu, H. Kotani, N. Kobayashi, T. Kojima, Phys. Chem. Chem. Phys. 2015, 17, 15001. 4) Y. Saegusa, T. Ishizuka, T. Kojima, S. Mori, M. Kawano, T. Kojima, Chem. Eur. J. 2015, 21, 5302. 111 Quantum Molecular Spintronics Based on Single-Molecule Magnets: How to Increase Hysteresis Temperature Yamashita, M Tohoku University, Sendai, Japan Spintronics, based on the freedoms of the charge, spin, and orbital of the electron, is a key technology in the 21st century. Magnetic random access memory, which uses giant magnetoresistance or tunneling magnetoresitance, have several advantages over conventional systems, such as nonvolatile information storage, high operation speeds on the order of nanoseconds, high storage densities, and low power consumption. Although bulk or classical magnets composed of transition metal ions are normally used, in our study, we use single-molecule magnets (SMMs). However, the hysteresis temperatures for SMMs are still very low. To increase hysteresis temperatures, we must suppress quantum tunneling and increase the energy gaps between the ground and the first excited states for f-metal SMMs. For this purpose, we have used derivatives of double-decker bis-phthalocyaninato-Tb(III) SMMs (TbPc2). In order to suppress quantum tunneling, we have incorporated an exchange bias via intermolecular interactions among TbPc2 molecules. First, we have synthesized the clamshell type dinuclear [TbPc2]2 bridged with the dibenzyl-ethor moieties. The hysteresis temperature is 25 K. Then, we synthesized a fused dinuclear complex, [TbPc2]2, where two TbPc2 moieties are connected with benzyl group on one of the Pc ligands. In the crystals, one TbPc2 and one of a neighboring [TbPc2]2 weakly interact. Thus, the hysteresis temperature increased to 27 K. Next, we synthesized the liquid crystals of TbPc2 derivatives by introducing the long alkyl chains. A hysteresis temperature of 31 K was observed. 112 Multifunctional Magnetic Complexes Based on Redox-active Tetrathiafulvalene and Its Derivatives Jing-Lin Zuo, Hai-Ying Wang, Long Cui, Bin Chen State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China Email: [email protected] With the rapid development of electronics, information science and material science, the design and synthesis of new multifunctional molecular materials with an interplay or synergy between two or more properties have attracted increasing attention. Tetrathiafulvalene (TTF, C6H4S4), a sulfur rich -conjugated core with two reversible and easily accessible oxidation states, can act as an effective linker to construct novel functional materials. Particularly, materials possessing electrical and magnetic properties have received increasing interest due to the important applications in molecular spintronics. Electrochemically active TTF units can be used to link magnetic centers to form many interesting structures and multifunctional materials such as magnetic semiconductors or magnetic conductor._ENREF_15_ENREF_11_ENREF_14_ENREF_15_ENREF_18 In our group, different π-conjugated ligands containing tetrathiafulvalene unit are used in the assembly of multinuclear or polymeric metal complexes. Recently, several coordination polymers based on the tetra(4-pyridyl)-tetrathiafulvalene (TTF(py)4) have been studied. _ENREF_19Some of these compounds retained the redox activity of the TTF moiety. Furthermore, we exploited the TTF(py)4 ligand for the construction of new Fe(II)-based MOFs. Chemical oxidation of the frameworks via iodine doping leads to pronounced variations in these properties, demonstrating the significant potential for redox-modulated multifunctional behavior as the basis of novel molecular electronics and magnetic devices. 113 Nano/ Mesoscale ‘Soft’ Metal-Organic Frameworks: Interplay between Morphology/Size and Functionality Tapas Kumar Maji e-mail: [email protected] Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064. ABSTRACT Recently, there has been growing interest for fabrication of nanoscale porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) of different morphologies for controlling and tuning the size dependent properties.1-6 The lesser the particle size of MOFs, the smaller is the diffusion barrier and it is expected to strongly influence the catalytic activities, separation processes, sensing and sorption properties over the respective bulk MOFs. Nanoscale MOFs also show enhanced solution processability which is useful for biological applications and also for device fabrication. But in order to understand these aspects in nanoscale, the structural periodicity of bulk MOFs should be invariant even in nanoscopic dimension. This talk would try to introduce versatile morphologies in nano/mesoscale scale MOFs and their diverse applications including changeable surface area and selective adsorption, bimodal imaging, self-cleaning behavior and tunable emission for sensing and light harvesting applications.1-6 References 1) Lin, W.; Rieter, W. J.; Taylor, M. L. K. Angew Chem. Int. Ed., 2009, 48, 650 2) Sikdar, N.; Hazra, A.; Maji, T. K. Inorg. Chem., 2014, 53, 5993 3) K. Jayaramulu, Sai krishna, K.; George, S. J.; Eswaramoorthy, E.; Maji, T. K. Chem Commun., 2013, 49, 3937. 4) Suresh, V. M.; George, S. J.; Maji, T. K. Adv. Funct. Mater., 2013, 23, 5585. 5) Sutar, P., Suresh, V. M., Maji, T. K. Chem. Commun., 2015, 51, 9876. 5) Sutar, P., Maji, T. K. Chem. Commun., 2016, 52, 8055 7)Syamantak, R.; Suresh, V. M.; Maji, T. K. Chem. Sci., 2016, 7, 2251 . 114 Nanomaterials for Imaging and Therapy De Cola, L Institute de Science et d'Ingénierie Supramoléculaires (I.S.I.S.), University of Strasbourg, France and KIT, Germany Nanoparticles, porous materials and capsules are interesting nano/micro system able to entrap desired molecules and act as delivery or imaging species. They can be created using soft species such as gels or polymers or inorganic precursor to obtain particles, microporous and mesoporous silica based nanoparticles. In this talk I will focus I will shortly discuss the use of ultrasmall silicon nanoparticles for in vitro and in vivo imaging. Indeed their small size allows the elimination of the materials from the body of animals. More complex is the quantitative and fast elimination of silica-based materials. Indeed the issue related to the use of materials for therapy in living organism, is their accumulation in vital organs that often prevent their use. Recently, a new generation of breakable hybrid nanoparticles, able to response and degrade upon external stimuli (e.g. reductive agents, pH, etc.), have been developed in our group1,2. The insertion of responsive linkers in the framework of these particles, results not only in the destruction and safe excretion of the nanoparticles from the cells, but also in a faster and better delivery of the payloads. Moreover, to expand the breakability properties of this material for other purpose, the possibility to entrap proteins into a breakable silica shell has also been realized in our laboratory3. Experiments on the use of these materials for the treatment of hepatocarcinoma will be discussed. Acknowledgements: The financial support by the Helmholtz Virtual Institute Nano- Tracking (Agreement Number VH-VI-421) and the ARC project TheraCC are gratefully acknowledged. 115 NANOSPACE-SPECIFIC MOLECULAR BEHAVIORS Shionoya, M The University of Tokyo, Tokyo, Japan ABSTRACT: The behavior of molecules in nanosized confined spaces is quite different from their behavior in bulk media. Porous crystals with a well-defined nanospace have great potential to provide a specific space for molecular recognition and reactions on the inner surfaces. Recently, we have reported a single-crystalline metal–macrocycle framework (MMF) with nano-channels, formed from trinuclear Pd(II) macrocyclic complexes [1]. The inner surface of the channel pore possesses five types of enantiomerically-paired guest binding pockets in a single unit structure. This structural feature enables site- and orientation- selective binding of a wide variety of aromatic molecules and metal complexes to the pockets as well as co-encapsulation of multiple different molecules [2]. In most cases, the guest binding takes place reversibly in a crystal-to-crystal manner. Therefore, the position and orientation of the adsorbed guest molecules can be precisely described by single- crystal X-ray diffraction at the atomic resolution, which allows in situ X-ray snapshot analysis of a transient state of multi-step molecular adsorption prior to equilibrium [3]. Molecular size-specific acid-catalysed reactions [4], photo-induced olefin migration reactions, and photoredox reactions of metal complexes will be also presented. References [1] J. Am. Chem. Soc. 2012, 134, 2461. [2] Angew. Chem., Int. Ed. 2014, 53, 8310. [3] Nat. Chem. 2014, 6, 913. [4] Chem. Commun. 2016, 52, 7657. 116 Near-IR Mn(IV) spin-flips in Photosystem II Morton, J1, Cox, N1, Shen, J-Y2, Krausz, E1 e-mail: [email protected] 1 Australian National University, Canberra, Australia 2 Okayama University, Okayama, Japan Magnetic Circular Dichroism of PS II core complexes of T. vulcanus provide a powerful and direct new window on the Mn4Ca05 cluster of the Oxygen Evolving Center. MCD profiles have been determined and analysed for each of the metastable S-states of nature’s water splitting enzyme. The S1, S2 and S3 states exhibit narrow bands in the 730 nm – 850 nm spectral region. These can be unambiguously assigned to 4A->2E spin flips of the d3 configuration of Mn(IV) each species present. Spin-flip assignments are supported by measurements on model compounds such cubium+, a Mn-oxo cubane. Mn(IV) spin-flips are spin-forbidden and inherently weak. Spin-flip intensity in the cluster is induced by an exchange-coupled mechanism. The decrease in Mn(IV) spin upon optical excitation is balanced by an increase in spin of the cluster. The sign and magnitude of the MCD reflects the magnitude and direction of the cluster spin projection at each Mn(IV). 3 The energy of a spin-flip is determined by electron repulsion terms within a Mn(IV) t2g configuration. Variations of repulsion terms can be described via a nephelauxetic effect. Spin-flip energies are little affected by orbital splittings and thus report the nature of Mn(IV) 2- - coordination as by harder ( 0 ) or softer (OH , OH2, N-) ligands. The number of distinct spin-flips seen helps unambiguously determine the redox configuration of the OEC. The S2 state spin flips show g=2 saturation behaviour whilst the S3 state exhibits ~g=4 behaviour. The S1 state is determined to be weakly diamagnetic S=1 with J = -0.2 cm-1. 117 Neomycin B–cyclen conjugates and their Zn(II) complexes as RNA-binding agents Joshi, T1,2, Kong, B2, Tor, Y3, Graham, B2, Spiccia, L2 e-mail: [email protected] 1,2Helmholtz-Zentrum Dresden-Rossendorf, Dresden, Germany 2Monash University, Melbourne, Australia 3University of California, San Diego, La Jolla, California, United States Aminoglycosides are one of the most well-studied classes of naturally occurring antibacterial agents [1]. Their antibiotic activity derives from their selective binding to the bacterial ribosomal RNA Asite, which ultimately leads to disruption of protein synthesis. Unfortunately, despite exhibiting a promising antibacterial profile, the widespread use of amingolycosides has been hampered by their adverse side effects and the emergence of bacterial resistance. Herein, we present the synthesis of a series of new neomycin B conjugates featuring a polyazamacrocycle, 1,4,7,10-tetraazacyclododecane (cyclen), appended to the d-ribose ring, together with an examination of their A-site binding properties, as well as those of the corresponding Zn(II) complexes (C1–C3 and Zn(II)-C1– Zn(II)-C3). Since the high affinity of aminoglycosides for RNA is associated with the formation of complementary electrostatic interactions between protonated amine groups on the aminoglycosides and the RNA, the tethered cyclen macrocycle enhances affinity for the A-site RNA motif due to the introduction of additional ionisable amino groups [2,3]. Furthermore, in agreement with previous findings that Zn(II)-cyclen complexes form reasonably strong interactions with phosphate groups as well as the deprotonated imide groups of the nucleobases, uracil and thymine, complexation of Zn(II) by cyclen in the neomycin B conjugates serves to enhance the affinity further still by allowing the conjugates to form coordination bonds with the RNA target [2,3]. The conjugates are worthy of further investigation as potential new antibiotic agents. 118 References: [1] Y. Tor, ChemBioChem 2003, 4, 998. [2] B. Kong, T. Joshi, et al., J. Inorg. Biochem. 2016, 162, 334. [3] T. Joshi, et. al., Acc. Chem. Res. 2015, 48, 2366. 119 New Approaches to Crystalline Modular Porous Materials Kimoon Kim Center for Self-assembly and Complexity, Institute for Basic Science, Pohang, Korea and Department of Chemistry, Pohang University of Science and Technology, Pohang, Korea. In recent years, considerable efforts have been devoted to the creation of mesopores over 5 nm in metal-organic frameworks (MOFs). So far, such mesoporous MOFs are produced by several different methods including template-assisted synthesis, which often require rather elaborated synthetic procedures. Therefore, it is highly desirable to develop a simple and reliable method to produce mesoporous MOFs. Furthermore, porous materials having both micro- and mesopores are expected to be useful for many practical applications, but the synthesis of MOFs with such hierarchical pore structures in a controlled manner is still challenging. We recently reported a new approach to the synthesis of hierarchical micro- and mesoporous MOFs from microporous MOFs by a simple hydrolytic post-synthetic procedure. This method produced mesopores in the range of 3 to 20 nm in the MOF while maintaining the original microporous structure, at least in part. The degree of micro- and mesoporosity can be controlled by adjusting the time and temperature of hydrolysis. The resulting hierarchical porous MOFs can be utilized to encapsulate nanometer-sized guests such as proteins and the enhanced stability and recyclability of an encapsulated enzyme has been demonstrated. While MOFs and covalent-organic frameworks (COFs) have been extensively studied over the last two decades, relatively little attention has been paid to organic molecular porous materials, even though they have potential benefits over extended frameworks, such as processability and easy functionalization. Recently, we reported the porphyrin boxes, rationally designed porous organic cages with a large cavity using well-defined and rigid 3-connected triangular and 4-connected square shaped building units. The organic cages have a large cavity (~2 nm in diameter) which can be modulated using different sized building units while maintaining the topology of the cages. Beside the high chemical stability in a broad pH range in aqueous media, they exhibit a high surface area and interesting gas sorption behavior in the solid state. We are currently studying other interesting properties of the new organic cages such as selective ion transport, and exploring their applications including construction of hierachical nanostructures. Most recent results on crystalline modular porous materials from our lab will be presented. 120 NEW GADOLINIUM AGENTS FOR BINARY CANCER THERAPIES Rendina, LM1, Busse, M1, Hall, AJ1, Kardashinsky, M1, Morrison, DE1, Robertson, A1, Windsor, MSA1, Aitken, JB1,2,3, de Jonge, MD2, Harris, HH4 1 School of Chemistry, The University of Sydney, Sydney, NSW, Australia. 2 Australian Synchrotron, Clayton, Victoria, Australia. 3 Institute of Materials Structure Science, KEK, Tsukuba, Ibaraki, Japan. 4 School of Chemistry and Physics, The University of Adelaide, Adelaide, SA 5005, Australia. GdIII complexes such as Magnevist® have already found extensive use in medicine as water relaxation agents to improve contrast in MRI but the therapeutic application of Gd is only in its infancy. Gd is the only f-block element which can be exploited in two cutting- edge binary cancer therapies, viz: photon activation therapy (PAT) and neutron capture therapy (NCT). In NCT, the Auger Coster-Krönig (ACK) electrons represent the main therapeutic entity derived from the thermal neutron capture reactions of the naturally- occurring and non-radioactive 157Gd isotope, which possesses the highest neutron-capture cross-section of all stable nuclides. In PAT, emission of ACK electrons from high-Z atoms can be achieved by means of X-ray photons due to the photoelectric effect and, unlike NCT, is independent of isotope. Thus, two related binary therapies for the treatment of aggressive and intractable cancers such as malignant gliomas can be considered for Gd. The most critical aspect of both NCT and PAT is the design of tumour-selective agents containing Gd which can localize in high quantities (>200 ppm) near important sub-cellular components, e.g. DNA or mitochondria. We have designed the first examples of GdIII complexes which include an arylphosphonium group for tumour-cell targeting of mitochondria. We also have demonstrated their favourably low in vitro cytotoxicity in the absence of neutrons or X-ray photons, excellent in vitro tumour selectivity, preferential localization within the mitochondria of treated cells, and a capacity to deliver remarkably high levels of Gd into human glioblastoma multiforme (T98G) tumour cells (up to 1011 Gd atoms/cell, or ca. 3000 ppm) by means of both ICP-MS analysis and synchrotron XRF quantitation. Preliminary synchrotron GdPAT experiments, the first such experiments ever conducted in Australia, have been performed at the Australian Synchrotron. The key results of this work will be presented. 121 New reactions and new reaction channels of nonheme iron oxidation catalysts Comba, P.1 Universität Heidelberg, Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Im Neuenheimer Feld 270, 69120 Heidelberg, Germany l Bispidine ligands are extremely rigid, easy to synthesize and available in a large variety. They enforce coordination geometries derived from cis-octahedral, and the two vacant coordination sites with the tetradentate ligand systems are sterically and electronically distinct; with the isomeric pentadentate ligands, the site of the oxo group is enforced by the ligand (see Figure). Coligands coordinated trans to N3 generally have strong and short bonds, those trans to N7 are more labile. Reasons are thoroughly analyzed on the basis of computational work as well as experimental structural data, thermodynamics, spectroscopy and reactivities. Implications with respect to the mechanism of formation and the structure and spin state of high valent iron oxidants are analyzed, and possibilities to tune the spin state, structure and reactivity of high valent iron complexes are discussed. Special emphasis will be on the question why different families of supporting ligands and the variation of the metal center (e.g. FeIV vs. MnIV) may lead to subtle changes in the reaction mechanism. The problem of the experimental determination and computation of accurate FeIV/III redox potentials will also be addressed, and a novel environmentally important reaction, the anaerobic formation of methane from methionine and from acetic acid will be discussed. 122 Organelle-Targeting and Microenvironment-Sensitive Anticancer Phosphorescent Metal Complexes Tan, CP1, Ji, LN1, Mao, ZW1 Presenting author’s e-mail: [email protected] 1 MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, P. R. China According to the unique characteristics of the metal complexes, we have successfully designed multi-functional anticancer metal complexes integrating imaging and therapeutic capability in a single molecule/platform. Our study is mainly focus on the following three aspects: (1) By introducing the organelle-targeting or microenvironment-sensitive groups into the structures of phosphorescent iridium complexes, we have realized real-time damaging and tracing of mitochondria/lysosomes during apoptosis/autophagy simultaneously.1‒7 The anticancer mechanisms including the impact of these complexes on mitochondrial functionalities and lysosomal integrities have been investigated in detail. (2) We have designed multifunctional metal-based anticancer agents targeting histone deacetylases incorporating phosphorescent imaging, photodynamic therapy (PDT) and subcellular targeting properties.8‒10 (3) By using a supramolecular strategy, we assemble a cyclodextrin-functionalized anticancer Ru(II) complex with a tumor-targeting peptide into discrete nanostructures that can induce tumor cell death with high selectivity.11 We use a nanohybrid composed of reduced nanographene oxide (rGO) sheet and a Ru(II) complex for combined PTT and PDT of cancer.12 In all, our study provides insights into the rational design and anticancer mechanisms of phosphorescent metal complexes. References (1) He, L, Tan, CP, Ye, RR, Zhao, YZ, Liu, YH, Zhao, Q, Ji, LN, Mao, ZW. Angew Chem Int Ed 2014, 53 (45), 12137. (2) Li, Y, Tan, CP, Zhang, W, He, L, Ji, LN, Mao, ZW. Biomaterials 2015, 39, 95. (3) He, L, Liao, SY, Tan, CP, Lu, YY, Xu, CX, Ji, LN, Mao, ZW. Chem Commun 2014, 50 (42), 5611. (4) Cao, JJ, Tan, CP, Chen, MH, Wu, N, Yao, DY, Liu, XG, Ji, LN, Mao, ZW. Chem Sci 2017, 8 (1), 631. (5) He, L, Li, Y, Tan, CP, Ye, RR, Chen, MH, Cao, JJ, Ji, LN, Mao, ZW. Chem Sci 2015, 6 (10), 5409. (6) Ye, RR, Tan, CP, Chen, MH, Hao, L, Ji, LN, Mao, ZW. Chem Eur J 2016, 22 (23), 7800. (7) Chen, MH, Wang, FX, Cao, JJ, Tan, CP, Ji, LN, Mao, ZW. ACS Appl Mater Interfaces 2017, DOI: 10.1021/acsami.7b01735. (8) Ye, RR, Ke, ZF, Tan, CP, He, L, Ji, LN, Mao, ZW. Chem Eur J 2013, 19 (31), 10160. (9) Ye, RR, Tan, CP, He, L, Chen, MH, Ji, LN, Mao, ZW. Chem Commun 2014, 50 (75), 10945. (10) Ye, RR, Tan, CP, Lin, YN, Ji, LN, Mao, ZW. Chem Commun 2015, 51 (39), 8353. (11) Xue, SS, Tan, CP, Chen, MH, Cao, JJ, Zhang, DY, Ye, RR, Ji, LN, Mao, ZW. Chem Commun 2017, 53 (5), 842. (12) Zhang, DY, Zheng, Y, Tan, CP, Sun, JH, Zhang, W, Ji, LN, Mao, ZW. ACS Appl Mater Interfaces 2017, 9 (8), 6767. 123 Organometallic Dendrimer with Zinc(II) Porphyrin Core for Optics PAUL-ROTH, C. O. e-mail: [email protected] INSA-ISCR-UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes cedex, France In 2004, we synthesised a porphyrin possessing four fluorenyl arms (TFP) presenting a remarkably high fluorescence quantum yield. To exploit this fluorescence, a series of pure organic porphyrin dendrimers based on TPP porphyrin core and bearing fluorenyl dendrons as light harvesting antennaes were prepared [1]. In parallel, porphyrin organic cores bearing ruthenium or iron peripheral donor groups appended at the meso positions have also been synthesized in our group. Once metallated, these assemblies are composed of a zinc porphyrin ZnTPP heart surrounded by a metallic crown of redox-active Fe(II) or Ru(II) acetylide complexes as peripheral substituents [2]. Their effective two- photon absorption (TPA) cross-sections have been measured by Z-scan. More generally, these molecular assemblies exhibit particularly strong cubic NLO activities compared to all- organic analogues of the same size [2]. To exploit these results further, polymetallic analogues have been designed, synthesized, characterized and their NLO response was measured [3]. We will notably report the synthesis from a dodecaruthenium assembly, its spectroscopic characterization, and the investigation of its cubic NLO properties [4]. References: [1] C. Paul-Roth, G. Williams, J. Letessier, G. Simonneaux Tetrahedron Lett. 2007, 48, 4317 [2] S. Drouet, A. Merhi, G. Grelaud, M.P. Cifuentes, M.G. Humphrey, K. Matczyszyn, M. Samoc, L. Toupet, C.O. Paul-Roth, F. Paul, New J. Chem., 2012 36, 2192; S. Drouet, A. Merhi, D. Yao, M.P. Cifuentes, M.G. Humphrey, M. Wieglus, J. Olesiak-Banska, K. Matczyszyn, M. Samoc, F. Paul, C.O. Paul-Roth, Tetrahedron 2012 68,10351. [3] Merhi, A.; Grelaud, G.; Ripoche, N.; Barlow, A.; Cifuentes, M. P.; Humphrey, M. G.; Paul, F.; Paul-Roth, C.O. Polyhedron 2015, 86, 64. [4] Merhi, A.; Grelaud, G.; Green, K. A.; Barlow, A.; Wang, G.; Minh, N. H.; Reynolds, M.; Ledoux, I.; Cifuentes, M. P.; Humphrey, M. G.; Paul, F.; Paul-Roth, C. O. Dalton Trans. 2015, 44, 7748. 124 ORGANOMETALLIC TRIARYL ISOCYANURATES WITH PERIPHERAL METAL ALKYNYLS SUBSTITUENTS: SYNTHESIS AND THIRD-ORDER NLO PROPERTIES Paul, F. Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, University of Rennes 1, Rennes, France Octupolar molecules with three-fold rotational symmetry (D3h, C3v or D3) have attracted sustained interest in the field of nonlinear optics (NLO) due to their potentially large second-order nonlinearities.1 More recently, it has been argued that such symmetries were also beneficial to third-order NLO properties such as multiphotonic absorption.2 To challenge this assertion, we will report the synthesis of several organometallic derivatives of that kind presenting various metal alkynyl endgroups at their periphery,3 disclose their redox properties when relevant, and measure their linear and nonlinear optical properties. Some key structure-property relationships will also be delineated. Finally, focussing on third-order NLO properties, some facets of the applied potential of such organometallic assemblies will be briefly presented. References 1. Zyss, J. Ledoux, I. Chem. Rev. 94 (1994) 77. 2. B.R. Cho et al., J. Am. Chem. Chem. 123 (2001), 10039. 3. Argouarch, G. et al., Chem. Eur. J. 18 (2012), 11811. 4. Trujillo, A. et al., Dalton Trans. 41 (2012), 7454. 125 Osmium(VI) Nitrido Complexes as Potent Anticancer Agents Wen-Xiu Ni1, Peng-Chao Ji1, Tai-Chu Lau2 E-mail: [email protected] 1 Shantou University Medical College, Guangdong 515041, PR China 2 Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China. Since the discovery of the anticancer properties of cisplatin and its derivatives, research on metallopharmaceuticals has received considerable interest. Besides platinum, complexes of gold, titanium and ruthenium have been reported to exhibit promising anticancer activities. In contrast, the anticancer properties of osmium complexes are newly developed. We have synthesized a high-valent osmium bearing tridentate Schiff-base ligand complexes through making use of a nitrido ligand to stabilize the osmium ion in the +VI oxidation state. [1] As expected, these complexes show significant in vitro antiproliferative activity against some human cancer cell lines. The results of cell cycle modification and apoptosis induction indicate that some of osmium(VI) complexes exhibit effective cell growth inhibition and inducing apoptosis. Preliminary in vivo study shows that VI nitridoosmium(VI) complex [Os (N)(sap)(OH2)Cl] (H2sap = N-salicylidene-2-aminophenol) (Figure 1) is active in suppressing tumor growth in a nude mice model for 30 days suppressed (48.2%) tumor growth when compared with that of the PET control. Because Hazole ligands are commonly present in metal complexes that show good antiproliferative activity, we also incorporated these ligands into the OsVIN platform. Complexes with pyrazole derivatives were found to possess significant in vitro cytotoxicity. Further studies indicate that they induce S phase arrest in cancer cells followed by apoptosis, possibly as a result of binding with DNA. [2] These results suggested that the OsVIN platform may be a promising platform for designing new anti-cancer drugs. VI Figure 1 The structure of nitridoosmium(VI) complex [Os (N)(sap)(OH2)Cl] (left), in vivo anticancer evaluation in nude mice model (right). References [1] W.-X. Ni, W.-L. Man, M. T.-W. Cheung, R. W.-Y. Sun, Y.-L. Shu, Y.-W. Lam, C.-M. Che and T.- C. Lau, Chem. Commun., 2011, 47, 2140. [2] W.-X. Ni, W.-L. Man, S.-M. Yiu, M. Ho, M. T.-W. Cheung, C.-C. Ko, C.-M. Che, Y.-W. Lam and T.-C. Lau, Chem. Sci., 2012, 3, 1582. 126 Pd(III)-Br Chain Complexes with High Conductivity and Thermal Stability Mian, M1, Iguchi, H1, Takaishi, S1, Okamoto, H2, Tanaka, H3, Kuroda, S3, Yamashita, M1 Presenting author’s e-mail: [email protected] 1 Tohoku University, Sendai, Japan 2 The University of Tokyo, Tokyo, Japan 3 Nagoya University, Nagoya, Japan ABSTRACT One-dimensional electron system has attracted much attention in both applied and basic sciences due to its unique conducting and optical properties which depend strongly on the oxidation state of metal. For example, gigantic third-order nonlinearities1 and ultrafast optical switching2 has been discovered so far in Ni(III) chain complexes. Recently we have successfully synthesized bromine-bridged Pd(III) chain complexes by using chemical pressure.3 However, their low crystallinity and fragility prevents to study their electronic states and to realize intrinsic unique properties. Therefore, a new synthetic strategy is necessary. In this work, we have focused on investigation of unique electronic properties of bromide- bridged Pd chain complex (Pd-Br chain) with uncommon Pd(III) oxidation state. A new strategy (multiple hydrogen-bond approach) was applied to synthesize Pd-Br chain. [Pd(dabdOH)2Br]Br2 (1), [Pd(dabdOH)2Br]SO4·3H2O (2) (dabdOH = (2S,3S)-2,3- diaminobutane-1,4-diol), containing additional hydrogen bonds between hydroxy group in the in-plane ligand and Br– counteranion. This approach strengthens the hydrogen-bond network among the Pd-Br chains and achieve (i) shortest Pd–Br–Pd distance of all reported Pd-Br chains, which stabilizes Pd(III) oxidation state up to decomposition temperature (443 K for 1); (ii) high electrical conductivity (3-38 S cm-1 for 1 and 0.01 S cm-1 for 2 at RT), making 1 one of the most conducting 1D coordination polymers; (iii) high crystallinity and robustness suitable for optical and physical property measurements. 1. Kishida et al., Nature 2000, 405, 929. 2. Tao et al., Adv Mater. 2007, 19, 2707. 3. S. Takaishi et al., J. Am. Chem. Soc. 2008, 130, 12080. 127 PENTANUCLEAR IRON CATALYSTS FOR WATER OXIDATION Okamura, M1,2, Kondo, M1,3, Masaoka, S1 Presenting author’s e-mail: [email protected] 1 Institute for Molecular Science, Okazaki, Japan 2 Nagoya University, Nagoya, Japan 3 JST ACT-C, Saitama, Japan + – Water oxidation (2H2O → O2 + 4H + 4e ) is considered the main bottleneck in the production of chemical fuels from sunlight and/or electricity. In nature, the oxidation of water is efficiently catalysed by the oxygen-evolving complex (OEC) in photosystem II (PSII). Because extraction of the OEC is extremely difficult, various synthetic molecular catalysts have been investigated over the last decades. However, the development of efficient, robust and abundant metal-based molecular catalysts remains a challenge. In this work, we show a water oxidation reaction catalysed by a pentanuclear iron complex. Electrochemical analysis revealed that the pentairon complex exhibits rich redox flexibility II III III with six different oxidation states between Fe 5 and Fe 5, in which the Fe 5 state is the active species for oxidising water. A computational investigation indicated that the O-O II III IV bond formation proceeds from the mixed-valence Fe 2Fe (Fe =O)2 intermediate with a reaction barrier of less than 10 kcal mol–1. The turnover frequency of the water oxidation catalyst was determined to be 1,900 s–1, which is considerably greater than that of the OEC (100-400 s–1). Our findings indicate that efficient water oxidation catalysts can be created based on multinuclear iron complexes with redox flexibility and adjacent water-activation sites. (1) M. Okamura, M. Kondo, R. Kuga, Y. Kurashige, T. Yanai, S. Hayami, V. K. K. Praneeth, M. Yoshida, K. Yoneda, S. Kawata, S. Masaoka, Nature, 2016, 530, 465– 468. (2) M. Kondo, S. Masaoka, Chem. Lett. [Highlight Review], 2016, 45, 1220-1231. 128 PHOSPHINE COMPLEXES CATALYSED ASYMMETRIC P-H AND As-H ADDITION REACTIONS LEUNG P. H. Nanyang Technological University, Singapore A chiral PC-cyclometalated palladium complex (R-1) is an efficient catalyst for the asymmetric hydrophosphination reactions of achiral chalcones. For example, it facilitates the large scale synthesis of the chiral bulky PCP-pincer ligand (S,S-2) via a “double” P-H addition reaction on the same di-chalcone substituted substrate. Subsequently, the optically pure (S,S-2) pincer ligand is able to form highly stable complexes with Ni(II), Pd(II) and Pt(II). These readily available chiral pincer metal complexes are also found to be efficient catalyst for similar P-H and the novel As-H addition reactions. However, the PC- and PCP-complexes show very different reactivity and chemo-selectivity. For example, when (R-1) was used as the catalyst, addition of the P-H bond to α,β,γ,δ-unsaturated malonate ester gave the 1,4-addition product exclusively. When the same reaction was catalysed by (Pd-S,S-2), the sole 1,6-addition product was generated. Similarly, only (Ni- S,S-2) is able to catalyze the analogous As-H addition reaction in high yields with high ee. Both (R-1), (Pd-S,S-2) and (Pt-S,S-2) could not activated the hydroarsination reaction efficiently. The catalyst-product specificity is due to the fact that these catalysts operate via different reaction mechanisms. The stereo-electronic features of (R-1) and (M-S,S-2) and their catalytic applications will be discussed in this seminar. 129 Photochemical Hydrogen Evolution Based on Metal Complexes Bearing Redox- active Ligands Matsumoto, T.1,2 and Chang, H.-C.1 Presenting author’s e-mail: [email protected] 1Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan 2 Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 4‐1‐8 Honcho, Kawaguchi, Saitama 332‐0012, Japan Abstract Molecular hydrogen is one of candidates as clean energy carrier.1 Because of the difficulty in the storage and transportation of hydrogen, the development of hydrogen- storage/-evolution materials is strongly desired. Among a several materials, organic compounds, known as organic hydrides, are fascinating candidate. Recently, quinoline/1,2,3,4-tetrahydroquinoline system was reported as efficient hydrogen-storage/- evolution material that can evolve hydrogen at relatively low temperatures (ca. 110-140 °C), under the presence of Ir-catalyst.2 However, even in the excellent example, the operating temperature in the hydrogen-evolution reaction (HER) is still high. Therefore, the creation of a HER operable at moderate temperature with use of nonprecious-metal catalysts is an important issue. Recently, we reported interesting and important reactions of transition metal complexes with redox-active ligands.3 For example, Fe(II) complex with o-phenylenediamine (opda), II [Fe (opda)3](ClO4)2, was reported to show the photochemical HER at room temperature (Fig. 1).4 In this reaction, the protons and electrons in opda ligand were found to be the source of photochemically evolved hydrogen. These results indicate the possibility for creation of novel hydrogen storage materials operable under room temperature based on the nonprecious metal-based complexes with redox-active ligands. Here, we report the photochemical reaction of Fe(II) complex with redox-active ligand bearing heteroleptic coordination sites via one amino and the deprotonated hydroxyl group, o-aminophenolato (apH–)(Fig. 1). By the photoreaction of the complex in MeOH, the light- driven MeOH dehydrogenation under room temperature could be observed, and the detailed investigation on the elucidation of reaction mechanism, including photochemical hydrogen radical generation, will be presented.5 References [1] K. Mazloomi, et al., Renew. Sust. Energ. Rev. 2012, 16, 3024. [2] R. Yamaguchi, K.-i. Fujita, et al., J. Am. Chem. Soc. 2009, 131, 8410. [3] T. Matsumoto, H.-C. Chang, et al., (a) Inorg. Chem. 2011, 50, 2859. (b) Dalton Trans. 2012, 41, 8303. (c) Bull. Chem. Soc. Jpn. 2015, 88, 74. (d) Chem. Lett. 2017, 46, 232. [4] T. Matsumoto, H.-C. Chang, et al., J. Am. Chem. Soc. 2013, 41, 8646. [5] M. Wakizaka, T. Matsumoto, R. Tanaka, H.-C. Chang, Nat. Commun. 2016, 7, 12333. 130 Photofunctional bis(dipyrrinato)zinc(II) coordination nanosheets Sakamoto, R1,2, Nishihara, H1 [email protected] 1 The University of Tokyo, Tokyo, Japan 2 JST-PRESTO, Saitama, Japan Two-dimensional polymeric nanosheets have recently gained much attention, particularly top-down nanosheets such as graphene and metal chalcogenides originating from bulk- layered mother materials. Although molecule-based bottom-up nanosheets manufactured directly from molecular components can exhibit greater structural diversity than top-down nanosheets, the bottom-up nanosheets reported thus far lack useful functionalities. Here we show the design and synthesis of a bottom-up nanosheet featuring a photoactive bis(dipyrrinato)zinc(II) complex motif. A liquid/liquid interfacial synthesis between a three- way dipyrrin ligand and zinc(II) ions results in a multi-layer nanosheet, whereas an air/liquid interfacial reaction produces a single-layer or few-layer nanosheet with domain sizes of >10 μm on one side. The bis(dipyrrinato)zinc(II) metal complex nanosheet is easy to deposit on various substrates using the Langmuir–Schäfer process. The nanosheet deposited on a transparent SnO2 electrode functions as a photoanode in a photoelectric conversion system, and is thus the first photofunctional bottom-up nanosheet.[1] [1] Nature Commun. 2015, 6, 6713; Angew. Chem. Int. Ed. 2017, 56, 3526. 131 PHOTOFUNCTIONAL TRANSITION METAL COMPLEXES AS INTRACELLULAR SENSORS AND BIOORTHOGONAL PROBES Lo, K. K.-W. E-mail: [email protected] Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Hong Kong, P. R. China ABSTRACT The coordination of functional ligands to d-block elements results in transition metal complexes with new and useful properties. We are particularly interested in the photophysical and photochemical characteristics of photoactive transition metal polypyridine complexes because they offer new opportunities for the development of innovative diagnostic and therapeutic reagents. Of particular importance is the environment-sensitive luminescence and photoactivatable properties of these metal complexes. In this presentation, we will describe our design of luminescent rhenium(I), ruthenium(II), and iridium(III) polypyridine complexes as intracellular sensors for small molecular targets, photocytotoxic agents, and phosphorogenic bioorthogonal probes for specific labeling and staining of live cells. We will focus on the photophysical and photochemical properties, cytotoxic activity, cellular uptake behavior, and intracellular functions of these photofunctional transition metal complexes. REFERENCES 1. Lo, K. K.-W. Acc. Chem. Res. 2015, 48, 2985. 2. Lee, L. C.-C.; Lau, J. C.-W.; Liu, H.-W.; Lo, K. K.-W. Angew. Chem. Int. Ed. 2016, 55, 1046. 3. Tso, K. K.-S.; Leung, K.-K.; Liu, H.-W.; Lo, K. K.-W. Chem. Commun. 2016, 52, 4557. 132 PHOTOPOLYMERIZATION UNDER VISIBLE LIGHT: TADF COMPLEXES AS NEW PHOTOINITIATORS Dumur, F1, Lalevée, J2, Gigmes, D1 1 Aix Marseille Univ., CNRS, Institut de Chimie Radicalaire, UMR 7273, F-13397 Marseille, France 2 Institut de Science des Matériaux de Mulhouse IS2M – UMR CNRS 7361 – UHA, 15, rue Jean Starcky, 68057 Mulhouse Cedex, France Considering the serious environmental pollution and energy crisis resulted from human activities, light-activated chemical reactions are of critical importance for the sustainable development of mankind. In this regard, photocatalysis has attracted great interest and researchers from academia, industry, and government research laboratories have made remarkable progress in this field, including solar fuels (CO2 capture, water splitting, etc.), pollutants degradation, and chemical synthesis. Recently, the concept of visible-light photoredox catalysis has been successfully adopted in polymer synthesis upon soft conditions. Organometallic compounds with excellent photochemical properties (e.g. strong visible light absorption, long excited state lifetimes) have a great potential as photoinitiators for free-radical initiated [(meth)acrylates)] and cation initiated (epoxides or vinyl ethers) polymerizations. Over the years, a series of ruthenium-, iridium-, zinc-, or copper-based complexes have been successfully developed and applied as photoinitiators. However, the search of photocatalysts based on low-cost and none-toxic metals and allowing efficient polymerization reactions at low concentrations in the photocurable formulation remains today highly interesting and challenging. Since 2012 and the impressive works of Chihaya Adachi on Thermally Activated Delayed Fluorescence (TADF) materials, this new family of luminescent materials has been the focus of numerous research. Herein, we present unprecedented works of TADF metal complexes used as photoinitiators of polymerization. These results pave the way towards the development of third generation visible-light photoinitiators operating under soft irradiation conditions. 133 -ELECTRON QUANTUM MAGNETISM IN IONIC POLYAROMATIC HYDROCARBONS Prassides, K WPI-AIMR, Tohoku University, Sendai, Japan Molecular solids whose cooperative electronic properties are based purely on -electrons from carbon atoms offer a fertile ground in the search for exotic states of matter, including unconventional superconductivity and quantum magnetism. The field was ignited by reports of high-temperature superconductivity in materials obtained by reaction of alkali metals with polyaromatic hydrocarbons (PAHs) such as phenanthrene and picene. However, despite the flare of experimental and theoretical activity, the results have not been reproduced and the identities of all compounds in this family have remained unknown, reflecting the unavailability of phase-pure samples. Recently we have been successful in devising new reproducible synthetic routes of ionic salts of PAHs under mild conditions that avoid the competing decomposition of PAH molecules at high temperature. As a result, highly-crystalline single-phase materials with variable oxidation states of reduced PAHs such as phenanthrene, pentacene and picene are now available for structural and electronic characterization for the first time [1,2]. Prominent among these are the multi-orbital strongly-correlated Mott insulating binary phenanthrene salts, Cs(C14H10) and Cs2(C14H10). Whereas Cs2(C14H10) is diamagnetic due to orbital polarisation, Cs(C14H10) is a Heisenberg antiferromagnet with a gapped spin-liquid state emerging from the highly-frustrated -chain magnetic topology of coupled alternating-exchange spiral • tubes of S=½ (C14H10) radical anions. The absence of long-range magnetic order renders the compound an excellent candidate of a spin-½ quantum spin liquid arising purely from carbon -electrons. [1] Y. Takabayashi et al., Nature Chem. 2017, in press. [2] F.D. Romero et al., Nature Chem. 2017, in press. 134 POLYARYLCYCLOPENTADIENYL-LANTHANOID COMPLEXES – SYNTHETIC CHALLENGES Deacon, G.B.1, Jaroschik, F.2, Junk, P.C.3, Kelly, R.P.4 1 School of Chemistry, Monash University, Clayton, Victoria 3800, Australia 2 Institut de Chimie Moleculaire de Reims, CNRS 1312, Université de Reims, France 3 College of Science, Technology & Engineering, James Cook University, Townsville, Qld 4811, Australia 4 ISIC, Ecole Polytechnique de Lausanne, 1015 Lausanne, Switzerland ABSTRACt The preparation and characterization of bis(pentaphenyl)lanthanoid metallocenes present major problems owing to the low solubility of the compounds and the ready formation of the ’ C5Ph5 radical. A number of approaches have enabled a rich and attractive chemistry to be uncovered. These include: 1. Use of half-sandwich compounds which are more soluble [1] 2. Use of 4-butylphenyl substituents to provide solubility [2] 3. Dissolution as solvent separated ion pairs and deposition by desolvation [3] e.g. Yb(C5Ph5)2 + 6thf [Yb(thf)6][C5Ph5]2 4. Use of the tetraphenylcyclopentadienyl ligand which gives more soluble metallocenes [4] Examples of these approaches are discussed together with the structures of the resulting products. 1. C.M Forsyth et al, Chem. Commun., 2006, 1003. 2. S. Harder et al, Angew. Chem. Int. Ed., 2008, 47, 2121. 3. G.B. Deacon et al, Organometallics, 2008, 27, 4772. 4. G.B. Deacon et al, Organometallics, 2015, 34, 2369; G.B. Deacon et al, Chem. Commun., 2014, 50, 10655; R.P. Kelly et al, Organometallics, 2015, 34, 5624. 135 POLYMORPHISM, INTERPENETRATION AND SUPRAMOLECULAR ISOMERISM – A PERSONAL PERSPECTIVE Park, I-H., 1 Lee, S.S.,1 VITTAL, J.J.,2 Presenting author’s e-mail: [email protected] 1Department of Chemistry, Gyeongsang National University, Jinju-52828, South Korea, 2Department of Chemistry, National University of Singapore, 117543, Singapore ABSTRACT TEXT If a compound exists in more than one crystal structures for a given molecular formula, it is called polymorphism. Polymorphism is widespread in organic solids and extended inorganic structures, but rare in coordination polymers (CPs) and metal-organic frameworks (MOFs). However, when the same repeating unit is connected in different ways to produce different topologies, it has been termed as supramolecular isomerism. The well-known concept of isomerism in coordination complexes and organic molecules has been extended to CPs. Examples like conformational supramolecular isomerism, structural supramolecular isomerism and supramolecular isomerism catenane are known in the literature. Nonetheless new types of supramolecular isomers akin to coordination complexes and organic molecules are yet to be discovered. Likewise, interpenetration is also a common occurrence in MOFs and CPs, which are closely related to both polymorphism and supramolecular isomerism. Recently we have encountered several solid state structural variations in the CPs and MOFs for the same building block and molecular formula. Classification and terminology for such solid state structures become challenging. A number of such cases that we encountered in our laboratory will be presented in this talk. References (1) Moulton, B.; Zawarotko, Chem. Rev. 2001, 101, 1629. (2) Robin, A.Y.; Fromm, K.M. Coord. Chem. Rev. 2006, 250, 2127. (3) Hennigar, T. L.; MacQuarrie, D. C.; Losier, P.; Rogers, R. D.; Zaworotko, M. J. Angew. Chem., Int. Ed. Engl. 1997, 36, 972. (4) Desiraju, G.R.; Vittal, J.J.; Ramanan, A. Crystal Engineering – A Textbook, World Scientific Publishers, Singapore, 2011. 136 POLYOXOMETALTES AS ARTIFICIAL PROTEASES Parac-Vogt, T.N., Ly, H.G. T., Sap, A., Quanten, T., Vandebroek, L. Presenting author’s e-mail: [email protected] KU Leuven, Department of Chemistry, 3001 Leuven, Belgium. Selective cleavage of proteins is one of the most required and most important procedures in biochemical and bioengineering practice. However, the extreme kinetic inertness of the peptide bond, with a half-life estimated up to 600 years under physiological conditions, makes this a challenging task. We have recently reported on a conceptually new way of achieving selective cleavage of proteins by combining the enzyme-like molecular recognition ability of a polyoxometalate (POM) scaffold with the hydrolytic activity of a strong Lewis acid metal cation imbedded into the POM structure. In our approach the POM acts as a ligand for the Zr(IV) ion, and due to its three-dimensional shape and negative charge it also induces the selectivity that is necessary for a controlled fragmentation of the polypeptide backbone. Zr(IV)-substituted POMs were proven to be catalytically active towards the hydrolysis of the highly inert amide bond in dipeptides and oligopeptides. More importantly, these POMs were shown to display unprecedented hydrolytic activity and selectivity towards a range of different proteins, including insulin chain B, lysozyme, myoglobin and albumins. The hydrolysis occurs at peptide bonds which are located either at clearly defined positive patches that are able to accommodate the POM ligand, or on the interface of positive surface zones containing negatively charged Asp or Glu residues that allow for additional anchoring of Zr(IV). A range of biophysical and spectroscopic techniques has been applied in order to elucidate the molecular interactions between POMs and proteins under investigation. 137 POROUS METAL-ORGANIC FRAMEWORKS WITH ENHANCED GAS UPTAKE AND LUMINESCENCE PROPERTIES Fedin, V.P. [email protected] Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia Selective gas adsorption properties and detection of small organic molecules are among the most valuable properties of metal-organic framework (MOF) based materials. Here we describe our recent results on synthesis, structural characterization and investigation of functional properties for two types of novel metal-organic frameworks. Isoreticular porous MOFs based on Zn2–paddle wheels, connected through thiophenedicarboxylates and N-donor linkers [Zn2(tdc)2L] are very similar to the prototypic terephthalate [Zn2(bdc)2dabco]. However, the substitution of benzene to thiophene linker substantially increases the carbon dioxide adsorption as well as CO2/N2 adsorption selectivity. The CO2 uptake on [Zn2(tdc)2dabco] approaches the best values reported in the literature although this compound possesses no basic amine functions nor open metal sites, which is manifested by a low isosteric heat of adsorption. The quantum chemical calculations confirm the definitive role of heterocycles and, particularly, sulfur atoms in CO2 binding via induced dipole interactions. Substitution of both pyridine and pivalate ligands in the molecular complex 2– [Li2Zn2(piv)6(py)2] with bpy and terephthalate bridges (R-bdc , R = H, Br, NH2, NO2) results in isoreticular porous frameworks [Li2Zn2(R-bdc)3(bpy)]. The introduction of different substituents R onto the terephthalate linkers affects the free volume of the porous compounds and the N2 adsorption behavior. The CH4 and CO2 adsorption and relative selectivities have been investigated in detail, and interestingly, a fascinating interplay of luminescence properties with wavelength of excitation and nature of the host aromatic guest molecules has been observed. Our work was supported by the Russian Science Foundation (Grant No. 14-23-00013). 138 Porous Molecular Magnets Miyasaka, H Tohoku University, Sendai, Japan The design of multiply sensing materials whose intrinsic nature is variable/tunable mutually by chemical and physical external stimuli is a pivotal challenge in the field of materials science. A class of metal-organic frameworks (MOFs) composed of electron-donors (D) and/or –acceptors (A): we call this group “D/A-MOFs”, is one of the favorable candidates [1]. Since the charge transfer (CT) and electron transfer (ET) of D0A0 ↔ D+A– could be rationally controlled by tuning the ionization potential of D and the electron affinity of A, they are intriguing targets for functional materials with magnetic, conducting, and their synergistic properties, as well as their porous nature for gas/solvent sorption or ionic transportation. We have designed such materials in the combinations of paddlewheel-type II,II diruthenium(II, II) complexes ([Ru2 ]) as D and TCNQ or DCNQI derivatives as A, and demonstrated the rational control of CT/ET on D/A-frameworks to obtain electronic and magnetic functionalities [1-11]. Among the series, most of D2A compounds provide layered systems containing crystallization solvents or void space between layers. A class of neutral layered D2A systems preventing to undergo electron transfer is only paramagnetic [3]. 0.5+ – Meanwhile, one-electron transferred D2A systems, i.e., D 2A , allowed to be magnets [3- 6], but many of layered D2A compounds fall down to an antiferromagnetic ground state, because of the existence of interlayer antiferromagnetic dipole interactions [3,4], or to fluctuated magnetism due to the partial elimination of crystallization solvents from between layers [4,5]. These magnetic properties are thus strongly affected by: i) the oxidation state of layers, and ii) the structure or environment between layers. The rational design of layered systems, including post-synthetic methods that construct artificial lattices [12,13], is a key factor to create novel porous magnetic materials. [1] Miyasaka, H., Acc. Chem. Res. 2013, 46, 248. [2] Motokawa, N. et al., Angew. Chem. Int. Ed. 2008, 47, 7760. [3] Miyasaka, H. et al., J. Am. Chem. Soc. 2010, 132, 1532. [4] Motokawa, N. et al., J. Am. Chem. Soc. 2010, 132, 11943. [5] Motokawa, N. et al., CrystEngComm 2009, 11, 2121. [6] Fukunaga, H. et al., Chem. Commun. 2015, 51, 7795. [7] Miyasaka, H. et al., J. Am. Chem. Soc. 2011, 133, 5338. [8] Nakabayashi, K.; Miyasaka, H., Chem. Eur. J. 2014, 20, 5121. [9] Nakabayashi, K. et al., Inorg. Chem. 2016, 55, 2473. [10] Nishio, M. et al., J. Am. Chem. Soc. 2013, 135, 17715. [11] Fukunaga, H.; Miyasaka, H., Angew. Chem. Int. Ed. 2015, 54, 569. [12] Taniguchi, K. et al., Angew. Chem. Int. Ed. 2016, 55, 5238. [13] Taniguchi, K et al., Adv. Func. Mater. 2017, 27, 1604990. 139 PORPHYRIN-LIKE GOLD(III) COMPLEXES CONTAINING FOUR N-HETEROCYCLIC CARBENE LIGANDS Mageed, A,1,2 Skelton, B W,1 Baker, M V*,1 Presenting author’s e-mail: [email protected] 1 The University of Western Australia, Perth, Australia 2 The University of Kufa, An-Najaf, Iraq This presentation will describe the synthesis of new Au(III) complexes containing an Au(NHC)4 core. The complexes are derived from bis- and tetrakis(imidazolium) ions. The complexes have been structurally characterised by X-ray diffraction studies, and their solution behaviour has been explored using NMR spectroscopy and conductance measurements. Depending on the ancillary ligands available, the complexes can be of form [Au(NHC)4X2]X + or [Au(NHC)4]X3. In D2O, the [Au(NHC)4] cation undergoes H/D exchange reactions. 140 PROBING ELECTRONIC INTERACTIONS IN METAL-ORGANIC FRAMEWORKS Leong, C. F.1 and D’Alessandro, D. M.1 1 University of Sydney, Sydney, Australia ABSTRACT TEXT Metal-organic frameworks (MOFs) are robust materials which exhibit unique electronic and optical properties, which has seen applications in a wide range of areas including gas separations, chemisensing, heterogeneous catalysis, light harvesting, and more recently, conductivity. In particular, the modular and porous nature of MOFs opens up the possibility of developing tunable, functional materials. Towards enhancing the conductive properties of MOFs, which are typically insulating in nature, we draw on concepts from the rich field of organic CT salts such as TTF-TCNQ (tetrathiafulvalene-tetracyanoquinodimethane) which has been shown to exhibit metallic-like conductivity. This work investigates the structure—property relationships of a range of electroactive MOFs which integrate the canonical redox-active moieties TTF, naphthalene diimide (NDI) and porphyrin as functional units. These materials are probed via a suite of techniques including single crystal X-ray diffraction (XRD), powder XRD, UV-vis-NIR and Raman spectroscopies, as well as solid state electrochemistry and spectroelectrochemical methods to elucidate local and long range electronic interactions. As targeted design of conductive MOFs is slowly coming to light, further insight into the effects of structure on the electronic properties of these extended coordination materials is imperative to fully unlock the potential of MOFs as modular, tunable conductors. 141 PtIII and related species produced via oxidation of the PtII anticancer compound Ojha, R1, Bond, A1*, Deacon, G1*, Junk, P2*, Best, S3* 1School of Chemistry, Monash University, Clayton, VIC 3800, Australia, 2College of Science, Technology & Engineering, James Cook University, Townsville, Qld, 4811, Australia 3University of Melbourne, School of Chemistry, Parkville 3010 VIC, Australia, Recently we established that highly non-coordinating media provide conditions conducive to formation of monomeric PtIII derivatives in the electrochemical oxidation of the anticancer II compound trans-[Pt {(p-BrC6F4)NCH2CH2NEt2}Cl(py)] under short voltammetric time scales.[1] Almost quantitative transformation of PtII to PtIII occurred under short time scale voltammetric conditions. Small concentrations of the paramagnetic monomeric PtIII species remaining after longer timescale bulk electrolysis experiments were identified by EPR spectroscopy. We now report the characterization of some of the products (PtII organoenamineamides) formed by chemical oxidation of the platinum anticancer compound and by exhaustive bulk electrolysis. Relationships between PtIII intermediates and PtII organoenamineamides isolated in this study are considered. Interestingly, some but not all products obtained from chemical oxidation (see Figure 1) are the same as those derived from electrochemical oxidation. Substituted PtII organoenamineamide (A) generated by chemical oxidation gives more stable monomeric PtIII on its electrochemical oxidation and it is stable at longer time scales. Figure 1. X-ray crystal structures of substituted (A) and non-substituted (B) organoenamineamides II obtained after chemical oxidation of trans-[Pt {(p-BrC6F4)NCH2CH2NEt2}Cl(py)] with hydrogen peroxide. References [1] R. Ojha, A Nafady, M. J. Shiddiky, D. Mason, J. F. Boas, A. A. J. Torriero, A. M. Bond, G. B. Deacon, P. C. Junk, ChemElectroChem. 2015, 2, 1048-1061 142 Rare-earth Metal Imido and Alkylidene Complexes: Synthesis, Structure and Reactivity Yaofeng Chen State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Shanghai, China. Rare-earth metal (Sc, Y and lanthanide metal) complexes have diversified coordinating structure, interesting physical properties and rich reactivity, and have been extensively studied. Numerous of rare-earth metal complexes been synthesized. However, most of them are the complexes containing rare-earth metal-main group element single bonds, and the examples of rare-earth metal-main group element double bonds are very scared. This is not due to the lack of interests in these types of rare-earth metal complexes, but because of the challenges in synthesis of these complexes. HOMO/LUMO orbital energies between the d0 rare-earth metal ions and the imido (or alkylidene) groups are mismatched, the rare- earth metal-main group element double bonds (Ln = E) are highly polar and reactive. The rare-earth metal species containing Ln = E double bonds once formed easily assemble into the more stable µ or µn (n = 3, 4) bridged bimetallic or multi-metallic species, or undergo reactions with solvents via C-H bond activation. Meanwhile, such complexes are of great concern, not only for the fundamental coordination chemistry but also the expected rich reactivity from the highly reactive Ln = E double bonds. Recently, our group synthesized and characterized the first rare-earth metal terminal imido complexes, the scandium terminal imido complexes. We also synthesized and characterized a series of mononuclear rare-earth metal alkylidene complexes. These new types of complexes showed high and intriguing reactivity for small molecule activation. 143 Ratiometric sensing of metals in biology Shen, C, Kolanowski, JL, New, EJ University of Sydney, Sydney, Australia The cell’s reliance on metal-binding proteins necessitates the existence of labile and rapidly exchangeable metal pools. For example, substantial evidence has shown the labile copper pool to be sensitive to fluxes in the physiological conditions of the cell, and is therefore linked to diseases of the brain, and degeneration of neuronal cells. Our research focuses on the strategic development of methods for the ratiometric sensing systems of labile metal pools, which enable collection of unambiguous information on the target metal ion, separate from any background effects. Ratiometric fluorescent sensors report on their environment by a change in emission colour rather than intensity. By considering the interaction between fluorescence mechanisms and the binding of metals to covalently linked groups, we have rationally designed fluorescent scaffolds and metal- binding receptors to build useful probes. In this manner we have developed a picomolar- affinity Cu(I) sensor, InCCu1, with high selectivity for Cu(I) over other biological metals. InCCu1 is able to enter cells and shows a clear ratiometric emission profile change when bound to copper in the mitochondria. This probe was also used to investigate the effect of cisplatin on copper levels in cancer cells. We have also investigated the use of other sensing modalities, such as fluorescence lifetime imaging microscopy, for the development of probes that provide ratiometric fluorescence output. 144 Rational Design of Noncentrosymmetric (NCS) Materials Ok, K. M.1 Presenting author’s e-mail: [email protected] 1 Chung-Ang University, Seoul, Republic of Korea ABSTRACT Noncentrosymmetric (NCS) materials revealing superb functional characteristics such as nonlinear optical (NLO), pyroelectric, piezoelectric, and ferroelectric properties have been attracting massive recognition owing to their various applications in optical communications, detectors, sensors, and memories. Although many synthetic efforts have been made to obtain novel NCS materials for the past several decades, most of crystalline compounds exhibit centrosymmetric (CS) structures attributed to the facile antiparallel alignment of the local asymmetric units. Therefore, it should be very important to understand factors influencing the framework structures of the extended solid materials during the crystallization in order to discover novel NCS materials more effectively. In this presentation, a few key factors such as cation size effects, hydrogen bonding interactions, and framework flexibility will be discussed by using newly discovered solid state materials with asymmetric coordination environment. Recently discovered coordination polymers consisting of unsymmetrical units and their reactivities are also introduced. 145 Reactivity of Electrophilic d2 Nitrido Complexes Lau, T C City University of Hong Kong, Hong Kong, P.R. China. Nitrido complexes (M≡N) are believed to be key intermediates in chemical and biological nitrogen fixation. They are also useful reagents for nitrogenation of organic compounds. We will describe our recent results on the reactivity of nitrido complexes of ruthenium(VI), osmium(VI) and manganese(V) bearing Schiff base ligands. These nitrido complexes exhibit rich chemical reactivity, including reaction with various nucleophiles, CH bond activation, NN coupling, catalytic oxidation of organic compounds, and anti- cancer activities. Ruthenium(VI) nitrido complexes bearing Schiff base ligands, such as VI + [Ru (N)(salchda)(CH3OH)] , is highly electrophilic, and it reacts readily at ambient conditions with a variety of nucleophiles. Nucleophilic addition to coordinated Schiff base ligands can also be very facile in OsVI≡N and RuVI≡N. These additions are often stereospecific, suggesting that the nitrido ligand has a directing effect on the incoming nucleophile. M≡N is also a potential platform for the design of new oxidation catalysts. For example, [OsVI(N)(salen)Cl] catalyzes the oxidation of alkanes by a variety of oxidants. The catalytic oxidation is greatly accelerated by the addition of Lewis acids. M≡N is also potentially able to bind to and exert various effects on biomolecules. For example, a number of OsVI≡N complexes are found to exhibit novel anti-cancer properties, which may be related to their ability to bind to DNA or other biomolecules. This work was supported by the Hong Kong University Grants Committee (AoE/P-03-08) [1] Man, W. L.; Lam, W. W. Y.; Lau, T. C. Acc. Chem. Res. 2014, 47, 427-439. 146 RECENT PROGRESS IN ORGANOSILVER CHEMISTRY O’Hair, RAJO1,2, Weske, S2, Auth, T2, Wan, V1, Koszinowski, K2, Ariafard, A3, Canty, AJ3, 1 University of Melbourne, Melbourne, Australia 2 Georg-August-University, Göttingen, Germany 3 University of Tasmania, Hobart, Australia Due to their importance in organic synthesis, the structure and reactivity of organocopper and organogold species have been widely reported. In contrast, organosilver compounds have been less well studied. In this lecture, recent progress on the use of electrospray ionization (ESI) coupled with multistage mass spectrometry experiments to explore fundamental organosilver chemistry will be discussed, with an emphasis on: (1) Establishing the nature of organo(I)argentates that are formed by transmetallation of appropriate silver salts with either RLi or RMgCl in tetrahydrofuran. (2) Examining the relationship between organoargentates in the +1 and +3 oxidation states by treating solutions of organo(I)argentates with electrophiles and interrogating the resultant products. (3) Using collision induced dissociation (CID) to examine transmetallation reactions between organoborates and silver cations. (4) Unraveling the role of organosilver intermediates in catalytic C-C bond coupling reactions. 147 RECHARGEABLE BATTERIES USING POLYOXOVANADATE RELATED COMPOUNDS AS CATHODE ACTIVE MATERIALS Yoshikawa, H1, Wang, H1, Shimizu, T1 1 Kwansei Gakuin University, Sanda, Japan Rechargeable lithium ion batteries have great utility for applications ranging from consumer electronics and electric vehicles to large scale application such as electric grid balancing. There is a significant interest to develop high performance and cost effective electrode materials for next generation lithium ion batteries. Recently, we have developed a new type of rechargeable battery, the molecular cluster battery (MCB), which consists of a lithium metal as an anode and molecular clusters such as Mn12 clusters and polyoxometalates as cathode active materials, and found that these MCBs exhibited a larger capacity compared with those of the usual lithium ion batteries due to super- reduction of molecular clusters during discharge process. Here, to develop these MCBs furthermore, we tried to use polyoxovanadate clusters such as Li7[V15O36(CO3)] and [H2Metf]3[V10O28] (Metf: metformin) as cathode active materials since it is expected that their battery capacities per the weight become higher due to lighter atomic mass of vanadium. Firstly, we tested the battery performance of the annealed Li7[V15O36(CO3)] since the as-prepared one didn’t work as the battery. Powder XRD measurements demonstrated that Li7[V15O36(CO3)] was transformed into -LiV2O5 by annealing at 200 ºC under argon atmosphere, and this-LiV2O5 cathode exhibited a large discharge capacity of 250 Ah/kg and a good cycle performance. On the other hand, a lithium battery using the as-prepared [H2Metf]3[V10O28] as cathode active materials showed a discharge capacity of 150 Ah/kg in the first cycle. The details of their reaction mechanism revealed by XAFS and XRD will be given in the presentation 148 Redox Active Metal-Organic Frameworks with Multi-Components in Order Tu, B.1, Li, Q.1 1 Department of Chemistry, Fudan University, Shanghai, China Aiming for multi-functions of the materials, metal-organic frameworks (MOFs) with multiple components can be assembled from multiple inorganic and organic building units. However, it remains a challenge to further increase the number of components in one single framework, due to the difficulties in designing structures in which all components can participate in order and the complications in avoiding the exponentially increased possibilities of obtaining unwanted mixed phases. In this talk, we will report the creation of ordered metal vacancies and linker vacancies in a cubic MOF by symmetry guided removing the metal ions and the linkers1. By filling the vacancies with new metals and new linkers, new single-crystalline MOFs with multi- components (two metals and two linkers) in absolute order are introduced. Furthermore, a multi-component MOF structure was prepared from three kinds of SBUs, which are 3-, 5-, and 6- connected vertices, by topological induction2. Recently, by incorporating Cu ion into the multi-component framework, we have shown that the valence of the Cu ion can be switched between Cu(I) and Cu(II) without destroying the framework. The redox activity of these open metal sites was further evidenced by H2O2 decomposition, CO oxidation, and alcohol oxidation reactions. (1) Tu, B.; Pang, Q.; Wu, D.; Song, Y.; Weng, L.; Li, Q. J. Am. Chem. Soc. 2014, 136, 14465. (2) Tu, B.; Pang, Q.; Ning, E.; Yan, W.; Qi, Y.; Wu, D.; Li, Q. J. Am. Chem. Soc. 2015, 137, 13456. 149 RHENIUM N-HETEROCYCLIC CARBENE COMPLEXES: FROM PHOTOCHEMISTRY TO THERAPY Max Massi Curtin University, Perth, Australia Luminescent rhenium tricarbonyl complexes have been the centre of many investigations due to their favourable photophysical properties. These complexes have in fact been investigated in many areas including optical materials, photocatalysis, sensing and cellular staining.1-3 The classical formulation of these complexes typically includes the coordination of a conjugated diimine system, such as 1,10-phenanthroline. On the other hand, the replacement of the diimine for a bidentate N- heterocyclic carbene (NHC) ligand has not been investigated with the same level of detail. In the past few years, our aim has been focused on elucidanting the photophysical properties of Re NHC complexes.4,5 This presentation will illustrate some of our most important finding, which include unique photochemical ligand substitution reaction as well the elucidation of the origin of the anticancer properties of rhenium tricarbonyl systems.6 1 R. A. Kirgan et al., Top. Curr. Chem., 2007, 281, 45–100. 2 M. P. Coogan et al., Chem. Commun., 2013, 50, 384–399. 3 K. K.-W. Lo et al., Dalton Trans., 2012, 41, 6021–6047. 4 L. A. Casson et al., Dalton Trans., 2011, 40, 11960–11967. 5 J. G. Vaughan et al., Inorg. Chem., 2014, 53, 3629–3641. 6 J. G.. Mukuta, et al., Inorg. Chem., 2017, in press, DOI: 10.1021/acs.inorgchem.6b02936 150 RuO2 hydrates as efficient cocatalysts for Z-scheme water splitting Suzuki, H, Higashi, M, Abe, R E-mail: [email protected] Kyoto University, Kyoto, Japan ABSTRACT Loading a cocatalyst onto a photocatalyst is a well-known effective way to improve the efficiency of both one-step water splitting and Z-scheme water splitting with a redox – – mediator. In Z-scheme water splitting systems with an IO3 /I redox couple, the reduction of – IO3 on O2-evolving photocatalysts via a six-electron process often represents the rate- determining step of the overall process, and therefore necessitates effective cocatalysts such as PtOx and RuO2. However, these cocatalysts cannot be loaded onto thermally unstable materials via conventional impregnation processes involving calcination. In the present study, we introduce a new Ru-based cocatalyst that can be loaded without – calcination and effectively promotes the reduction of IO3 on various photocatalysts, including non-oxide materials. The results reveal for the first time that the Ru species adsorbed via simple stirring of photocatalyst particles such as WO3 in an aqueous RuCl3 – solution effectively trigger O2 generation in the presence of IO3 as electron acceptor; moreover, the O2 evolution rate on the present Ru-loaded WO3 sample was much higher than that obtained with conventional RuO2-loaded WO3. The structural analysis indicates that the Ru species adsorbed on WO3 are highly dispersed and characterized by octahedral RuO6 environments similar to those found in RuO2·nH2O. The newly developed Ru-based cocatalyst was also applicable to thermally unstable materials such as H2WO4 – and Ta3N5, thus enabling them to generate O2 in the presence of IO3 151 Ruthenium(VII) alcohol oxidations understood Zerk, T.J., Moore, P.W., Williams, C.M., Bernhardt, P.V. School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, Australia One of the most fundamental organic transformations is the oxidation of an alcohol to an aldehyde. Three protocols dominate the synthetic landscape in this regard; these are 1) the Swern oxidation, 2) use of hypervalent iodides such as the Dess-Martin periodinane (DMP) or 2-iodoxybenzoic acid (IBX), and 3) the Ley-Griffith reaction. Each of these facilitates the transformation under mild conditions without over-oxidation to the acid (in the case of a primary alcohol). The Ley-Griffith protocol1 is particularly attractive because it is effective even in the presence of other reactive functional groups. The reaction is catalysed by the oxido-Ru(VII) complex tetrapropylammonium perruthenate (TPAP) with the stoichiometric oxidant typically being N-methylmorpholine N-oxide (NMO) (Scheme 1). Although organic chemists have utilised this protocol extensively, there is virtually no understanding of the reaction mechanism. We have set out to explore how TPAP and NMO are involved in this reaction. The mechanisms for both the oxidation and catalytic re- generation steps have been elucidated. The results provide several suggestions for improving the synthetic method; one of these is to simply leave out one of the starting materials. Scheme 1. The Ley-Griffith alcohol oxidation, catalysed by TPAP. References 1. Griffith, W. P.; Ley, S. V.; Whitcombe, G. P.; White, A. D. J. Chem. Soc. Chem Comm. 1987, 1625-1627. 152 153 Sandiwch-type Tetrapyrrole Lanthanide-based Single Molecule Magnets Jiang, Jianzhuang Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China A series of bis/tris/tetrakis(phthalocyanine)lanthanide complexes have been designed and synthesized for the purpose of affording good single molecule magnets (SMMs) and understanding the structure-function relationship. References 1. H. Wang, B. Wang, Y. Bian, S. Gao, J. Jiang, Coord. Chem. Rev., 2016, 306, 195-216. 2. W. Cao, C. Gao, Y. Zhang, D. Qi, T. Liu, K. Wang, C. Duan, S.Gao, J. Jiang, Chem. Sci., 201 6, 5947-5954. 3. X. Kong, X. Zhang, D. Gao, D. Qi, Y. Chen, J. Jiang, Chem. Sci., 2015, 6, 1967-1972. 4. H. Wang, K. Qian, D. Qi, W. Cao, K. Wang, S. Gao, J. Jiang, Chem. Sci., 2014, 5, 3214. 5. J. Kan, Y. Chen, D. Qi, Y. Liu, J. Jiang, Adv. Mater., 2012, 24, 1755. 154 6. J. Jiang, D. K. P. Ng, Acc. Chem. Res., 2009, 42, 79. 155 SELECTIVE ANION TRANSPORT Philip A. Gale1 [email protected] . 1 School of Chemistry, University of Sydney, NSW 2006, Australia Synthetic transmembrane anion transporters (anionophores) have potential as tools for biomedical research and as therapeutic agents for diseases associated with anion channel dysfunction such as cystic fibrosis (CF). However, the issue of potential H+ or OH- transport by anionophores has received little attention and proven Cl--selective anionophores that do not facilitate the transport of H+ or OH- transport are currently unavailable. HCl co-transport may be useful in the development of anti-cancer agents1 as proton transport processes have been linked to toxicity. For example, we have recently shown that pH dissipation within cells triggered by a squaramide-based transporter can disrupt autophagy.2 However, other applications such as the development of channel replacement therapies for CF require selective transport. We have developed new assays to measure the chloride vs. proton transport selectivity of small molecule anion transporters3 and shown that proton transport may be facilitated by receptor deprotonation (weak acid protonophore mechanism) or by facilitating the transport of carboxylate fatty acid head groups through membranes.4 We have developed the first examples of chloride transporters that show selectivity for chloride transport in the presence of fatty acids.5 References: 1. E.N.W. Howe, N. Busschaert, X. Wu, S.N. Berry, J. Ho, M.E. Light, D.D. Czech, H.A. Klein, J.A. Kitchen and P.A. Gale, J. Am. Chem. Soc., 2016, 138, 8301-8308. 2. N. Busschaert, S.-H. Park, K.-H. Baek, Y.P. Choi, J. Park, E.N.W. Howe, J.R. Hiscock, L.E. Karagiannidis, I. Marques, V. Félix, W. Namkung, J.L. Sessler, P.A. Gale and I. Shin, Nature Chem., 2017, DOI: 10.1038/nchem.2706. 3. X. Wu, L.W. Judd, E.N.W. Howe, A.M. Withecombe, V. Soto-Cerrato, H. Li, N. Busschaert, H. Valkenier, R. Pérez-Tomás, D.N. Sheppard, Y.-B. Jiang, A.P. Davis and P.A. Gale, Chem, 2016, 1, 127-146. 4. X. Wu and P.A. Gale, J. Am. Chem. Soc., 2016, 138, 16508-16514. 5. H.J. Clarke, E.N.W. Howe, X. Wu, F. Sommer, M. Yano, M.E. Light, S. Kubik and P.A. Gale, J. Am. Chem. Soc. 2016, 138, 16515-16522. 156 Self-assembled Cu(I) Complexes: Synthesis, Characterization and Optical Spectroscopy Khan, M.S., Haque, A., Al-Balushi, R.A., Maharaja, J., and Al-Suti M.K. Department of Chemistry, Sultan Qaboos University, Muscat, Oman. Presenting author’s e-mail: [email protected]. Conjugated organometallics constitute a fascinating class of solution-processable and property- tunable materials for applications in various opto-electronic (O-E) devices [1]. In organometallic complexes, the photo-physical properties of the metal fragments are coupled to those of the conjugated organic ligands to produce advanced functional materials. Among them, luminescent Cu(I) complexes have attracted attention due to the their diverse structural and photophysical properties. These complexes have potential applications in different areas including optoelectronics. Cu(I) is well known for its ability to form, in association with various types of bridging and terminal ligands, polynuclear (cluster) species of various shapes and sizes [2,3]. The design and development of coordination-driven self-assembled Cu(I) clusters incorporating acetylide-functionalized ligands have opened the opportunity to explore the chemistry and photo- physics of novel metal organic framework (MOF) materials. [4] By changing the combination of ligands and Cu(I) salts, different Cu(I) complexes can be achieved which possess colorful emissive excited states [1]. Recently, we reported some interesting Cu(I) clusters with a pyridine functionalized ethynylferrocene ligand [4,5]. Here in, the synthesis of a series of new arylethynylpyridine ligands incorporating different carbocyclic, heterocyclic and mixed hetero-cycles - - - and their CuX complexes (X = Cl , Br and I ) in the presence of varying co-ligands (PPh3, P(o-tol)3 and PBu3) will be presented. The structural (Figure 1), electrochemical and optical properties of the new materials will be discussed. Figure 1. Crystal structure of Cu(I) complex with pyridinylethynylflourenyl and PPh3 ligands. References [1] Peng, R.; Li, M.; Li, D. Coord. Chem. Rev. 2010, 254, 1−18. [2] Angamuthu, R.; Byers, P.; Lutz, M.; Spek, A. L.; Bouwman, E. Science 2010, 327, 313 [3] Noorduin, W. L.; Grinthal, A.; Mahadevan, L.; Aizenberg, J. Science, 2013, 340, 832. [4] Shah, H. H., Al-Balushi, R. A., Al-Suti, M. K., Khan, M. S., Woodall, C. H., Kociok-Köhn, G., Raithby, P.R., Molloy, K.C., Dalton Trans., 2014, 43(25), 9497-9507. [5] Shah, H. H., Al-Balushi, R. A., Al-Suti, M. K., Khan, M. S., Woodall, C. H., Sudlow. A. L, Raithby, P.R., Kociok-Köhn, G., Molloy, K.C. and Marken, F., Inorg. Chem. 2013, 52, 12012 – 12022. 157 Single Molecule- and Single Toroidal Magnetism in Heptanuclear MLn6 Clusters Murray K. S.1, Langley, S. K.2, Moubaraki, B.1, Vignesh, K. R.3, Rajaraman, G.4, Soncini, A.5, Wernsdorfer, W.6 Presenting author’s e-mail: [email protected] . 1 Monash University, Clayton, Australia 2 Manchester Metropolitan University, Manchester, U.K. 3IITB-Monash Academy, Powai, Mumbai, India 4IITB, Powai, Mumbai, India 5University of Melbourne, Parkville, Australia 6Institut Neel, CNRS, Grenoble, France Some years ago Powell et al. discovered the first lanthanide triangular cluster, containing a {Dy3(μ3-(OH)2)} core, to exhibit toroidal moment (SMT) behaviour [1]. Theoretical analysis followed shortly afterwards [2]. As part of our heterometallic Cr/Ln SMM investigations [3] we recently isolated the first single molecule ferrotoroidal example in which two {Dy3-o- toluate} triangles are linked by a 6-coordinate Cr(III), S = 3/2, centre. The toroidal moments are con-rotatory in regard to each other (see Figure). Theoretical analysis of the characteristic S-shaped magnetisation isotherm reveals that dipolar coupling between the Dy3 moieties induces the ferrotoroidally- coupled molecular ground state. Intriguingly, the Cr(III) linker is calculated to play no part in the coupling mechanism, rather it keeps the triangles apart at a certain distance. To check this out further, new compounds with other linkers, including diamagnetic Al(III) and Co(III), are being explored. New toroidal analogues containing, for the first time, Ln ions other than Dy viz. Tb, Ho, Er, with a Cr(III) linker, are also discussed. Dy3+ Dy3+ O Dy3+ Cr3+ Dy3+ O Dy3+ Dy3+ [1] Tang, J. Hewitt, I., Madhu, N. T., Chastanet, G., Wernsdorfer, W., Anson, C. E., Benelli, C., Sessoli, Powell A. K.. Angew. Chem. Int. Ed. 45, 1729 (2006). [2] Ungur, L., Lin, S.-Y., Tang, J., Chibotaru, L. F. Chem. Soc. Rev. 43, 689 (2014). [3] Langley, S. K., Wielechowski, D. P., Moubaraki, B., Murray, K. S. ChemComm, 2016, 52, 10976 158 Single molecule conductance of Ru(dppe)2-containing organometallic molecular wires Kato, Y, Sugimoto, K, Tanaka, Y, Akita, M e-mail: [email protected] Tokyo Institute of Technology, Yokohama, Japan Organometallic molecular wires have been studied extensively as key components of molecular devices and circuits, and their performance has been evaluated conveniently on the basis of physical parameters such as Kc (comproportionation constant) and Vab (electronic coupling) values. Recently, surface science technique has been applied to this issue. Herein we will report on (1) synthesis of a series of organometallic molecular wires consisting of the Ru(dppe)2 unit and the oligoynediyl bridges and (2) their wire-like performance estimated by the STM-BJ (break junction) method. The organometallic molecular wires were prepared following the reaction sequence of 1n 2n 3n. n n n X-(CC)n-Ru(dppe)2-(CC)n-X (X= SiMe3 (1 ), H (2 ), Au{P(OMe)3} (3 ); n= 2, 3, 4) The terminal groups play crucial roles in the conductance and, therefore, the complexes with the H (2n) and gold termini (3n) were designed; both termini are expected to form C- Au junctions with the gold electrode surfaces via C-H activation (2n) and transmetallation- like reaction (3n), respectively. The distances between the terminal acetylide carbon atoms are 1.16 (12), 1.68 (13) and 2.17 Å (14) as determined by X-ray crystallography. STM-BJ analysis of these molecules shows that their performance is superior to that of organic molecular wires with the similar molecular lengths. Dependence of the performance on the molecular lengths (n) and possible mechanisms will be also discussed. 159 SITE SELECTIVITY OF METAL COMPLEXATION AT LARGE POLYCYCLIC AROMATIC HYDROCARBONS Kovalenko, N, Hall, TBJ, Hoggard, BR, Larsen, CB, Lucas, NT Department of Chemistry, University of Otago, Dunedin, New Zealand Since the discovery of ferrocene, a multitude of metal complexes of 6π-aromatic ligands such as η5-cyclopentadienide and arenes have been synthesised. In parallel to these advances, the coordination chemistry of polycyclic aromatic hydrocarbon (PAH) compounds such as indenide and naphthalene have been developed.1 As the size of the PAH ligand increases through fusion of additional benzenoid rings, the number of possible isomers grows, along with the possibility of accommodate multiple metal fragments and the interconversion of isomers via a haptotropic shift. To better understand the factors that influence the site of π-complexation of ligated metal centres at PAHs, we have prepared systematically-varied medium-to-large PAHs.2 Peripheral substituents with a range of steric bulk and electron-donating abilities have been incorporated, in addition to the cyclopenta-fused derivatives as extended of analogues of indene and fluorene. One such PAH studied here is hexa-peri-hexabenzocoronene (HBC). HBC was first prepared by Clar in the 1950s who ascribed its high stability to the accommodation of all π- electrons in discrete sextets.3 The π-complexation of HBCs provides an opportunity to probe the electronic distribution of the aromatic core and evaluate the effect of peripheral substituents. Some recent results will be presented, including complexes with the arenophilic [RuCp*]+ fragment. R1 R1 [RuCp*]+ R1 R2 R1 = t-Bu, R2 = H R1 R1 [1] (a) P. L. Pauson, G. Wilkinson, J. Am. Chem. Soc. 1954, 76, 2024. (b) C. Elschenbroich, R. Möckel, Angew. Chem. Int. Ed. Engl. 1977, 16, 870. [2] B. R. Hoggard, C. B. Larsen, N. T. Lucas, Organometallics 2014, 33, 6200. [3] E. Clar, The Aromatic Sextet. John Wiley and Sons: London, 1972. 160 Six- Coordinated Iron(III) Porphyrin Complexes with Axially Substituted Pyridine N- oxides Ikeue, T1, Ide, Y1, Mori, S2, Nakamura, M3 Presenting author’s e-mail: [email protected] 1 Shimane University, Matsue, Japan 2 Ehime University, Matsuyama, Japan 3 Toho University, Funabashi, Japan ABSTRACT TEXT Iron porphyrin complexes exist for heme within an organism and have a very important role of oxygen transport, electron transfer, and enzyme. There are the axial ligand exchange binding to the iron porphyrin and the change of oxidation number for iron ions. In particular, the model compound of Compound I with the very high reactivity has not been report and attracts an interest of many scientists. As the precursor of the catalase model compound, the six-coordinated iron(III) porphyrin complexes with neutral oxygen ligands adopt high spin (S = 5/2) or intermediate spin (S = 3/2) states by the difference of axial ligand fields(Hoshino et al., 2005). We purpose the synthesis of heme mimic and to reveal their electronic state. In this study, the five-and six-coordinated iron(III) porphyrin complexes of + + meso-tetramesitylporphyrin ([Fe(TMP)L] and [Fe(TMP)L2] ) with axially substituted pyridine N-oxides (L = 4-XPyNO) were synthesized and confirmed the structure by the X- ray crystal structure analyses, which have studied the magnetic properties both in solution and in the solid by the SQUID, ESR, and NMR measurements. The five-coordinated iron(III) porphyrin complexes with substituted pyridine N-oxides show the structural feature and the magnetic properties of the high spin state. The six-coordinated iron(III) porphyrin complexes with suitably substituted pyridine N-oxides as axial ligands exhibit a quite rare spin-crossover phenomena between high-spin (S = 5/2) and low-spin (S = 1/2) states, if the ligand field of substituted pyridine N-oxides as axial ligands is stronger. 161 Spin Crossover and Postsynthetic Modification within Porous Hofmann-Type Materials Clements, J1, Price, J2, Neville, S1, Kepert, C1 Email: [email protected] 1University of Sydney, Sydney, Australia 2Australian Synchrotron Company Limited, Clayton, Australia The ability to understand and control structure and properties is a key challenge in the pursuit of multifunctional materials. Over the past two decades, metal-organic frameworks (MOFs) have emerged as class of these materials, drawing significant attention due to their facile syntheses, broad range of building units and demonstrated applications. Although significant progress has been made in this area with regards to synthetic control, challenges still remain in incorporating components with desired functionality into target framework topologies. In order to overcome these difficulties, postsynthetic modification (PSM) – a stepwise synthetic strategy using thermal, photochemical and synthetic transformations to obtain functionalised linkers – has been employed to generate materials that cannot be produced in a single step via reactions of their constituents. To this end, we have sought to use this approach to exert control over the structure- property relationships within porous MOFs that incorporate spin crossover, a highly sensitive phenomenon where high spin and low spin material states are switched with external stimuli (e.g., temperature, pressure and light). As materials of this type demonstrate remarkable behaviours originating from synergistic interplay between porosity and magnetic switching, PSM is an attractive means for adjusting these properties at the molecular level. In this body of work, we demonstrate via variable temperature X-ray diffraction, spectroscopy and magnetic susceptibility, how seemingly small changes to structure and composition can have a drastic impact on material responses.[1-2] As‐Synthesised PSM Figure 1: a) Changes in magnetic susceptibility with covalent postsynthetic modification. b) Magnetic susceptibility from material generated from ex situ prefunctionalised ligands. [1] Clements, J. E., Price, J. R., Neville, S. M., Kepert, C. J., Angew. Chem. Int. Ed. 2014, 53, 10164-10168. [2] Clements, J. E., Price, J. R., Neville, S. M., Kepert, C. J., Angew. Chem. Int. Ed. 2016, 55, 15105-1510 162 Spin Crossover: Structure – Function Properties Suzanne M. Neville,1 Natasha F. Sciortino,1 Michael J. Murphy,1 Cameron J. Kepert,1 Florence Ragon,1 Gregory J. Halder,2 J. A. Real3 Presenting author’s e-mail: [email protected] 1 The University of Sydney, Australia 2 X-ray Science Division, Advanced Photon Source, USA 3 The University of Valencia, Spain Spin crossover (SCO) materials can be converted between two local spin states (high and low spin) with differing magnetic, optical, electrical and structural properties.[1] Iron(II) complexes show a particularly assorted set of SCO behaviours, encompassing gradual, abrupt, hysteretic, and multi-step spin transitions. Materials that display stepwise transitions are particular sought after as they conceptually lead to high order data storage possibilities such as ternary and quaternary processing but are comparatively rare in existence. We have generated a structural platform of 2-D framework materials that intrinsically support the structural distortions requisite of multi-stepped SCO. Through tailoring host-host and host-guest interactions in these materials we have produced a diverse range of multi-stepped (two-,[2] three-[3] and four-stepped[4]) and guest-modulated[5] spin transitions (Figure 1). Detailed structure – function studies on these materials have provided important information on the relative importance of weak and strong interactions and structural distortions on lattice cooperativity (i.e., elastic versus frustrated elastic states). Figure 1 Examples of four-step (left) and guest programmable multistep (right) SCO transitions. [1] M. A. Halcrow, Spin-Crossover Materials: Properties and Applications, John Wiley & Sons, 2013. [2] Y. M. Klein, N. F. Sciortino, F. Ragon, C. E. Housecroft, C. J. Kepert, S. M. Neville, Chem. Comm. 2014, 50, 3838-3840. [3] M. J. Murphy, K. A. Zenere, F. Ragon, P. D. Southon, C. J. Kepert, S. M. Neville, J. Am. Chem. Soc. 2017, 139, 1330-1335. [4] N. F. Sciortino, K. A. Zenere, M. E. Corrigan, G. J. Halder, G. Chastanet, J.-F. Létard, C. J. Kepert, S. M. Neville, Chem. Sci. 2017, 8, 701-707. [5] N. F. Sciortino, F. Ragon, K. A. Zenere, P. D. Southon, G. J. Halder, K. W. Chapman, L. Piñeiro- López, J. A. Real, C. J. Kepert, S. M. Neville, Inorg. Chem. 2016, 55, 10490-10498. 163 STABILITY ENHANCED OF CYCLOPHOSPHAZANES BY OXIDIZATION WITH CHALCOGEN ELEMENTS. Shi Xioayan, Sim Ying and Felipe Garcia* Presenting author’s e-mail: [email protected] 1 Nanyang Technological UniversityFlinders University, Adelaide, Australia ABSTRACT Throughout the past five decades, organic frameworks have been extensively studied and developed across a myriad of applications. Analogous inorganic frameworks composed of non-carbon backbones, are merely chemical curiosities by contrast as their bonds have a much greater kinetic lability; due partly to their bond polarity and partly to their variable hybridization and oxidation states. The design of robust molecular inorganic frameworks still represents a major synthetic challenge compared to their organic counterparts. Since the isolation of the first P-N heterocycle in the early 19th century, there has been growing interest in the chemistry of such systems.[1] However, the instability of these systems, in particular saturated P-N frameworks, has previously handicapped their broader use in technological applications. Our on-going studies are focused on the stability and chemical reactivity of functionalized cyclophosph(III/III)azanes and cyclophosph(V/V)azane frameworks (e.g., nitrile, carboxylic acid, etc.). Intrinsic bond lability is a common property of cyclophosphazanes that renders these species incapable of withstanding standard reaction conditions required for many simple organic transformations. We report the synthesis and characterization of a series of new cyclophosph(III/III)azane frameworks and their air-stable, chalcogen oxidized derivatives (E = O, S and Se).[2],[3] References [1] Chivers, T.; Manners, I. Inorganic rings and polymer of the p-block elements. from fundamentals to applications, RSC: Cambridge, U.K., 2009. [2] (a) X.-Y. Shi, R.-Z. Liang, K. A. Martin, D. G. Starr, J. D., Y. Li, R. Ganguly and F. García. Chem. Commun., 2015, 51, 16468 – 16471. (b) X.-Y. Shi, Z.-R. Liang, K. A. Martin, N. Weston, S. Gonzale-Calera, R. Ganguly, Y. Li, Y. Lu, A. Ribeiro, M. Ramos, P. Fernandes, F García. Inor. Chem., 2015, 54, 6423 – 6432. (c) F.Garcia et al., unpublished results. 164 Stimuli Responsive Metal-Organic Frameworks – An Insight from Molecular Modelling Babarao, R,1,2 Huang, R3 and Medhekar, N.V.4 1 School of Science, RMIT University, Melbourne, Australia 2CSIRO Manufacturing, Clayton, Australia 3University of California, Riverside, California, USA 4Monash University, Clayton, Australia With increasing energy demand and global energy consumption, there is s serious threat on the concentration of atmospheric CO2, a major cause for the global warming effect. Carbon capture and storage technologies represent a promising solution towards mitigating the anthropogenic CO2 emissions. Metal-organic frameworks (MOFs) have attracted a growing interest as a promising class of materials for low-energy CO2 capture and release. Furthermore, several recent studies have demonstrated that external stimuli such as pressure, heat, and in particular, light, can enable the changes in conformations and chemistry of a host of chemical compounds that can be introduced into the crystal structure of MOFs. Light-responsive Metal-organic frameworks(MOFs) have attracted a growing 1,2 interest as a promising class of materials for low-energy CO2 capture and release. However, the underlying mechanisms for gas adsorption mechanisms and structural characterization of stimuli responsive MOFs remain a mystery. In this work, we investigated the CO2 adsorption and release mechanism in two stimuli responsive MOFs, using a combination of Grand Canonical Monte Carlo (GCMC) methods, density functional theory (DFT) and molecular dynamic (MD) simulations.3 References 1. R. Lyndon, K. Konstas, B. P. Ladewig, P. D. Southon, P. C. J. Kepert, M. R. Hill, Angew. Chem., Int. Ed., 2013, 52, 3695-3698. 2. J. Park, D. Yuan, K. T. Pham, J.-R. Li, A. Yakovenko, H.-C. Zhou, J. Am. Chem. Soc., 2011, 134, 99-102. 3. R. Huang, M.R. Hill, R. Babarao and N. V. Medhekar, J. Phys. Chem. C 2016, 120, 16658−16667. 165 STRUCTURAL INFLUENCES DICTATING THE ANTIMICROBIAL ACTIVITY OF BISMUTH COMPLEXES Andrews, P. C. Monash University, Clayton, Melbourne, VIC 3800, Australia Antibacterial resistance is identified by the World Health Organisation as one of the greatest threats we face globally, now and into the future.1 Since the introduction of antibiotics 80 years ago the quantum of effective drugs has diminished dramatically. Unfortunately, this has coincided with a diminution of industry-based research and development into new antibiotics.2 Metal-based antibiotics are not new and those based on silver still attract much attention; both as metal-organic compounds (eg silver sulfadiazine) and more recently as nanoparticles.3 However, there are significant problems; environmental contamination and persistence, human toxicity, and emerging resistance have all been identified as future limiting factors which may lead to greater regulation.4 Alternatives to silver which provide equal if not better benefits will need to be found. This presentation describes our recent efforts in developing bismuth(III) compounds which display excellent antimicrobial activity, particularly against multi-resistant strains of bacteria, while showing negligible toxicity towards mammalian cells. The focus will be on the design and development of homo- and heteroleptic bismuth(III) complexes;5,6 their syntheses, stability, solubility, and the structural chemistry which influences their antimicrobial activity. The results of assays against a range of gram positive and gram negative bacteria will be presented and the implications for developing new bismuth-based antibacterial drugs and materials discussed. 1. World Health Organisation: Antimicrobial Resistance: global report on surveillance (2014). 2. T. Gottlieb, G. R. Nimmo, Med. J. Aust., (2011), 194, 281. 3. L. Rizzello, P. P. Pompa, Chem. Soc. Rev., (2015), 43, 1501. 4. J-Y. Maillard, P. Hartemann, Crit. Rev. Microbiol., (2013), 39, 373. 5. For example: A. Pathak, V. L. Blair, R. L. Ferrero, M. Mehring, P. C. Andrews, Chem. Commun., (2014), 50, 15232. 6. For example: A. Luqman, V. L. Blair, R. Brammananth, P. K. Crellin, R. L. Coppel, P. C. Andrews, Chem. Eur. J., (2014), 20, 14362. 166 Super Bulky Amides: New Ligands for Low-Valent Main Group Complexes Cameron Jones Monash University, Melbourne, Australia Considerable progress has been made over the last decades towards the stabilisation of very low oxidation state s- and p-block compounds. These systems are often very reactive and are finding a variety of applications, the most topical of which is the "transition metal- like" activation of small molecules. Very bulky chelating ligands are normally required to kinetically protect such compounds from decomposing via disproportionation, and other, pathways. Surprisingly little work has been carried out in recent years dealing with monodentate amido complexes of s- and p-block metals in low oxidation states. In this lecture the development of a new class of extremely bulky amido ligands will be discussed, as will their use in the preparation of previously inaccessible, coordinatively unsaturated low oxidation state s-, p- and first row d-block complex types, e.g. 1-4. The extremely facile "transition metal-like" reactivity of these compounds towards small molecule (e.g. H2, CO2, NH3 etc.) activations, and related catalytic processes, will also be detailed. It is now clear that such complexes have considerable potential as viable alternatives to expensive (and often toxic) late transition metal catalysts, which are employed in numerous synthetic transformations. Ar* N Ge Ar* SiPh3 i SiPri Pr 3Si 3 N Mg Mg N Ge N Ph Si Ar* Ar* = Ar* 3 1 2 Ph Ph Ph Ph Mes N Ar* Ar* Ar* Mes = mesityl Mg Mn N N Zn Zn Zn N N i i SiPri Pr 3Si SiPr 3 Mes 3 3 4 167 Supporting Lanthanoid Clusters with Tetrazole-Functionalised Calixarenes) Phe, R1, Massi, M1, Ogden, M.I.1 Presenting author’s e-mail: [email protected] 1 Curtin University, Perth, Australia We have reported the synthesis of calix[4]arene ionophores functionalized at the lower rim with tetrazole moieties [1,2] These ligands were envisaged as a new class of lanthanoid ionophores with the potential for improved photophysical properties compared to the more typical ester or amide-functionalised calixarene, through increased rigidity. Against expectations, the tetra-tetrazole derivative proved to be a poor ionophore for lanthanoids.[2] The bis-tetrazole, in contrast, readily formed mononuclear complexes in the presence of strong base,[1] whereas in the presence of ammonium carboxylates, remarkable “bottlebrush” shaped clusters were isolated.[3] Here, we will report our most recent efforts to control the formation of these unusual clusters through structural variation of the calixarene ligands, as well as further efforts to characterize the cluster properties in solution- and solid-phase. [1] D. D’Alessio, S. Muzzioli, B.W. Skelton, S. Stagni, M. Massi, and M.I. Ogden, Dalton Trans., 2012, 41, 4736-4739. [2] D. D’Alessio, B.W. Skelton, N.A. Lengkeek, B.H. Fraser, A.M. Krause-Heuer, S. Muzzioli, S. Stagni, M. Massi, and M.I. Ogden, Supramol. Chem., 2015, 27, 787. [3] D. D’Alessio, A.N. Sobolev, B.W. Skelton, R.O. Fuller, R.C. Woodward, N.A. Lengkeek, B.H. Fraser, M. Massi, M.I. Ogden, J. Am. Chem. Soc., 2014, 136, 15122. 168 Supramolcular Cyclotricatechylene Assemblies Abrahams, B. F., Ahveninen, A., Boughton, B. A., FitzGerald, N. J., Holmes, J. L., Hudson, T. A., Robson, R. University of Melbourne, Parkville, Australia The tri-catechol molecule, cyclotricatechylene (ctcH6) commonly adopts a bowl-shaped conformation as shown below. The anionic form, ctc6-, is able to combine with a variety of metal centres to form a wide range of cage-like assemblies including tetrahedra, trigonal prisms, cubes and rhombic dodecahedra. Supramolecular assemblies are formed with metal centres ranging from lithium to uranium. The internal electron-rich, aromatic surfaces interact with various organic and inorganic guest species. Cations such as Cs+ and Rb+, which are commonly located within the bowl-shaped cavities of the ctc ligands, have a special affinity for the ctc unit. 6- Of recent interest is a covalent Si-based tetrahedral cage of composition [(PhSi)6(ctc)4] (below). The crystal structure determination of the anion reveals a highly symmetric face- 6- centred cubic structure. The [(PhSi)6(ctc)4] cage has been shown to be particularly robust with electrospray ionisation mass spectrometry and NMR clearly indicating the stability of 6- the cage in solution. Initial exploration of the host-guest chemistry of the [(PhSi)6(ctc)4] cage, in both solution and the solid-state, has yielded very promising results and opens up exciting possibilities especially if the phenyl group, bound to the Si centre, can be functionalised. 6- H6ctc [(PhSi)6(ctc)4] 169 SUPRAMOLECULAR ASSOCIATIONS PECULIAR TO COORDINATION COMPLEXES Tiekink, E R T Research Centre for Crystalline Materials, School of Science and Technology, Sunway University, Bandar Sunway, Selangor Darul Ehsan, Malaysia ABSTRACT In order to achieve the ultimate goal of crystal engineering, the deliberate and rational design of the molecular packing in crystals, a thorough understanding of the way molecules self-assemble in the condensed phase is required. A particular favourite mode of assembling molecules, for both organic compounds and coordination complexes, relies on conventional hydrogen-bonding; halogen bonding is increasingly being recognised as being able to provide reliable supramolecular synthons. The formation of dative/coordinate bonds between donor bases and metal centres is a hugely important mode of self- association of coordination complexes, often leading to the ubiquitous coordination polymers/metal-organic frameworks. The aim of this presentation is to explore other modes of supramolecular assembly pertaining to coordination complexes exclusively. For example, it turns out that chelate rings can participate in supramolecular synthons much in the same way as arene rings do. Thus, chelate rings may assemble via stacking interactions of the type (chelate)…(chelate) resembling (arene)…(arene) interactions, and they can function as acceptors in C–H…(chelate) interactions akin to C–H…(arene) contacts. A survey of these, and more, will be presented to highlight the supramolecular assemblies they sustain along with theoretical considerations to explain the nature of the supramolecular association and the energies of stabilisation they impart to the molecular packing. 170 Supramolecular Conjugate of Porphyrin and Phthalocyanine Tanaka, K. Nagoya University, Nagoya, Japan Organized assemblies of metalloporphyrinoids are feasible for generating higher functionalized systems including photochemical, catalytic, magnetic, materials. We have recently reported supramolecular arrays consisted of metalloporphyrins and metallophthalocyanines based on four-fold rotaxane linkages [1-9]. In the conjugate, a porphyrin and a phthalocyanine formed a heterodimer in a cofacial fashion (Figure). The conjugate is a promising platform for supramolecular catalysts based on dinuclear porphyrinoid complexes, because various metal ions are able to be arrayed in the conjugate to be a functional center. In this paper, we will present regioselective metal arraying in the conjugate [2, 7, 8] and the supramolecular catalytic functions. The dinuclear iron complex exhibited good catalytic activity in electrochemical reduction of molecular oxygen to water. [9] 1) Y. Yamada, M. Okamoto, K. Furukawa, T. Kato, and K. Tanaka, Angew. Chem. Int. Ed., 51, 709 (2012). 2) Y. Yamada, N. Mihara, and K. Tanaka, Dalton Trans., 42, 15873 (2013). 3) Y. Yamada, N. Mihara, S. Shibano, K. Sugimoto, and K. Tanaka, J. Am. Chem. Soc., 135, 11505 (2013). 4) Y. Yamada, M. Okada, and K. Tanaka, Chem. Commun., 49, 11053 (2013). 5) Y. Yamada, T. Kubota, M. Nishio, and K. Tanaka, J. Am. Chem. Soc., 136, 6505 (2014). 6) Y. Yamada, S. Akine, K. Sugimoto, and *K. Tanaka, Chem. Euro. J., 22, 12371 (2016). 7) N. Mihara, Y. Yamada, S. Akine, K. Sugimoto, and K. Tanaka, Chem. Commun., 53, 2230 (2017). 8) N. Mihara, Y. Yamada, and K. Tanaka, Bull. Chem. Soc. Jpn., 10.1246/bcsj.20160423. 9) N. Mihara, Y. Yamada, H. Takaya, Y. Kitagawa, S. Aoyama, K. Igawa, K. Tomooka, and K. Tanaka, Chem. Euro. J., 10.1002/chem.201700082. 171 Supramolecular Thermocell Consisting of Ferrocene Derivatives and β-CD Yamada, T1,2, Zou, X1, Kimizuka, N1 [email protected] 1 Kyushu University, Fukuoka, Japan 2 Japan Science and Technology Agency, Saitama, Japan ABSTRACT Thermoelectric conversion becomes more and more important for the effective usage of large amount of wasted heat. Thermocell is one of the thermoelectric conversion system that utilize the shift of equilibrium redox potential emerging by difference of temperature, and attracts much interest due to the high voltage per unit temperature difference (Seebeck coefficient, Se). Recently Pringle, Macfarlane and coworkers reported high Se of over 2 mV 1 / K by Co(bpy)3 complex in organic solvent. We introduced host–guest chemistry in the thermocell. High Se of 2.0 mV / K was achieved in aqueous solution by introducing α- − – 2 cyclodextrin (α-CD) into a thermocell consisting of an aqueous redox pair of I and I3 . The − α-CD encapsulates I3 selectively at cold side of the cell and releases it at elevated − temperature, and the difference of concentration of I3 evokes the voltage in addition to the conventional thermocell. Here we report the supramolecular chemistry to another thermocell consisting of ferrocene + monocarboxylic acid (1). We evaluated the Se value of the thermocell of 1 / 1 , and it increases with addition of β-CD. β-CD is known to show selective host–guest interaction with ferrocene, which enhance the Se of the cell. This result shows the versatility of the supramolecular strategy for the thermocell. [1] T. J. Abraham, D. R. MacFarlane, J. M. Pringle, Energy Environ. Sci., 2013, 2639. [2] H. Zhou, T. Yamada, N. Kimizuka, J. Am. Chem. Soc., 2016, 10502 172 SYMMETRY STRATEGY TOWARDS HIGH-PERFORMANCE SINGLE- MOLECULE MAGNETS Liu, J-L1, Chen, Y-C1, Liu, J1, Wernsdorfer, W2, Chibotaru, L F3, Tong, M-L1 Email: [email protected] 1 Sun Yat-Sen University, Guangzhou, P. R. China 2 Institut Néel, CNRS & Université Joseph Fournier, Grenoble, France 3 Katholieke Universiteit Leuven, Leuven, Belgium Inspired by the large intrinsic magnetic anisotropy of lanthanide ions, great synthetic efforts have been devoted to, not only the pure 4f single-molecule magnets (SMM), but also d-f SMMs since 2003. We have focused on the employment of molecular engineering and magnetic engineering to synthesis novel molecular magnets with large magnetic reversal barrier and high blocking temperature. Herein we pursue the pentagonal bipyramidal symmetry to supress the QTM and present pentagonal bipyramidal lanthanide(III) SIMs, in which the lanthanide centres with D5h symmetry can hold both large energy barriers and record magnetic hysteresis temperature up to 20 K as suggested by ab initio calculations 173 Synthesis and luminescence of Cu(I) and Zn(II) halide complexes with 6- (hydroxyphenyl)pyrimidines Katerina A. Vinogradova,1,2 Alexey S. Berezin,1 Viktor P. Krivopalov,3 Elena B. Nikolaenkova,3 Dmitrii Yu. Naumov,1,2 Natalia V. Pervukhina,1 Arkady S. Kupryakov,4 Marianna I. Rakhmanova,1 Danila B. Kal’nyi,1,2 and Mark B. Bushuev1,2 Presenting author’s e-mail: [email protected] 1 Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Akad. Lavrentiev Ave., Novosibirsk, 630090, Russia 2 Novosibirsk State University, 2, Pirogova str., Novosibirsk, 630090, Russia 3 N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, 9, Akad. Lavrentiev Ave., Novosibirsk, Russia 4 Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences, 3, Institutskaya str., Novosibirsk, 630090, Russia Emissive organic compounds and metal complexes having short intramolecular hydrogen bonds have attracted great attention due to possibilities of excited-state intramolecular proton transfer (ESIPT). ESIPT-emissive fluorophores tend to show large Stokes shifts, dual emission, etc. Working with pyrimidine derivatives, we introduced a hydroxyphenyl substituent in the C6 position of the pyrimidine ring and synthesized two hybrid ligands, 4-(3,5-diphenyl-1H- pyrazol-1-yl)-6-(hydroxyphenyl)pyrimidine (HL1) and 4-(3,5-dimethyl-1H-pyrazol-1-yl)-6- 2 n (hydroxyphenyl)pyrimidine (HL ), two mononuclear zinc(II) complexes, [Zn(HL )Cl2], and n n four Cu(I) complexes, [Cu2(HL )2I2] and [Cu(HL )(PPh3)I], (n = 1 ,2, Fig 1.). According to X- ray single crystal data, both free ligands and their complexes have a very short intramolecular OH…N hydrogen bond (O…N 2.58 – 2.61 Å). Fig. 1. Scheme of synthesis of complexes In the solid state free ligands HL1 and HL2 и copper(I) complexes show one broad 1 emission band in the yellow region of spectrum (λmax = 590 nm for HL and 550 nm for nm 2 HL ; λmax = 650-680 nm for complexes). Upon excitation at 300 nm both complexes demonstrate red emission (λmax = 650 nm), whereas upon excitation at 450 nm they show yellow emission (λmax = 560 nm). Emission of complexes and ligands in solutions strongly depends on solvent. DFT calculations (B3LYP/TZP) of the excited states of ligands and Zn(II) complexes predict intramolecular proton transfer upon excitation. 174 Synthesis of chirality specific SWCNTs with potential Perovskite Solar-Cell applications Sharali Malik,1 Masooma Ibrahim,1 Annie Powell1,2 Presenting author’s e-mail: [email protected] 1Karlsruhe Institute of Technology, Institute of Nanotechnology, D-76131 Karlsruhe, Germany, 2Karlsruhe Institute of Technology, Institute of Inorganic Chemistry, D-76131 Karlsruhe, Germany. ABSTRACT TEXT Carbon Nanotubes have potential applications for photovoltaics because of their excellent optical and electronic properties. Their application to the field of stable perovskite solar cells is increasing as organo-lead halide perovskites with a direct bandgap play important roles in solar cells not only as strong light harvesters, but also as efficient carrier conductors because of their large absorption coefficients and high charge carrier mobilities. For the reasons of high conductivity, and chemical stability single-walled carbon nanotubes (SWNTs) make excellent candidates as charge transporting materials in optoelectronic devices and are being extensively studied for photovoltaic applications. However, it is well known that small changes in the diameter and chiral indices (n, m) of single-walled carbon nanotubes (SWCNTs) will change the bandgap. Therefore, the production of just one type of SWCNT by controlling its structure during growth is an important goal. Here we show, that by using the protocol described by Yan Li et al. (Nature. 2014, 510, 522), we have produced template growth of SWNTs with a specific (n, m) by using a range of new nanocrystal polyoxometalate (POM) based catalysts synthesized in our laboratory. Thus, it is envisaged that the performance of perovskite solar cells can be enhanced by the usage of single diameter SWCNTs and this will be the ultimate goal of these studies. 175 SYNTHESIS OF COORDINATION AND ORGANOMETALLIC COMPOUNDS BASED ON POLY(AZOLYL)ALKANE LIGANDS Semitut, E1,2, Zatonskaya, L3, Sukhikh, T2,4, Potapov, A.1,3 Presenting author’s e-mail: [email protected] 1 Tomsk Polytechnic University, Tomsk, Russia 2 Nikolaev Institute of Inorganic Chemistry, Novosibirsk, Russia 3 Altai State Technical University, Barnaul, Russia 4 Novosibirsk State University, Novosibirsk, Russia First examples of discrete molecular complexes and linear coordination polymers from a bitopic 1,1,2,2-tetrakis(pyrazol-1-yl)ethane (Pz4) ligand and transition metal ions were prepared and structurally characterized. Depending on metal-to-ligand ratio and reaction conditions copper(II) nitrate formed dinuclear molecular complexes or two types of linear coordination polymers – 1D metal-ligand chains or ladder-type copper-nitrate double chains with bridging Pz4 ligands. Silver(I) formed only 1D coordination polymers of different structures. Pyrazolium salts based on bis(4-iodopyrazol-1-yl)alkanes were used to prepare new types of mesoionic N-heterocyclic carbene palladium(II) complexes, in which palladium ions are coordinate bis(pyrazol-1-yl)alkane ligands through carbene center of on pyrazole cycle and nitrogen atom of another cycle forming a bimetallomacrocycle. Coordination sphere of palladium is completed to square planar by two additional iodine atoms. As far as we are aware, structures of this type has never been observed before for mesoionic carbene complexes. Bis(1,2,4-triazol-1-yl)alkanes with zinc and cadmium ions formed a variety of coordination polymers of different topologies – 1D, 2D and 3D structures, including porous coordination polymers. Structural peculiarities and properties of all newly synthesized compounds will be discussed. The reported study was supported by the Russian Science Foundation, grant No. 15-13- 10023. 176 Synthesis of Ene-Diamido Rare-earth Complexes and Their Catalytic Applications Li, J. –F.,1 Liu, J.,1 Cui, C.1,2 Presenting author’s e-mail: [email protected] 1State Key Laboratory of Elmento-Organic Chemistry, Nankai University, Tianjin, China 2Collaborative Innovation Center Of Chemical Science and Engineering (Tianjin), Tianjin 300072, China Well-defined rare-earth complexes have emerged as powerful catalysts for a number of transformations given their unique selectivity and mechanistic distinctions derived from the high electrophicility of rare-earth centers.1 Herein, we report the synthesis and characterization of rare-earth ene-diamido complexes and their applications in selective catalytic hydrosilylation, hydrophosphination and polymerization of styrenes. These complexes exhibit high regioselectivity and stereoselectvity for these important transformations. The samarium methoxide 1 appeared to be the most regioselective catalyst for hydrosilylation of both styrenes and non-activated alkenes reported so far. In addition, polymerization of styrene led to the formation of silyl-capped, highly syndiotactic polystyrene. The experiments and density functional theory (DFT) calculations disclosed the highly selective formation of the samarium hydride intermediates, which, in combination with the electronic and steric factors of the ligand, is responsible for the high regio- and stereoselectivity. In addition, the corresponding samarium alkyl complex enabled highly regioselective hydrosilylation of internal alkenes. Reference (1) (a) Molander, G. A.; Romero, J. A. C. Chem. Rev. 2002, 102, 2161. (b) Gottfriedsen, J.; Edelmann, F. T. Coord. Chem. Rev. 2006, 250, 2347. (c) Edelmann, F. T. Coord. Chem. Rev. 2006, 250, 2511. (2) Li, J.; Zhao C.; Liu, J.; Huang, H.; Wang, F.; Xu, X.; Cui. C. Inorg. Chem. 2016, 55, 9105. 177 SYNTHESIS OF NEW HETEROBIMETALLIC LANTHANOID CLUSTERS AND THEIR LUMINESCENCE PROPERTIES Bousrez, G1, Werrett, M2, Thielemann, D2, Andrews, P2, Junk, P1 1 James Cook University, Townsville, Queensland, Australia 2 Monash University, Clayton, Victoria, Australia The X-ray computed tomography (CT) is a non-invasive method for the visualization of in vivo tissue surfaces by means of optical contrast based on tissue-specific X-ray attenuation, and serves therefore as a major imaging modality in clinical radiology. To obtain a good CT attenuation a good contrast agent is necessary. New contrast media based on metal complexes, particular metals have the potential to provide CT attenuation like the rare earth metals (Scandium, Yttrium and Lanthanoids). Complexes with a “cage” structure can provide, once encapsulated, the required stability and solubility. We report here the synthesis of new mono- and bimetallic lanthanoid cluster compounds. The metal-to metal ratios of pentanuclear clusters were determined by energy dispersive X-ray spectroscopy (EDS). The EDS results show that, for an equal proportion of lanthanide salts introduced, different metal-to-metal ratios are achieved in the clusters. This ratio appears to be dependent on the size and electron density of the metal atoms. Studies realized the best conditions to achieve a 1:1 ratio. A luminescence study of the clusters will be presented and will show the influence of each metal centre. 178 Synthesis, characterisation, and properties of p-cymene Ruthenium(II) 6 tetracarboxylate bipyridine complexes [(ƞ -p-cymene)Ru(Rn,Rnˊ-tcbpy)Cl][Cl] Rüther, T1, Woodward, C P1, Jones, T W2, Coghlan, C J1, Hebting, Y3, Cordiner, R L3, Dawson, R E3, Robinson, D E J E3, Wilson, G J2 Presenting author’s e-mail: [email protected] 1 CSIRO Energy, Clayton, Australia 2 CSIRO Energy, Newcastle, Australia 3 Dyesol Australia Pty Ltd, Queanbeyan, Australia The detailed investigation of organometallic half-sandwich ƞ6-arene-ruthenium(II) complexes led to their successful development for a wide range of applications including anti-cancer and antibacterial drugs, ring-opening metathesis, alkene polymerization, olefin oxidation, hydrogen transfer catalyst precursors, oxidative water splitting and as a convenient starting material for generating stable and redox active photosensitizers for dye sensitized solar cells which was the starting point of the present work. We present the synthesis and properties of the new ruthenium complexes [(ƞ6-p- cymene)Ru(L)Cl][Cl] prepared from tetracarboxylic acid ligands L = 3,3ˊ,4,4ˊ- tetracarboxylic acid-2,2ˊ-bipyridine (3,3ˊ,4,4ˊ-H4tcbpy), their methyl and ethyl ester derivatives (R4tcbpy), and 4,4ˊ-di-n-nonylbipyridine (4,4ˊ-dnbpy). The complexes were fully characterized by NMR, IR, MS, elemental analysis, UV/vis spectroscopy, and cyclic 6 voltammetry. The single-crystal structure of [(ƞ -p-cymene)Ru(4,4ˊ,5,5ˊ-H4tcbpy)Cl][Cl] 2 shows a ‘piano stool’ geometry with Ru-C, Ru-N distances and an N-Ru-N bond angle (77.4) similar to equivalents in the 4,4ˊ-dicarboxylic acid sister complex. Compared to the latter and also the 4,4ˊ-dnbpy derivative 3, the UV/vis spectra show MLTC absorptions of the tetracarboxylates shifted favourably, in terms of photochemical applications, to lower energy. Depending on the ligand substitution, the CVs show Ru(II/III) oxidation processes at 0.56−0.98 V (vs Fc/Fc+). Changes in the electronic situation at the Ru centre reflected in the UV/vis and voltametric data are correlated to HOMO levels calculated from photoelectron spectroscopy spectra recorded for all complexes. 179 A unique feature revealed in NMR experiments is rapid ligand dissociation and/or decarboxylation in DMF, the latter leading to the clean isolation of the 4,4ˊ-dicarboxylic acid complex derivative. 180 Synthesis, Structure and Application of Titanium-Oxo Clusters Zhang, L Fujian Institute of Research on the Structure of Matter, Fuzhou, China ABSTRACT TEXT Water-splitting hydrogen production has been considered to be a promising solution for the global energy and environment crisis. TiO2 is a widely applied photocatalyst in this area [1]. As its model complexes, titanium-oxo clusters (TOCs) have also attracted increasing interest during the past decades [2]. To prepare new kinds of TOCs, we applied esterification reactions between carboxylates and alcohols to control the water amounts during the hydrolysis of isopropyl titanate. With this novel synthetic strategy, the first fullerene-type TOC and the largest Ti52-oxo cluster reported to date have been prepared [3,4]. Taking advantages of the labile coordination sites, we systemically investigated the influence of organic ligands and transition metal ions on the bandgaps of TOCs [5]. Moreover, we have also developed several effective protocols for the construction of TOCs based composite materials with excellent visible-light driven H2 evolution activities [6,7]. As a further step, we now report a new cluster-doping model that can allow the combination of titanium-oxo clusters with large polymetallic cluster, resulting in an effective increment of sunlight absorption. Moreover, the application of TOCs as single-source precursors for the fabrication of TiO2 will also be presented, where the improvement of photocatalytic H2 generation behaviors is achieved by ligands effect on TOCs. References [1] X. Chen, S. S. Mao, Chem. Rev. 2007, 107, 2891. [2] P. Coppens, Y. Chen, E. Trzop, Chem. Rev. 2014, 114, 9645. [3] M. Y. Gao, F. Wang, Z. G. Gu, D. X. Zhang, L. Zhang, J. Zhang, J. Am. Chem. Soc. 2016, 138, 2556. [4] W. H. Fang, L. Zhang, J. Zhang, J. Am. Chem. Soc. 2016, 138, 7480. [5] J. X. Liu, M. Y. Gao, W. H. Fang, L. Zhang, J. Zhang, Angew. Chem. Int. Ed. 2016, 55, 5160. [6] Z. G. Gu, H. Fu, T. Neumann, Z. X. Xu, W. Q. Fu, W. Wenzel, L. Zhang, J. Zhang, C. Wöll, ACS Nano 2016, 10, 977. [7] Z. Jiang, J. Liu, M. Gao, X. Fan, L. Zhang, J. Zhang, Adv. Mater. 2017, 29, 1603369. 181 Synthesis, Structure, and Superoxide Dismutase Activity of Salen- Manganese(III) Perchlorate Complex Deawati, Y1,2, Bustaman, I S K1, Onggo, D1, Mulyani, I1, Hastiawan, I2, Nurrahmajanti, A1, Lönnecke, P3, Hey-Hawkins, E3 Presenting author’s e-mail: [email protected], [email protected] 1 Institut Teknologi Bandung, Bandung, West Java, Indonesia 2 Universitas Padjadjaran, Bandung, West Java, Indonesia 3 Universität Leipzig, Leipzig, Saxony, Germany ABSTRACT TEXT One dimeric salen-manganese(III) complex, [Mn2(salen)2(EtOH)1.4(H2O)0.6](ClO4)2 .1 EtOH.0.6 MeOH, has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, electrospray-ionization mass spectrometry, infrared spectroscopy, and room temperature magnetic susceptibility measurement. The complex was synthesized from MnCl2.4H2O and H2salen in methanol solution following by an addition of NaClO4 saturated water solution. The product yielded 78-82% dark brown crystals indicative of the presence of manganese(III) metal ions. An elemental analysis showed that the compound contained: C = 42.10%; H = 3.64%; and N = 6.16%. It proved that the formula structure of the complex is C37,4H46N4O15,6Cl2Mn2. The complex is paramagnetic at room temperature with the magnetic moment of 5.0 BM. The single crystal of the complex has been grown in ethanolic solution. A suitable size of crystal has been solved as a dimeric structure of the complex. Each of the two Mn center is octahedrally coordinated with the equatorial positions being occupied by the salen ligand, while the axial positions are occupied by the two Mn-O bridge which link the dimeric unit, water, and ethanol molecules from the solvent used. The two positive charges are neutralized by – ClO4 anions located between the chains. Superoxide dismutase activity of the complex has been measured by indirect non-enzymatic assay of photoreduction riboflavin-nitroblue tetrazolium (NBT). The complex is capable to scavange superoxide anion radical produced by illumination of riboflavin, thereby competing with NBT as indicator. The assay showed that the [Mn2(salen)2(EtOH)1.4(H2O)0.6](ClO4)2 .1 EtOH.0.6 MeOH complex with a concentration of 0.8 ± 0.1 µM can inhibit as much as 50% of NBT works. Keywords: dimeric, salen-manganese(III), perchlorate, superoxide dismutase, non-enzymatic, riboflavin-NBT, photoreduction 182 TACN LIGANDS – A JOURNEY TROUGH RADIOPHARMACEUTICAL APPLICATIONS Stephan, H1, Graham, B2, Spiccia, L2 Presenting author’s e-mail: [email protected] 1 Helmholtz-Zentrum Dresden-Rossendorf, Dresden, Germany 2 Monash University, Melbourne, Australia The design of tailor-made bifunctional copper radionuclide-complexing agents for nuclear medical application as well as acquisition of reliable information about the biodistribution of different materials represents an intensive and rapidly developing field of research. In this context, the tridentate macrocycle 1,4,7-triazacyclononane (TACN) is of special interest since it forms stable complexes with Cu(II) and the ligand structure can be easily modified. The introduction of further donor groups on the ligand scaffold, such as pyridine units, significantly enhances the thermodynamic stability as well as the kinetic inertness of the Cu(II) complexes formed. TACN ligands containing one or two pendant 2-picolyl arms prefer the formation of square-pyramidal coordination geometry with Cu(II). A hexadentate ligand with two picoline coordination groups as well as a carboxylic functionality, 2-[4,7- bis(2-pyridylmethyl)-1,4,7-triazacyclononan-1-yl]acetic acid (DMPTACN-COOH), enforces a six-coordinate, distorted octahedral structure. DMPTACN-based ligands rapidly chelate copper(II) radionuclides under ambient conditions and the resulting complexes show high in vivo stability. The carboxylic acid group in DMPTACN-COOH allows for the ready introduction of linker groups, such as maleimide or isothiocyanate, thereby facilitating coupling of targeting molecules and bio(nano)materials. Examples of target-specific peptides and bio(nano)materials equipped with DMPTACN ligands for labeling with 64Cu as an ideal positron emitter are discussed. This enables tumor imaging and the biodistribution of the materials to be studied over a period of days via positron emission tomography (PET). 183 Templation of a 2D Coordination Network by a 3D Network Abrahams C. T.,1 Abrahams, B. F.,2 Hudson, T. A.2 Robson, R.,2 1 La Trobe University, Bundoora, Australia 2 University of Melbourne, Parkville, Australia 2- The sulfite ion, SO3 is able to provide a reducing environment in water in which ions such as Cu(I) can exist. If air is excluded, then it is possible to isolate Cu(I) species from such solutions. Exposure of these solutions to the atmosphere leads to slow oxidation of both the sulfite and Cu(I) ions, making it possible to obtain mixed Cu(I)-Cu(II) complexes. The addition of an ethanolic solution of 4,4'bipyridine (4,4-bipy) to an aqueous solution of 7- Cu(SO3)4 yields block-shaped crystals which form upon slow oxidation by O2 from the atmosphere. Quite remarkably, the crystals are orange in the centre and blue on the outside (see photograph below). The orange crystal was found to be a 3D Cu(I)-Cu(II) I II coordination polymer of composition, [Cu Cu (4,4’bipy)4(H2O)2]-(S2O6)(NO3)·H2O. From a topological perspective, the 3D cationic framework has the PtS topology and the overall structure consists of four interpenetrating PtS networks. The blue component of the crystalline blocks does not contain any Cu(I) and has the II formula: [Cu (4,4’bipy)2(H2O)2](S2O6). This structure consists of square grid sheets of II [Cu (4,4’bipy)2(H2O)2], which interpenetrate. It would appear that orange Cu(I)-Cu(II) crystals are able to serve as templates for the blue crystals which begin to form when the all of the Cu(I) has been oxidised. The identification of structural and geometric relationships between the two coordination networks provides a rationale for the formation of these unusual composite crystals. 184 The Development of an Electronic-Structure Relationship in Metal-Alkynyl Spiropyran Complexes Jago, D1, Gluyas, J1, Wild, D1, Low, P1, Koutsantonis, G1. Presenting author’s e-mail: [email protected] Affiliations 1Chemistry, School of Molecular Science, University of Western Australia, Crawley, Australia Molecular electronics (ME) seeks to employ individual molecules to perform the tasks analogous to components in electronic devices, such as wires, switches and diodes. The spiropyran is a photochromic molecule that is beginning to be explored as a rectifier candidate in ME. Two complexes, one iron and one ruthenium were able to be synthesised by implementing similar literature protocols and were fully characterised. The Cp*Ru(dppe) based spiropyran complex showed considerable stability under oxidation. Spectroelectrochemical analysis showed that charge transfer was pertubated from the metal to the ligand with change in oxidation state. The Cp*Fe(dppe) based spiropyran complex displayed properties that indicate a change in equilibrium of spiropyran to merocyanine form, with the merocyanine gaining stability. However, this resulted in a loss of photochromic behaviour. A gold (I) based spiropyran complex was also synthesised as means to provide a transmetallation route due to the difficulties seen in the synthesis of alternative analogues. This complex displayed high stability and a loss of alkynyl infra-red stretch indicates similar mesomeric properties of the substituents. This initial investigation of metal complexed spiropyran provides ground work to build an understanding of how the spiropyran will behave as a molecular rectifier. Some unique behaviour was dependent on coupling strength based on the interaction with ruthenium or iron. 185 The Development of Hydroxamic Acid-based and 2-hydroxyisophthalamide-based Chelates for PET Imaging Karmis, R.E.1, Barnard, P.J.2 1 Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University, Bundoora, VIC, 3083, Australia. Positron emission tomography (PET) is a sensitive imaging modality that allows for the quantitative analysis of physiological and biochemical functions and processes in living organisms.1 The use of positron-emitting metal ions with longer half-lives such as zirconium-89 (89Zr) and gallium-68 (68Ga) allows for the use of large molecular weight targeting agents such as monoclonal antibodies.2 The design of bifunctional chelating agents (BFCs) to coordinate these metal ions with high affinity and stability that may be coupled to a biological vector is a key goal for the development of new improved imaging agents. Nature has provided siderophores which are produced and released by microbes to sequester and solubilize iron(III) from their surrounding environment. Siderophores have been found to chelate Zr(IV) and Ga(III) with high-selectivity and affinity, thus making them attractive for the development of PET imaging agents.3 A series of siderophore analogs have been synthesized baring the hydroxamate moiety in which the ligand systems contain tertiary substituted nitrogen atoms, providing stable structures. A second series of ligands containing the 2-hydroxyisophthalamide chromophore (IAM), which is a similar unit to the naturally occurring catecholate class of siderophores, have also been prepared which are isosteric structures of the naturally occurring enterobactin. The synthesis of these new molecules and their coordination chemical properties will be discussed. References [1] Simecek, J.; Schulz, M.; Notni, J.; Plutnar, J.; Kubicek, V.; Havlickova, J.; Hermann, P. Inorg. Chem. 2012, 51, 577. [2] Guerard, F.; Lee, Y. S.; Brechbiel, M. W. Chemistry 2014, 20, 5584. [3] Gorden, A. E.; Xu, J.; Raymond, K. N.; Durbin, P. Chem. Rev. 2003, 103, 4207 186 THE POWER OF THE COORDINATION CLUSTER Annie K. Powell [email protected] Institute of Inorganic Chemistry, KIT, Karlsruhe, Germany The concepts of coordination chemistry developed by Alfred Werner at the beginning of the 20th century were finally substantiated by the realisation that a metal centre can invoke chirality by providing a central anchor-point to fix achiral ligands into a chiral structure. This is demonstrated easily with bidentate ligands which form tris-chelates, adopting either left- or right-handed propeller structures. Thus metal centres play an important role in terms of influencing the potential chirality of a given system. This lecture will take examples from some of our recent work to illustrate these fascinating, but sometimes challenging, points. For example, intriguing chiral separations can be achieved when racemates of chiral ligands are used.[1] Furthermore, in addition to structural chirality induced by the presence of metal ions, we can consider the implications for the fourth dimension in terms of time-reversal symmetry with a particular perspective on magnetic behaviour.[2] [1] Ringing the changes in FeIII/YbIII cyclic coordination clusters, A. Baniodeh, C. E. Anson, A. K. Powell, Chem. Sci., 2013, 4, 4354–4361. [2] (a) Spin chirality in a molecular dysprosium triangle. The archetype of the noncollinear Ising model, J. Luzon, K. Bernot, I.J. Hewitt, C. E. Anson, A. K. Powell, R. Sessoli, Phys. Rev. Lett., 2008, 100, 247205; (b) Heterometallic CuII/DyIII 1D chiral polymers: chirogenesis and exchange coupling of toroidal moments in trinuclear Dy3 single molecule magnets, G. Novitchi, G. Pilet, L. Ungur, V. V. Moshchalkov, W. Wernsdorfer, L. F. Chibotaru, D. Luneau, A. K. Powell, Chem. Sci,, 2012, 3, 1169-1176; (c) Ligand field variations: tuning the toroidal moment of Dy6 rings, A. Baniodeh, N. Magnani, S. Bräse, C. E. Anson, A. K. Powell, Dalton Trans. 2015, 44, 6343-6347. 187 The Rich Chemistry of 1,1'-Bifunctional Octamethylferrocenes Max Roemer1, Duncan Wild1, Brian W. Skelton1,2, Alexandre N. Sobolev2, Gareth L. Nealon2, Matthew J. Piggott1 and George A. Koutsantonis1 Email: [email protected] 1 The University of Western Australia (UWA), Crawley, Australia 2 Centre for Microscopy, Characterisation and Analysis, UWA, Crawley, Australia Friedel-Crafts reactions have been essentially overlooked as a means for functionalisation of octamethylferrocene. We show that preparation of the hitherto unknown 1,1'- diacetyloctamethylferrocene (1) is facile under standard Friedel-Crafts acylation conditions using an appropriate work-up procedure. Chloroformylation of 1 affords an array of formylation products, including 1,1'-bis-(1-chlorovinyl) ferrocene (2) in high yield (Scheme 1).[1] Scheme 1. Synthesis of 1,1'-bis-(1-chlorovinyl) ferrocene (2) by chloroformylation. Reaction of compound 2 in DMF/NaOH yields a number of electron rich ferrocenophanes, including complex dimethylamino-ferrocenophanes 3a and 3b (Fig. 1). The product distribution depends on a variety of factors. We achieved control over the complicated system by altering the amount of NaOH the adjustment of which leads to either formation of 3a in high yield, or 3b in moderate yield. The initial step in the transformation is in-situ generation of an alkyne from 2, followed by cyclisation and further transformation into 3a by reaction with dimethylamine, generated from base induced decomposition of DMF. Under low concentrations of NaOH, 3a undergoes a cyclisation with unreacted alkyne intermediate to form 3b. The asymmetric derivative 3b forms with high diastereoselectivity. Based on control experiments and DFT calculations, we propose a mechanism involving a cascade of cyclisation reactions. Fig. 1. Formation of electron rich ferrocenophanes from 2 by unusual cyclisation reactions. [1] M. Roemer, B. W. Skelton, M. J. Piggott, G. A. Koutsantonis, Dalton Trans. 2016, 45, 18817-18821. 188 THEORETICAL STUDIES OF MIXED-VALENCE ORGANOMETALLIC SPECIES FOR POTENTIAL UTILIZATION AS QUANTUM CELLULAR AUTOMATA Thomas Groizard, Samia Kahlal, and Jean-François Halet* Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1- Ecole Nationale Supérieure de Chimie de Rennes, Avenue du Général Leclerc, F-35042 Rennes, France E-mail: [email protected] The chemistry of mixed-valence complexes1 joins that of molecular electronics in the quantum cellular automata (QCA) paradigm,2 a concept which has been demonstrated to be a possible alternative to the transistor-based technology, in which binary information is encoded in the configuration of charge among redox-active molecular sites.3 Indeed, the simplest molecular QCA cell is a symmetric mixed-valence system in which the binary states are represented by the location of a mobile electron at one center or the other. Experimental and theoretical efforts have recently been devoted to molecular mixed- valence organometallic systems containing two and four metal centers as candidates for QCA.4 Properties of specific examples based on recently synthesized5 (Scheme 1) and hypothetical ruthenium and iron molecules6 will theoretically be analyzed and discussed with the aid of DFT calculations. Ph P 2 PPh Ph P 2 PPh 2 Fe C C C C C C Fe 2 Ru Ph2P Ph2P C PPh PPh 2 Ru 2 (PF ) Ph P Ru C C C C C C C C 6 2 2 C Ph2P PPh2 C PPh C Fe C C C C C C Ru 2 Ph2P Ru PPh PPh 2 2 Ph2P Scheme 1. An example of a mixed-valence [Ru(II)2Ru(III)2] organometallic complex for potential QCA application.5 1. (a) P. J. Low, Coord. Chem. Rev. 2013, 257, 1507; (b) J.-P. Launay, Coord. Chem. Rev. 2013, 257, 1544; (c) J.-F. Halet, C. Lapinte, Coord. Chem. Rev. 2013, 257, 1584; (d) M. Parthey, M. Kaupp, Chem. Soc. Rev. 2014, 43, 5067. 2. (a) C. S. Lent, P. D. Tougaw, W. Porod, G. H. Bernstein, Nanotechnology 1993, 4, 49; (b) P. D. Tougaw, C. S. Lent, W. J. Porod, J. Appl. Phys. 1993, 74, 3558. 3. A. O. Orlov, I. Amlani, G. H. Bernstein, C. S. Lent, G. L. Snider, Science 1997, 277, 92; (b) I. Amlani, A. O. Orlov, G. Toth, G. H. Bernstein, C. S. Lent, G. L. Snider, Science 1999, 284, 289. 4. See for example J. Jiao, G. J. Long, L. Rebbouh, F. Grandjean, A. M. Beatty, T. P Fehlner, J. Am. Chem. Soc. 2005, 127, 17819. 5. A. Burgun, F. Gendron, P. A. Schauer, B. A.; Skelton, P. J. Low, K. Costuas, J.-F. Halet, M. I. Bruce, C. Lapinte, Organometallics 2013, 32, 5015. 6. T. Groizard, S. Kahlal, J.-F. Halet J. Organomet. Chem. 2017, 00, 000 (DOI: 10.1016/j.jorganchem.2017.02.021). 189 TOWARDS STABLE TRANSITION METAL ALKANE COMPLEXES Ball, GE1 Presenting author’s e-mail: [email protected] 1 University of New South Wales, Sydney, Australia ABSTRACT TEXT This presentation will describe our efforts to create more stable transition metal–alkane complexes, through the use of cationic metal centres. In this regard, we have generated cationic alkane complexes of the type f 6 [(HEB)Re(CO)2(alkane)][Al(OR )4] (HEB = η -hexaethylbenzene; alkane = cyclopentane or pentane; ORf = perfluoro-tert-butoxy) via photolysis of the precursor complex f 1 [(HEB)Re(CO)3][Al(OR )4] in the presence of the added alkane. Key to the success of this chemistry is the use of a solvent that binds to the metal centre more weakly than the alkane itself. In this case, the alkane complexes were generated in a hydrofluorocarbon (HFC) solvent, most often CF3CH2CF3, which is capable of simultaneously dissolving some ionic complexes and a small amount of alkane at low temperature (183 K). Use of the HFC solvent in tandem with the highly fluorinated, f − solubilizing, weakly coordinating Krossing anion, [Al(OR )4] , overcomes the technical difficulty of combining ionic species with alkanes in solution without the solvent molecules rapidly displacing the bound alkane ligand. More recent advances towards stabilizing transition metal–alkane complexes will also be presented. 1. H. M. Yau, A. I. McKay, H. Hesse, R. Xu, M. He, C. E. Holt and G. E. Ball, J. Am. Chem. Soc. 2016, 138, 281-288. 190 Triangles, guest sensors, immobilised SMMs, and active catalysts Sally Brooker e-mail: [email protected] Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, P.O. Box 56, Dunedin 9054, NZ Design of polydentate ligands, including macrocycles, which provide control over metal ion environments, is a long standing interest in my research group. The resulting complexes have many potential applications due to the reversible redox, spin crossover (SCO), single molecule magnetism (SMM), fluorescence, or catalytic activity exhibited. This talk will focus on four areas of recent activity (Figure): (a) breaking the ‘rules‘: unexpected self assembly of triangles, not [2x2] grids.1 (b) spin crossover:2 the first demonstration of reversible quantitative guest sensing by an SCO-active material,3 and a colourful cycle of ‘three guests three colours‘ sensing involving single-crystal-to-single-crystal transformations.4 (c) immobilisation of SMMs onto solid supports.5 (d) diphenylamine-based [2+2] imine macrocycles6 for (i) ‘turn-on fluorescence‘ detection of zinc7 and (ii) stable dizinc complexes as hyperactive catalysts for lactide polymerisation (in collaboration with Professor Williams).8 References 1 R. W. Hogue, S. Dhers, R. M. Hellyer, J. Luo, G. S. Hanan, D. S. Larsen, A. L. Garden and S. Brooker, J. Am. Chem. Soc., 2017, submitted. 2 P. Gütlich and H. A. Goodwin, Top. Curr. Chem., 2004, 233, 1; S. Brooker, Chem. Soc. Rev., 2015, 44, 2880. 3 R. G. Miller and S. Brooker, Chem. Sci., 2016, 7, 2501. 4 S. Rodríguez‐Jiménez, H. L. C. Feltham and S. Brooker, Angew. Chem. Int. Ed., 2016, 55, 15067. 5 H. L. C. Feltham, C. Dumas, M. Mannini, E. Otero, P. Sainctavit, R. Sessoli, C. J. Meledandri and S. Brooker, Chem. Eur. J., 2017, 23, 2517. 6 S. J. Malthus, S. A. Cameron and S. Brooker, Coord. Chem. Rev., 2016, 316, 125; S. A. Cameron and S. Brooker, Inorg. Chem., 2011, 50, 3697. 7 S. J. Malthus, S. A. Cameron and S. Brooker, 2017, in preparation. 191 8 A. Thevenon, C. Romain, M. S. Bennington, A. J. P. White, H. J. Davidson, S. Brooker and C. K. Williams, Angew. Chem. Int. Ed., 2016, 55, 8680; C. Romain, M. S. Bennington, A. J. P. White, C. K. Williams and S. Brooker, Inorg. Chem., 2015, 54, 11842. 192 Tuning the properties of molecular motors through metal complexation Wezenberg, S J1, Faulkner, A1, Feringa, B L1 Presenting author’s e-mail: [email protected] 1 Stratingh Institute for Chemistry, University of Groningen, Groningen, The Netherlands ABSTRACT TEXT Synthetic molecular rotary motors, in particular those that are driven by light, are highly promising for controlling the motion of nanoscale systems. To reach the same level of sophistication and complexity as is found in biological motors, however, it is crucial to design strategies that allow for dynamic modulation of the rotational behavior. Furthermore, light-driven molecular motors are typically operated by UV light, which is harmful to tissue and may cause material degradation. Strategies to shift the excitation wavelength to the visible range are therefore highly desired. To address these challenges, we have developed an overcrowded alkene-based molecular motor that is able to bind metal ions. Upon coordination to a ruthenium bipyridine complex, the photoisomerization process can be driven by visible (i.e. 450 nm) instead of UV light (ACIE 2015). Additionally we found that the rotational speed of this motor can be tuned via the reversible complexation with different transition metals (JACS 2016), which represents a significant step toward the integration of chemical regulation in light-operated nanomechanical devices. 193 While of interest as a possibly photoactive component of solid coordination polymers and frameworks, uranyl ion has coordination characteristics which favour the formation of layered structures assembling in three dimensions in ways leaving little space for substrate absorption. We have investigated, through crystal structure determinations, complexation of uranyl ion by a variety of polycarboxylates with different conformational preferences to see if this limitation can be overcome and have found in particular that the formation of heterometallic uranyl/(transiton or main group metal ion) complexes with such ligands can indeed lead to three-dimensional polymeric lattices. In some cases, however, the presence of an additional metal ion can lead to quenching of the uranyl ion luminescence. A promising approach to the formation of lattices containing three-dimensional cavities has been revealed in the formation of tetranuclear clusters with trans-1,2- cyclohexanedicarboxylate, although the cavity formed here is too small to accommodate polyatomic species. 194 Using Hypervalent Iodine To Unlock New Transition Metal Chemistry Dutton, J.L.1 Presenting author’s e-mail: [email protected] 1 La Trobe University, Melbourne, Australia ABSTRACT TEXT The use of hypervalent I(III) reagents for the oxidation of late transition metals is a topic of major interest. In particular the groups of Sanford and Ritter have used I(III) compounds such as PhICl2 and PhI(OAc)2 to access Pd(IV) complexes, which have been used mainly in stoichiometric and catalytic C-H activations. The Dutton group has been studying the use of dicationic I(III) complexes [PhI(pyridine)]2+ as oxidants for late metals for chemistry involving Pd(IV), Pt(IV) and Au(III). Most significantly we have used this method to synthesize homoleptic Au(III) trications, which represent a new family of gold compounds. These Au(III) trications can be used to access unique reactivity between gold and water, as well as an easy method to generate otherwise difficult to access Au(III) hydroxide, alkoxides and acetyloxy compounds simply using reagents as basic as water, methanol and acetic acid. 195 VIS-NIR PHOTOLUMINESCENCE MODULATION AND APPLICATION IN METAL- ORGANIC MATERIALS Pan, M, Zhang, LY, Chen, L, Yin, SY and Su, CY [email protected] Sun Yat-sen University, Guangzhou, China New metal-organic luminescent materials were designed and synthesized for multi-mode Vis-NIR modulation, energy transfer and conversion, as well as their application in opto- electronic devices such as OLEDs, opto-sensors, photocatalysis and anti-counterfeiting materials. Mono/poly/hetero-nuclear lanthanide/transition metal complexes or coordination polymers were designed, synthesized and their luminescence properties were thoroughly studied. The energy transfer models and light modulations of the luminescence in these complexes in the visible and near-infrared region via the excitation of OP (one-photon), TP (two-photon) or multi-photon absorptions were explored in detail, to understand the process and mechanism of the self-assembly of these metal-organic coordination materials, as well as their luminescence modulation, energy transfer, photoelectronic conversion, and device optimization. 196 WAVY-STACKED MACROCYCLIC HEXANUCLEAR COMPLEX CAPTURING GUEST MOLECULES VIA MULTIPOINT COORDINATION Nakamura, T, Kaneko, Y, Nishibori, E, Nabeshima, T [email protected]:[email protected] University of Tsukuba, Tsukuba, Japan A macrocyclic complex with an inner cavity surrounded by multiple metals works as a functional host molecule that captures guest molecules by coordination bonds. Such metallomacrocycles can be utilized for unique molecular recognition and for selective catalytic reactions. Here we introduce hexapap H61, a macrocyclic ligand with six inward N,N,O chelating moieties (Hpap). H61 was synthesized in 72% yield from a bifunctional monomer 2 that has o-aminophenol and acetal-protected 2-pyridinecarboxaldehyde units (Fig. a). Its hexanuclear zinc complex, Zn-hexapap [1Zn6Xn] (X = labile coordinating ligand), captured two molecules of pimelic acid (H2pim, HOOC(CH2)5COOH) in its cavity, and formed a wavy-stacked dimeric complex [12Zn12pim2Xn] (Fig. b,c). Furthermore, change of guest binding modes via multiple coordination bonds have been achieved utilizing acid/base as external stimuli. We will discuss the detailed structural analysis of the dimer of Zn- hexapap, and the regulation of the molecular recognition inside the wavy-stacked metallomacrocycle. Figure. (a) Synthesis of hexapap H61 and Zn-hexapap [1Zn6Xn]. (b) Binding of pimelic acid (H2pim) and formation of the wavy-stacked dimer. (c) The molecular structure of [12Zn12pim2(H2O)4Cl8] determined by X-ray crystallography. tBu groups and H atoms were omitted. 197 i J. M. Goicoechea and J. E. McGrady, Dalton Trans., 2015, 44, 6755. ii V. Arcisauskaite, D. Fijan, M. Spivak, C. de Graaf and J. E. McGrady. Phys. Chem. Chem. Phys., 2016, 18, 24006. 198 2D magnesium MOF with carboxyphosphonate ligand for sensoring Fe3+ ion Rongxin Yuan1，Yunsheng Ma1 E-mail: [email protected] 1School of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu, 215500, China Fe3+ ion is one of the most essential element for living organisms.1 The excess or deficient of Fe3+ ions will cause harmful effects on human health. Thus, the design of new fluorescent probes for Fe3+ ion is of great importance.2 Here, a 2-dimensional magnesium metal-organic framework (MOF) Mg(H2PCDC)2 (H3PCDC = 9-(2-(ethoxy(hydroxy)phosphoryl)ethyl) -9H- carbazole-3,6-dicarboxylic acid) was synthesized under hydrothermal condition and structurally characterized. The phosphonate groups link the adjacent Mg2+ ions to form an inorganic Mg–O–Mg chain, which are bridged by organic linker to form a 2D layer. Fe3+ ion can quench the luminescence entirely relative to other metal ions (Ag+, Al3+, Cd2+, Co2+, Cu2+, Pb2+, Zn2+) (Fig. 1). Considering this phenomenon, this compound may be used as a fluorescent probe for recognition of Fe3+ ion. Fig. 1 Structure (up) and emission spectra of Mg(H2PCDC)2 in the presence of different amount of Fe3+ ion (bottom) References (1) A. B. Bon, A. M. Costero, S. Gil, M. Parra, J. Soto, R. M. Máñez and F. Sancenón, Chem. Commun., 2012, 48, 3000-3002 (2) Z. Chen, Y.-W. Sun, L.-L. Zhang, D. Sun, F.-L. Liu, Q.-Q. Meng, R.-M. Wang and D.-F. Sun, Chem. Commun., 2013, 49, 11557-11559 199 Sky-blue Phosporescent Cyclometalated Iridium(III) Complexes Containing Carbazole-functionalized Carbene Ligand for Organic Light-Emitting Diodes (OLEDs): Energy Transfer from Carbazole Moiety to Iridium(III) Core Kim, Y-I1, Jeon, J1, Choi, J1, Jin, S-H1 e-mail: [email protected] 1 Department of Chemistry Education and Department of Chemical Materials, Graduate School, Pusan National University, Busan, Korea We synthesized and characterized cyclometalated heteroleptic iridium(III) complexes containing carbazole-functionalized carbene ligand ; tfpmpyIrchc (1), tfpmpyIrdfchc (2), dfpmpyIrimi (3), dfpmpyIrdfimi (4) ( tfpmpy = 4-methyl-2-(2,3,4-trifluoromethyl)pyridine ; chc = 1-phenyl-3-hexylcarbazolylimidazolin-2-ylidene; dfchc = 1-(2,4-difluorophenyl)-3- hexylcarbazolylimidazolin-2-ylidene ; dfpmpy = 2-(2,4-difluorophenyl)-4-methylpyridine ; imi = 3-hexyl-1-phenyl-1H-imidazol-3-ium ; dfimi = 1-(2,4-difluorophenyl)-3-hexyl-1H-imidazol- 3-ium). The photophysical and electrophysical properties of these complexes were investigated to apply for OLEDs. The photoluminescence(PL) spectra revealed that complexes (1), (2), (3) and (4) exhibited maximum emissions at 487, 474, 476(487sh.), 465(481sh.) nm with photoluminescence quantum yield (PLQY) of 74, 66, 24 and 44 % in dichloromethane solution, respectively. The emissions from the carbazole moiety at around 353 nm in solution were almost disappeared in films in (1) and (2), indicating that a Forster energy transfer from the carbazole moiety to the iridium(III) core was performed and resulted in an enhancement of luminescent efficiency. The OLED device based on complex (3) showed best performances of a maximum external quantum efficiency of 8.33 % with CIE coordinates of (0.16, 0.33) 1.0 1(sol) 2(sol) 1(film) 0.8 2(film) 0.6 0.4 0.2 Normalized PL Intensity PL Normalized 0.0 350 400 450 500 550 600 650 700 Wavelength (nm) 200 (E)-2-cyano-3-(4-(diphenylamino)phenyl) Acrylic Acid Extended-Conjugation Derivatives as Sensitizers for DSSCs Xu, M, Wang, H, Hu, X, Bao, B, Fang, J.-K* Nanjing University of Science and Technology, Nanjing, China As an efficient electron-donating group, triphenylamine motif is widely adopted in the organic dyes for dye-sensitized solar cells (DSSCs). To investigate the effects on dye property caused by the extended conjugation of electron donating group, three novel organic dyes (FWD1, FWD2 and FWD3) were synthesized by introducing extra phenyl units with different linkers (single bonds, double bonds and triple bonds, respectively) to the phenyl groups of (E)-2-cyano-3-(4-(diphenylamino)phenyl) acrylic acid. Starting from 4- (bis(4-iodophenyl)amino)benzaldehyde, single bonds, double bonds and triple bonds can be easily built by the Suzuki Reaction, Heck Reaction and Sonogashira Reaction, respectively. Following the Knoevenagel reaction, the (E)-2-cyano-3-(4- (diphenylamino)phenyl) Acrylic Acid Extended-Conjugation Derivatives were synthesized. These three dyes were characterized by 1H NMR, 13C NMR and HRMS, etc. The photophysical and electrochemical properties and photovoltaic parameters of DSSCs sensitized by these three dyes were systematically investigated. The results demonstrate that it is an efficient way to tune the molecular structures by adopting different linkers, which exhibit a significant influence on the dye performance. Furthermore, we can utilize this strategy to develop novel organic dyes for DSSCs. This work was supported by the Natural Science Foundation of Jiangsu Province (BK20140780). 201 2-(Pyridin-2-ylamino)naphtho[2,3-b]furan-4,9-diones as Novel Chemosensors Selectively Binding Hg2+ Ion Zhang, X1, Zhou, Z1,2 1 Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, China 2 Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, China Naphtho[2,3-b]furan-4,9-diones are privileged structural motifs of numerous natural products and synthetic analogues.1 Many of these derivatives exhibit diverse biological activities, including antitumor activity, anti-leukaemic activity, cytotoxic activity toward KB and Vero cells, trypanocidal activity as well as inhibitor of HaCaT cell growth. As a nitrogen heterocycle, the 2-aminopyridine scaffold is also a common structural unit found in a number of synthetic biologically active compounds. In contrast to the interesting applications of naphtho[2,3-b]furan-4,9-diones and 2-amniopyridines in the field of drug discovery, naphtho[2,3-b]furan-4,9-diones bearing 2-aminopyridine moiety possessing the potential as an important pharmacophore have not been constructed until now. The combination of such parent molecules to form 2-(pyridin-2-ylamino)naphtho[2,3-b]furan-4,9-diones systems will not only adds functional diversity but also offers a great opportunity for the therapeutic purposes. In addition, this type of novel naphtho[2,3-b]furan-4,9-diones possess rich functional groups, which offers unique possibilities to tune the chemical and/or physical properties and may open up unforeseen opportunities in material science. Herein, we report an efficient and straightforward synthesis of novel naphtho[2,3-b]furan-4,9-dione derivatives bearing 2-aminopyridine moiety and their application for recognition of Hg2+ ion in aqueous media. 1. (a) C.-H. Tseng, Y.-L. Chen, S.-H. Yang, S.-I. Peng, C.-M. Cheng, C.-H. Han, S.-R. Lin, C.-C. Tzeng, Bioorg. Med. Chem. 2010, 18, 5172. (b) F. A. Molfetta, A. T. Bruni, K. M. Honório, A. B. F. da Silva, Eur. J. Med. Chem. 2005, 40, 329. 2. M. Lainchbury, T. P. Matthews, T. McHardy, K. J. Boxall, M. I. Walton, P. D. Eve, A. Hayes, M. R. Valenti, A. K. de Haven Brandon, G. Box, G. Wynne Aherne, J. C. Reader, F. I. Raynaud, S. A. Eccles, M. D. Garrett, I. Collins, J. Med. Chem. 2012, 55, 10229. 202 A homogeneous fluorometric immunoassay for the detection of Arg-vasopressin Chen, L, Zhao, M E-mail: [email protected] Peking University, Beijing, China Arginine vasopressin (AVP) is an antidiuretic hormone, and is known to be related with cardiovascular disease and kidney disease. Understanding of the content and the function of AVP in the brain is urgently needed in order to help people get deeper comprehension about AVP and take advantage of it in the right way. Therefore, AVP measurements in the brain is a very important research issue. Above all, methods for real-time detecting of AVP with high sensitivity and selectivity are required. However, the conventional AVP measurements in clinical utility such as radioimmunoassay (RIA) and enzyme-linked immunosorbent assay (ELISA) are severely prevented due to the labor-intensive work and time-consuming procedures (exceeding 24 h). Furthermore, a number of newly developed aptasensors are limited in clinical application by labeling requirement[1] and insufficient sensitivity[2]. Herein, we present a novel and universal method for detection of AVP based on a polymerase-nicking enzyme synergetic isothermal amplication tools. We first synthesized and characterized ODN-AVP conjugate as the primer. The template contains a primer-binding domain, an amplification domain and a recognition sequence for nicking enzyme Nt.AlwI. Using molecule beacon (MB) as a signal reporter, the method achieved a detection limit of 460 pM and a linear working range from 1 to 100 nM. The method is simple, rapid and provides a useful tool that can potentially measure AVP in clinical applications. REFERENCES 1. Q. Lin, et al., ACS Nano, 2013, 7, 5350–5359 2. Y. Einaga, et al., Scientific Reports, 2016, 6:32429 203 A MICRODIALYSIS-BASED ANALYTICAL SYSTEM FOR DYNAMIC MONITORING OF ARSENIC TRANSFORMATION Hsu, Keng-Chang1, Chen, Ya-Ching2, Hsieh, Jing-Ru1, Huang, Yeou-Lih1,2 e-mail: [email protected] 1 Kaohsiung Medical University, Kaohsiung, Taiwan 2 Kaohsiung Medical University Hospital, Kaohsiung, Taiwan In this study, a microdialysis (MD) technique was combined with high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for continuous monitoring of the dynamic variations of arsenic species in a microbe-inoculated culture broth. After optimizing the analytical system, retrodialysis was applied to assess the probe recovery and analytical performance of the proposed method. The mean probe recoveries of four arsenic species (arsenite, As3+; arsenate, As5+; monomethylarsonic acid, MMA; dimethylarsinic acid, DMA) were in the range from 57.0 to 81.8%. To evaluate the practical applicability of this method, we monitored, continuously for 72 h, the dynamic variations of the concentrations of the four arsenic species in a standardized bacterial sample (ATCC 25922). After adding the arsenic species into the bacteria-inoculated broth, we found that the concentration of As3+ decreased over time, whereas As5+ increased in concentration. In addition, malondialdehyde (MDA) was also monitored to evaluate the effect of oxidative damage of the arsenic species on the studied microbial system. Our analyses revealed that the dynamic variations of the arsenic species and MDA could be observed continuously during the microbial growth period. This economical and eco-friendly method might also be helpful for monitoring the transformations of other metal species, oxidation processes, and the bioremediation ability of microbial systems. 204 A New Difluorocarbene Reagent Ji-Chang Xiao Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Orgnic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China Presenting author’s e-mail: [email protected] + - A new phosphonium salt, difluoromethylene phosphobetaine (Ph3P CF2CO2 ), was synthesized. It was found to be a good precursor of difluoromethylene ylide. The difluoromethylenation could be conducted under milder conditions without the addition of external base, giving the difluoroolefinated product in high yield. Moreover, it was found that this difluoromethylene phosphobetaine could be used as the precursor of difluorocarbene. The difluorocyclopropanation or the difluoromethylenation could be + - performed under milder conditions, which makes the Ph3P CF2CO2 a very good difluorocarbene reagent. In addition, the difluorocarbene derived from this phosphobetaine could be decomposed by DBU and further converted to trifluoromethyl anion without the addition of external fluoride ion. Mechanistic investigation revealed the detailed difluorocarbene conversion process in which the decomposed difluorocarbene was finally transformed into fluoride ion and carbon monoxide. This process was successfully applied in the trifluoromethylation of a variety of (hetero)aromatic iodides, which might turn many difluorocarbene precursors into efficient trifluoromethylation reagents. + - Ph3P CF2CO2 Ar CF3 RXCF2H (PDFA) (X=O,S,N) Ph P+CF CO - (PDFA) 3 2 2 F F Cu(I) Ar-I ' XH R DBU R- kilogram scale R R' R or + - :CF N Ph3P -CF2 2 2 R 1 R 2 0) - 18 - d( ) 2 S8 F or F P H 1 (O R-X (1~5 min) R F -B R 18 2 R-CF2H R-S-CF3 or R-S-CF2- F R F Figure 1: Conversion between carbene, ylide and trifluoromethyl anion. References 1. D. J. Burton, Z. –Y. Yang, W. Qiu Chem. Rev., 96, (1996) 1641-1715. 2. D. L. Brahms, W. P. Dailey Chem. Rev., 96, (1996) 1585-1632. 3. V. V. Tyuleneva, E. M. Rokhlin, I. L. Knunyants Russ. Chem. Rev., 50, (1981) 280-290. 4. J. Zheng. J. Cai. J. –H. Lin. Y. Guo. J. –C. Xiao. Chem. Commun. 2013, 49, 7513-7515. 5. J. Zheng. J. –H. Lin. J. Cai. J. –C. Xiao. Chem. Eur. J. 2013, 19, 15261-15266. 6. J. Zheng. J. –H. Lin. X. –Y. Deng. J. –C. Xiao. Org. Lett. 2015, 17, 532-535. 205 A Novel Catalytic Sensing System for Detecting Formaldehyde Wu, J1, Wu, Z1, Gao, P1, Sun, X1, and Shen, J1 1 College of Materials Science & Engineering, Huaqiao University, Xiamen, China Artificial enzymes have the catalytic activity similar to those of the natural enzymes. Employing artificial enzymes as the substitutes of the natural enzymes can overcome their intrinsic shortcomings including instability, harsh operating conditions and expensive cost. In recent years, nanomaterial-based artificial enzymes (nanozymes) have attracted considerable attentions due to their high catalytic activity, and facile synthesis. In this work, it is first time for reporting the oxidase- like activity of β-HgS nanocrystals. β-HgS nanocrystals were found to be able to catalyse traditional enzyme substrates such as 3,3’,5,5’-tetramethyl benzidine (TMB) and O-phenylenediamine (OPD) to form coloured and fluorescent products, respectively. However, α-HgS nanocrystals did not catalyse these reactions, indicating that α-HgS nanocrystals did not possess the oxidase- like activity. Detailed catalytic mechanism has also been explored. On the basis of the excellent catalytic performance of β-HgS nanocrystals, a catalytic sensing system for detecting formaldehyde has also been successfully developed. Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant no. 21377124), the project of new faculty (No. 15BS202), and Promotion Program for Young and Middle-aged Teacher in Science and Technology Research (No. ZQN-YX303) of Huaqiao University. 206 A Novel Ferrocenyl-based Multichannel Probe For Cu(II) And Hg(II) Junyang Dong[1]，Yufeng Liu[1]，Jianfeng Hu[1],[2]，Huricha Baigude[1] and Hao Zhang[1],[2],[3]* *Corresponding Author, tel.: +86-471-4994406, fax: +86-471-4994406, e-mail: [email protected]; [email protected] (Inner Mongolia University, Hohhot, P. R. China) [1] School of Chemical & Chemical Engineering,Inner Mongolia University, Hohhot 010021, P. R. China. [2] Inner Mongolia Key Laboratory of Fine Organic Synthesis, Hohhot 010021, P. R. China. [3] State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China Abstract: Ferrocenyl-based carbazole derivative has been synthesized by a simple one- step reaction and characterized by 1H NMR, 13C NMR, ESI-MS and X-ray analysis. Meanwhile, The newly synthesized receptor 1 displayed reversible fluorescent “turn on” response toward Hg2+ with good quantum yield in aqueous environment. The color of the solution containing receptor 1 changed from colorless to yellow upon the addition of Cu2+ ions. Therefore, receptor 1 can act as a fluorescent chemosensor for Hg2+ and a naked-eye probe for Cu2+ in aqueous environment. Quantification of absorption titration analysis shows that the detection limit was 6.15 × 10-7 M for 1-Cu2+ and 6.18 × 10-7 M for 1-Hg2+, respectively. Finally, the receptor 1 has been used successfully for determination of Hg2+ in living cells. Fig.1. 207 A combination strategy of UV-Visible spectroscopy and chemometrics method applied to simultaneous quantitative-determination on explosive and its byproducts in environmental water: Wang, L1, Xie J1, Yuan, Y2, Ding X D1, Pu X M1 1Sichuan University, Chengdu, China 2Southwest Minzu University, Chengdu, China 2,4,6-trinitrotoluene (TNT) and its byproductsdrinitrotoluene (DNT) pose a significant risk to human health and other living organisms. However, the conventionally analytical methods involved in bulky and expensive instruments are complicated and time-consuming, impeding quick and on-line determination. In the work, a facile yet effective strategy of utilizing UV-Vis spectroscopy coupled with partial least squares (PLS) was proposed, through which TNT and two isomers of DNT in nature water could be rapidly and simultaneously determined without any pre-separation. Variable combination population analysis (VCPA) was utilized to select important feather variables and significantly improves the predictive performance of the PLS model. The calibration set contains 25 samples constructed by orthogonal array design (OAD). The predictive ability of the models was validated by an independent prediction set including 15 samples, achieving up to 0.99 of the determination coefficients (R2) for each of the analyte. The optimized models were successfully applied to determine the three ingredients in eight environmental samples involving in tap, lake and two kinds of river water with the recovery values close to 100%. Finally, the proposed method is further validated by High Performance Liquid Chromatography, displaying high potential in environmental monitoring. 208 A Promising Analogue of Gefitinib with Improved Cancer Cell Cytotoxicity Wang, H, Hu, X, Bao, B, Xu, M, Fang, J.-K* Nanjing University of Science and Technology, Nanjing, China Gefitinib has been approved for the treatment of advanced non-small cell lung cancer. According to the previous research, the morpholino part of Gefitinib shows no interactions to its anticancer activities due to its weak electron density. In order to modify the electron density of Gefitinib’s sidechain, we previously synthesized a series of novel pyrrolidino analogues of Gefitinib that replace the morpholino groups with substituted pyrrolidino groups. We obtained a promising analogue by replacing of morpholino group in Gefitinib with 2-(2-hydroxypropan-2-yl)pyrrolidin-1-yl. We also found that the antitumor activity could be significantly improved by replacing of 3-chloro-4-fluorophenyl group in Gefitinib with 3- ethynylphenyl group. Based on these results, we reported a new Gefitinib analogue FXE-1 with replacing of both morpholino and 3-chloro-4-fluorophenyl groups in Gefitinib with 2-(2- hydroxypropan-2-yl)pyrrolidin-1-yl and 3-ethynylphenyl groups. FXE-1 can be easily synthesized by alkylation with 4-((3-ethynylphenyl)amino)-7-methoxyquinazolin-6-ol and (R)-2-(1-(3-chloropropyl)pyrrolidin-2-yl)propan-2-ol. FXE-1 shows higher potent activity against human cancer cell lines, H1975 and SK-OV-3 (human lung adenocarcinoma cell and ovarian adenocarcinoma cell) than Gefitinib. IC50 (half-maximal inhibitory concentration) of FXE-1 for H1975 and SK-OV-3 are 2711 nM and 5903 nM, while Gefitinib are 9875 nM and 10000 nM, respectively. It shows that FXE-1 is much more efficient than Gefitinib in term of killing cancer cell, especially for lung cancer cell. The result points that FXE-1 is a promising candidate and it might be an efficient way to develop new drug molecules by combination of efficient motifs in one molecule. This work was supported by the Natural Science Foundation of Jiangsu Province (BK20140780). 209 A Quantitative Structure-Activity Model based on Gradient Boosting Decision Tree Hui, L1, Yunlong, L1, Lihong, H1 1Northeast Normal University, Changchun, China Since an ensemble often has better performance than a single learner, it has achieved successes in many domains. In this paper, A cascaded and ensemble model is proposed to establish the quantitative structure-activity relationship (QSAR) between the overall power conversion efficiency (PCE) and quantum chemical molecular descriptors of all- organic dye sensitizers. The cascaded model is two-level network in which the outputs of the first level, such as Short-Circuit Photocurrent Density (Jsc), Open Circuit Voltage (Voc) and Fill Factor (FF) are the inputs of the second level, and the ultimate end-point is the overall PCE of dye sensitized solar cells (DSSCs). The ensemble method based on Gradient Boosting Decision Tree (GBDT) is adopted in two-level network. The best established cascaded and ensemble model predicts the PCE values of DSSCs with a mean absolute error (MAE) of 0.45, which is about 8.6% of the mean value PCE (5.21%). The validation parameter predictive squared correlation coefficient (Q2) can achieve 0.83. The results show that the cascaded and ensemble modeling method can effectively improve the computational accuracy of quantum chemical calculation methods, and provides an effective tool for predicting and designing new dye molecules. 210 A Radical Addition Reaction To Hydrazones “On Water” Nam, Tae Kyu, Jang, Doo Ok* Department of Chemistry, Yonsei University, Wonju, Republic of Korea Water is a highly attractive solvent from an economical and environmental point of view because it is cheap, readily available, non-flammable, and non-toxic. Moreover, the unique physicochemical properties associated with water result in the possibility of specific interactions such as polar, hydrophobic, trans-phase, and hydrogen bonding interactions that can significantly influence reactions. However, the major problem associated with the use of water as solvent for organic transformations is its low solubilizing ability towards most organic compounds. Generally, solvent effect is known to be negligible in radical reactions. Thus, water was employed as medium for radical reactions. In this context, research efforts on radical reactions employing water were towards increasing the solubility of reactants and initiators. Herein, we wish to report radical addition reactions to C=N bond “on water” at room temperature. In the course of the research, a significant solvent effect was observed. The advantages of this method include high yield, using green solvent, and easy workup. The protocol was applied to the synthesis of isoindolinone derivatives. 211 A Thiophene-containing Polyacetylene Probe for Salicylaldehyde Xin Wang1, Yan Feng2 E-mail: [email protected] 1Chizhou University, Chizhou, Anhui, China. 2Anhui University, Hefei, Anhui, China. Abstract A novel polyacetylene containing thiophene (poly(2-ethynylthiophene, PET) was designed and synthesized, and the structure was characterized by IR and NMR. The optical and thermal stability performance of PET was evaluated by TGA, FL, and UV-vis, respectively. The 85% emission of the sensor material was turned off, when salicylaldehyde (Sla) in ethanol was as low as to 0.72 mM. No doubt, the smart performance of the films guarantees that the films may be applied in the chemosensors for aldehydes. 1 salicylalldehyde 2 4‐Nitro‐benzaldehyde 3 benzaldehyde 4 pyridine‐2‐carboxaldehyde 5 butyraldehyde 6 formaldehyde 7 p‐tolualdehyde 8 p‐hydroxybenzaldehyde 9 3, 5‐di‐tert‐butyl‐4‐hydroxybenzaldehyde Fig. 1. Emission quenching profile for PET film. The inset shows the photographs of the films in different volatile aldehydes (c=7.0×10-5 M). Acknowledgements: This work was supported by the National Natural ScienceFoundation of China (21102001 and 21271035), Anhui Provincial Natural Science Foundation (1608085MB39), Natural Science Foundation of Education Department of Anhui Province(KJ2015A047) and 211 Project of Anhui University. 212 ACID-FUNCTIONALIZE METAL ORGANIC FRAMEWORK FOR CATALYTIC BIOMASS CONVERSION Tangsermvit, V1, Jumpathong, W2, Tharit L2, Lerdwiriyanupap, T2, Wannakao, S2 and Kongpatapanich, K2 Presenting author’s e-mail: [email protected] 1School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, Thailand 2School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, Thailand Conversion of biomass into value-added chemicals has been widely studied nowadays, because it is a renewable resource. Biomass-derived chemicals, 5-hydroxymethylfurfural (5-HMF) have attracted much interest from researchers in the last few years because of its versatile applications of plastic manufacturing and pharmaceutical industry. Metal-organic frameworks (MOFs) are crystalline porous materials composed of inorganic units and organic linkers. MOFs have been used as heterogeneous catalysts because of their tunable porosity for desired substrates to enter into the pore, as well as their suitable for modification of chemical compositions to meet the requirement for chemical reactions. In this work, conversion glucose to 5-HMF has been tested with new promising MOF catalysts which ligand part was modified with acidic functionalization. The acid concentration of the catalyst and reaction condition were optimized to achieve the highest conversion of glucose to 5-HMF. This work suggests the systematically way to functionalize different acidic sites to MOF structures and therefore an efficient heterogenous catalyst for conversion of glucose to 5-HMF has been obtained. 213 Acidic-Functionalized Ionic Liquid Catalyzed Cyclization of 2-Sustituted Aminoaromatics with β-Diketones Han, F, Li, Z, Xia,C G* E-mail: [email protected] State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, People’s Republic of China ABSTRACT TEXT Ionic liquids (ILs) are salts being composed of distinct cations and anions that are capable of facilely tuning, and whereby can be designed for task-specific applications through smart choice of the respective cation and/or anion. Based on their unique properties and accomplished capabilities, various ILs have been extensively investigated. [1] Nitrogen-containing heterocycles have been widely used as important building blocks in pharmaceutical synthesis.[2] Thus, the development of simple and practical methods for construction of these important N-heterocycles motifs has stimulated considerable interest. Nowadays, there are several methods to fulfill the construction of N-heterocycles. However, toxic metals, strong acids and hash conditions are often unavoidable.[3] Therefore, a milder, environmentally-friendly catalyst system for direct transformation of alcohols still remains to be explored. In our continuing effort on developing ionic liquids catalyzed reactions,[4] herein, we will display our recent progress in cyclization of 2-amino phenol/thiophenols/aniline with β-diketones by using acidic-functionalized ionic liquid as metal-free, recyclable, eco-friendly and highly efficient catalysts. Reference: [1] a) Welton T, Chem. Rev. 1999, 99: 2071-2084. [2] P. Thansandote, M. Lautens, Chem. Eur. J. 2009, 15, 5874-5883 . [3] M. S. Mayo, X. Yu, X. Zhou, X. Feng, Y. Yamamoto, M. Bao, Org. Lett. 2014, 16, 764-767. [4] a) Han F, Yang L, Li Z, Xia C, Org. Biomol. Chem. 2012, 10: 346-354; b) Han F, Yang L, Li Z, Xia C, Adv. Synth. Catal. 2012, 354: 1052-1060; c) Han F, Yang L, Li Z, Zhao Y, Xia C, Adv. Synth. Catal. 2014, 356: 2506- 2516. 214 Aloperine Derivatives: Novel Class of Anti-HCV Inhibitors with Different Mechanism Xin Zhang, ShengTang, Zonggen Peng, Danqing Song Email: [email protected] Institute of Medicinal Biotechnology, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, China Hepatitis C virus (HCV) infection is a chronic viral infection, which afflicts approximately 130–170 million people worldwide. It is emerged as a leading cause of chronic liver diseases, which has induced tremendous morbidity and mortality. Aloperine is a quinolizidine alkaloid isolated from sophora alopecuroides, which has a unique bridged tetracyclic ring system. However, little is known with the effect against HCV and the mechanism associated with its activity. Taking aloperine as the lead compound, thirty-nine novel aloperine derivatives were designed, synthesized and evaluated for their anti-HCV activities in vitro. Subsequently, compounds afforded good activities and SI values were selected to evaluate their PK and acute toxicity behaviors. Among them, the one with good activity, PK and safety profile was selected for further investigation like activities against drug-resistant HCV and with approved DAAs. Meanwhile, the primary mode of action was explored. SAR study indicated that introduction of a sulfonyl to 12-nitrogen atom might significantly improve the activity and decrease the cytotoxicity. Among them, compound 2f had the widest therapeutic window and good PK and safety profile. The mechanism study indicated that 2f suppressed HCV replication with a new host-targeting mechanism at an early stage of virus entrance which can decline the damage to the liver. The candidate 2f also showed similar magnitude of inhibitory on the drug-resistant HCV and displayed the synergistically activity When co-administrated with clinical drugs. Therefore, we consider compound 2f to be a novel-scaffold lead for further investigation against HCV. 215 AN EFFICIENT ONE-POT THREE-COMPONENT SYNTHESIS OF TRIFLUOROMETHYLATED 5H-SPIRO[FURAN-2,3'-INDOLIN]-2'-ONES Tao, L1, Fan, Z1, Chen, J1, Zhang, H1, Cao, W*1,2 1 Department of Chemistry, Shanghai University; 2 Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences ABSTRACT TEXT Indolinone is an important class of heterocyclic compounds. The structural units widely present in natural products, drug molecules and functional materials[1]. Numerous studies show that, when introduction of fluorine atom(s) into the heterocyclic compound, it’s physical, chemical and physiological properties could be improved significantly[2]. Thus, here we report an efficient method for the synthesis of trifluoromethylated 5H-spiro[furan-2,3’-indolin]-2’-one derivatives 4 involving a reaction of N-substituted isatins 1, isocyanides 2 and methyl 1,1,1- trifluorobut-2-ynoate 3 (Scheme 1 and Table 1). Table 1 Synthesis of trifluoromethylated 5H-spiro[furan-2,3’-indolin]-2’-one 4a Entry R1 R2 Product 4 Yield (%)b 1 H (CH3)3C 4a 93 2 H Cyclohexyl 4b 82 3 H Ph 4c 89 4 5-Br (CH3)3C 4d 83 5 5-CH3 (CH3)3C 4e 90 a Reaction condition: 1 (1 mmol), 2 (1.5 mmol) and 3 (1.5 mmol) were stirred in toluene (5 mL) at 100 oC for 3 h. b Isolated yields. ACKNOWLEDGEMENT We are grateful to the National Natural Science Foundation of China (Grant Nos. 21672138, 21272152, 21542005) for the financial support. REFERENCES [1] Fu, W.; Zhu, M.; Zou, G.; Xu, C.; Wang, Z. Asian J. Org. Chem. 2014, 12, 1273. [2] Gu, J.; Zhang, X. Org. Lett. 2015, 17, 5384. 216 AN EFFICIENT SYNTHESIS OF PERFLUOROALKYLATED FLUORENES Sun, Z1, He, D1, Chen, J1, Zhang, H1, Cao, W*1,2 1 Department of Chemistry, Shanghai University; 2 Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences ABSTRACT TEXT Fluorene is one of the simplest motifs in polycyclic aromatic hydrocarbons, and its derivatives have found broad applications in materials science, pharmaceutical chemistry and organic synthesis[1]. In recent years, the photoelectrical potential of fluorene and related derivatives has become well recognized. Herein we report a novel and efficient metal-free method for the synthesis of perfluoroalkylated fluorene derivatives 3 involving a reaction of 2-(2,3- dihydro-1H-inden-1-ylidene)malononitriles[2] 1 and methyl perfluoroalk-2-ynoates 2. A series of perfluoroalkylated fluorene derivatives 3 were synthesized in moderate to excellent yields (Scheme 1 and Table 1). Table 1 Synthesis of perfluoroalkylated fluorene derivatives 3a b Entry R RF Product 3 Yield (%) 1 H CF3 3a 96 2 5-Br CF3 3d 46 3 H C2F5 3b 94 4 5-Br C2F5 3e 32 5 H C3F7 3c 94 a Reaction condition: 1 (1 mmol), 2 (1.2 mmol), K2CO3 (0.1 equiv) were stirred in toluene (5 mL) at 80 oC for 6 h. b Isolated yields. ACKNOWLEDGEMENT We are grateful to the National Natural Science Foundation of China (Grant Nos. 21672138, 21272152, 21542005) for the financial support. REFERENCES [1] (a) Justin Thomas, K. R.; Baheti, A. Mater. Technol. 2013, 28, 71. (b) Miyatake, K.; Bae, B.; Watanabe, M. Polym. Chem. 2011, 2, 1919. [2] Xue, D.; Chen, Y.; Cui, X.; Deng, J. J. Org. Chem. 2005, 70, 3584. 217 An electrochemiluminescence sensor for Pb2+ based on DNAzyme Kang T.-F.*, Song H.-Y. E-mail: [email protected] College of Environmental and Energy Engineering, Beijing University of Technology, Beijing, P. R. China A novel electrochemiluminescence (ECL) sensing platform was developed to detect Pb2+ ions based on horseradish peroxidase-mimicking DNAzyme. Poly (diallyldimethylammonium chloride) (PDDA), graphene oxide (GO) and CdS quantum dots (QDs) (Zhang 2015) were used to prepare a composite (P-GO-QDs) which was immobilized on the surface of a glassy carbon electrode (GCE). CdS QDs can produce ECL signal using H2O2 as coreactant. The sequence of G-rich DNA strand which named modified T30695 is 5'-NH3-AAAAAAGGGTGGGTGGGTGGGT-3'. Modified T30695 was attached to P-GO-QDs composite by the reaction between amino group of modified T30695 and carboxyl group of QDs. Modified T30695 can combine with Pb2+ to form a stable parallel G-quadruplex (Zhan 2014). The G-quadruplex can further combine with hemin to form DNAzyme which can catalyze the reduction of H2O2 and cause the decrease of ECL signal. The signal was measured using a MPI-A analyser, a sensor as working electrode, a platinum wire as counter, and a Ag/AgCl as reference electrodes in 0.1 M phosphate buffer solution (pH 7.4) containing 72 mM H2O2. The potential window was from 0 to −1.5 V with a scan rate of 100 mV/s. The ECL signal was linearly dependent on the logarithm of Pb2+ concentration from 1.0×10-14 to 1.0×10-11 M with a detection limit of 9×10- 15 M. An excellent performance of the ECL sensor indicated that it is promising for Pb2+ detection in real samples. References Zhan, S., et al, Anal. Biochem., 462 (2014) 19–25. Zhang, J.-J., et al, Sens. Actuators, 214 (2015) 117–123. 218 Analysing Multiple Biomarkers for Cancer Diagnosis Based on Logic Gates Yahui Guo1, Xing Yu1, Renjun Pei2, Weirong Yao1, He Qian1* Presenting author’s e-mail: [email protected] 1 School of Food Science and Technology, Jiangnan University, Wuxi, China 2 Suzhou Institute of NanoTech and NanoBionics, Chinese Academy of Sciences, Suzhou, China ABSTRACT Some biomarkers are associated with only one type of cancer, whereas most are associated with two or more cancer types. For example, microRNA-141 shows correlations with nasopharyngeal carcinoma, bladder cancer, colorectal cancers, gastric cancer, pancreatic cancer, osteosarcoma, breast cancer and renal cell carcinoma; carcinoembryonic antigen is a wide-spectrum tumour marker expressed in many types of cancer cells. Besides, there can be opposite correlations between the related biomarkers with the same type of cancer. For instance, in lung cancer, microRNA-21 and epidermal growth factor receptor are overexpressed while microRNA Let-7 and micorRNA-29 are down-regulated. Therefore, a comprehensive and logical understanding of the combinational parameters is in urgent need for the clinical diagnosis and study of cancers. Molecular logic gate and computation provide an ideal solution to untangle the multiple and confused test parameters for a clear conclusion. We proposed a three-target DNA logic circuit, which could be applied for intelligent assay of multiple DNA/RNA targets. In the logic strategy, an “INHIBIT” system can be applied for the simultaneous assay of a positive biomarker and a negative biomarker. We think intelligent assay based on DNA logic gates and DNA computation must be promising and useful. REFERENCES 1. Yahui Guo et al. Label-free logic modules and two-layer cascade based on stem-loop probes containing a G-quadruplex domain. Chem-Asian. J. 2014, 9: 2397-2401. 2. Yahui Guo et al. Logic gates based on G-quadruplexes: principles and sensor applications. Microchim. Acta 2016, 183: 21-34. 3. Danish Sayed & Maha Abdellatif. MicroRNAs in development and disease. Physiol. Rev. 2011, 91: 827-887. 219 Anti-cancer activities of Fe3O4-Ce6s-PEG &FAs nanoparticles by photodynamic therapy Park, BJ1, Choi KH1, Kim, HJ2, Ji, HC3, Nam, KC3 1 Department of Electrical & Biological Physics, Kwangwoon University, Seoul, Republic of Korea 2 Department of Chemistry, Chosun University, Gwangju Republic of Korea 3 Department of Medical Engineering, Dongguk University College of Medicine, Goyang, Republic of Korea ABSTRACT Recent progress in nanomedicine has led to the development of magnetic nanoparticles that show great potential for application in early diagnosis, targeted therapy, and personalized medicine. To develop novel multifunctional magnetic nanoparticles (MNPs) with good magnetic properties, biocompatibility, and anticancer activities by photodynamic therapy (PDT), we synthesized multifunctional ferrite nanoparticles (Fe3O4-Ce6s-PEG & FAs) functionalized by coating them with chlorin e6 (Ce6) for introducing photo-functionality and by conjugating with folic acid (FA) for targeting cancer cells. The magnetic properties of iron ferrite (Fe3O4) nanoparticles in this study have been finely adjusted by controlling the size of the primary Fe3O4 nanograins and the secondary superstructed composited particles formed by an aggregation of the nanograins. Singlet oxygen generation from Fe3O4-Ce6s-FAs is also confirmed with indirect detection of 1, 3-diphenyl-isobenzofuran photodegradation. Furthermore, we evaluated the activities of the Fe3O4-Ce6s- PEG & FAs by checking magnetic resonance imaging (MRI) in vitro, its biocompatibility, and photodynamic anticancer activities on FA receptor (FR)-positive and FR-negative cancer cell lines, Hela, KB, MCF-7, and PC-3 cells, to use for clinical applications. In this study, we have demonstrated that the Fe3O4-Ce6s- PEG & FAs have good MRI and biocompatibility with non-cytotoxicity, and remarkable photodynamic anticancer activities at very low concentrations regardless of cell types. These results indicate that Fe3O4-Ce6s- PEG & FAs are suitable for effective photodynamic therapy (PDT) and have potential as a therapeutic agent for MRI based PDT, because they have a high value of saturation magnetization and superparamagnetism. 220 Anticancer activity of Cu(II) and Ni(II) complexes with anthryl thiosemicarbazone Bai, J, Wang, R.-H, Fang, C.-J Presenting author’s e-mail: [email protected] 1 Capital Medical University, Beijing, China Inherent and acquired multidrug resistance (MDR) is a huge obstacle to the successful chemotherapeutics of cancer, which is mainly mediated by a P-glycoprotein (P-gp). Much endeavour in overcoming MDR has been made to design and discover novel anticancer agents or P-gp inhibitors, which, up to date, remains still a principal area of anticancer investigation. The anticancer activity of thiosemicarbazones has attracted much attention. In the present work, we found that the chelate compounds Cu(MNS)2Cl2 and Ni(MNS-H)2 derived from 2-(anthracen-9-ylmethylene)-N-methylhydrazinecarbothioamide showed an improved anticancer activity, with IC50 value comparable to that of the clinically used first- line agent cisplatin, while they remained the potential to overcome MDR, which is verified with the standard MTT assay over MCF-7/ADR cells. The drug resistance index (DRI) of MCF-7/ADR cells after treated with Cu(MNS)2Cl2 and Ni(MNS-H)2 is less than 2, indicating that the chelate complexes could treat an extremely chemoresistant cell MCF-7/ADR as the drug-sensitive one. The cellular uptake experiments suggest that the intracellular concentration of Cu(MNS)2Cl2 and Ni(MNS-H)2 is almost identical to each other for both MCF-7 and MCF-7/ADR cells, indicating that the function of P-gp is not affect by Cu(MNS)2Cl2 and Ni(MNS-H)2. Further exploration is needed to reveal the mechanism of Cu(MNS)2Cl2 and Ni(MNS-H)2 to overcome MDR. Acknowledgements The authors thank the NSFC (21171120, 21571133) and Natural Science Foundation of Beijing Municipality (7132020) for financial support. 221 Application of gold nanoclusters in fingermarks development Huang. R Presenting author’s e-mail: [email protected] Chongqing Institutions of Higher Learning Center of Forensic Science Engineering and Research, College of Criminal Investigation, Southwest University of Political Science and Law, Chongqing, China ABSTRACT TEXT Based on the features of ultrasonic and microwave radiation methods, bovine serum albumin-protected gold nanoclusters have been efficiently and novelly synthesized via the ultrasonic-microwave heating method. Meanwhile, a novel emerging technique of latent fingermarks has been proposed. Compared with the traditional materials, Au NCs prepared by ultrasound-microwave heating, is more efficient and environmentally friendly. The protein-stabilized Au NCs can be prepared within 1h (microwave for 50 s and ultrasonic for 1h), and the fluorescence quantum yield reaches 7.1%. The maximum emission wavelength of Au NCs is 633nm when exited at 521nm. By optimizing the dosages of BSA, HAuCl4 and KOH, the concentration of BSA and HAuCl4 were fixed at 50 mg/mL and 0.01 mol/L, respectively. The optimal volume ratios of HAuCl4: Au is 10:1, and BSA: Au is 10:1. The experimental results show that the average diameter of Au NCs is about 3.3 nm, which possess a spherical shape with a smooth surface and a more uniform size, high monodispersity. The optimized Au NCs can be widely applied to develop latent fingermarks. The results show that Au NCs can simplify operations. Most promisingly, gold nanoclusters and even more metal nanoclusters will take a vital role in criminal science and application. 222 Applications of Nano-Materials in Fracturing Fluids: A Critical Review Wai Li1,2, Xionghu Zhao1, Hui Peng2 Presenting author’s e-mail: [email protected] 1 State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum (Beijing), Beijing, China 2 Beijing Oilchemleader Science & Technology Development Co., Ltd., Beijing, China ABSTRACT TEXT In the petroleum industry, fracturing has been one of the most important approaches for improving productivity, especially for unconventional reservoirs. Operational complexity and cost consideration in recent years put forward new challenges to fracturing fluid technology. Being promising and attractive, Nano-materials have exhibited their astonishing charm in this field. Innovative synthesis and modification chemistry endows a variety of novel properties to traditional materials thereby achieves new, high-performance fracturing fluids which are not possible to be obtained previously. Due to nano-materials’ special structure and high surface activity, they can bridge polymers and/or surfactants by intermolecular interactions, and form various nano-modified molecular aggregates and/or micelles which are easily broken under designed conditions. Compared to their conventional counterparts, nano- fracturing fluids have superior performance, more flexible behaviour and better controllability. Relevant studies currently focus on using nano-materials to fulfil better rheological behaviour, improved filtration property, enhanced fracture conductivity, more completed breaking, higher cleanup rates, thermal/shear tolerance, lower reservoir damage and good environmental acceptability. Involved materials include nano-metal, nano-metal oxide, nano-silicon, nano-carbon, nano-polymer, organic-inorganic hybrid and other nano- composites. They can be used as viscosifiers, crosslinkers, rheological modifiers, breakers, system stabilizers, clay stabilizers and cleanup additives in fracturing fluids. This paper comprehensively reviews these techniques, demonstrating the exciting prospect of nano- fracturing fluids. The action mechanisms of nano-materials are also discussed in detail. Further discussion in commercial cost and HSE issues is addressed as well. Having numerous benefits and advantages, nano-materials are expected to be fully accepted and widely utilized in fracturing operations in the future. 223 Ar Glow Discharge Plasma Reduction to Prepare Supported Pd Nanoparticles Liu, Y, Bai, X Presenting author’s e-mail: [email protected] Institute of Petrochemistry, Heilongjiang Academy of Sciences, Harbin, China ABSTRACT Pd nanoparticles supported on ordered mesoporous carbon (PdNPs/CMK-3) were prepared by Ar glow discharge plasma technology (P-PdNPs/CMK-3) without the use of any chemical additives or surfactants and chemical method using ascorbic acid as reducing agent (AA- PdNPs/CMK-3), respectively. It was shown from XRD and TEM characterization that the as- prepared PdNPs were of the face-centered cubic structure and the P-PdNPs had a narrow size distribution (1.6-6.2 nm) with an average particle size of 3.4 nm (lower than CMK-3 pore diameter of 3.7 nm), which corresponds to the size distribution(3.7-18.9 nm) with an average particle size of 11.1 nm for AA-PdNPs. P-PdNPs are mainly formed inside the pore channels of CMK-3, but AA-PdNPs on the outside surface of CMK-3. The above analysis results demonstrated that Ar glow discharge plasma technology realized the in-situ reduction of palladium ion to PdNPs and avoided agglomeration of the nanoparticles during the reduction process. The catlytic Suzuki coupling reaction yield reached 95% in the presence of 1 mmol‰ P-PdNPs/CMK-3 at 40 ℃ for 30 min towards the reaction of 4-bromonitrobenzene and phenylboronic acid, which corresponds to 86% for AA-PdNPs/CMK-3. The P- PdNPs/CMK-3 could be recycled five times without obvious activity loss due to a good stability. The hot filtration test confirmed that the few Pd atoms leached out from CMK-3 for P-PdNPs/CMK-3. 224 ARTESUNATE TARGETS THE HUMAN BCL-2 ANTAGONIST OF CELL DEATH PROMOTER Gotsbacher, M P1,3, Cho S2, Kim N H2, Liu F1, Kwon H J2, Karuso P1 Presenting author’s e-mail: [email protected] 1 Macquarie University, Sydney, Australia 2 Yonsei University, Seoul, Korea 3 The University of Sydney, Sydney, Australia Artemisinins are sesquiterpene lactones extracted from sweet wormwood (Artemisia annua) and constitute the most potent and safe antimalarials currently available. They also have selective anticancer activity, yet despite their clinical potential, no human target of the artemisinins is known and their mode of action still unclear [1]. In parallel to their antimalarial activity, it is widely believed that the endoperoxide bridge in artemisinins initiates oxidative stress in cancer cells through formation of reactive oxygen species (ROS), which leads to apoptosis [1,2]. Other evidence points to necroptosis or ferroptosis as modes of action. Starting from artemisinin, we synthesised biotinylated and fluorescently labelled version of artesunate (ART). Biotinylated artesunate was used as bait to interrogate several human cancer cDNA libraries, displayed on the surface of bacteriophage T7. After several rounds of biopanning, we identified a single human target of ART; the Bcl-2 antagonist of cell death promoter (BAD). Fluorescently labelled artesunate was shown to colocalise with BAD antibody in HeLa cells and that the cytotoxicity of ART was abrogated by knocking down BAD with siRNA. We show that ART interacts with BAD in HeLa cells and inhibits the phosphorylation of BAD, thereby promoting the formation of the proapoptotic BAD/Bcl-xL complex and the subsequent intrinsic apoptotic cascade resulting in cell death. This unanticipated role of BAD as a target of ART points to new avenues for clinical exploitation of artemisinins in the Bcl-xL life/death switch. [1] Y. Odaka, et al., Carcinogenesis 2014, 35, 192-200 [2] K.Q. Tran, A.S. Tin, G.L. Firestone, Anti-Cancer Drugs 2014, 25, 270-281 225 Asymmetric Synthesis of Secondary Borylalkanes through Domino Hydrocupration and Allylation Han, J. T.1, Yun, J1 Presenting author’s e-mail: [email protected] 1 Sungkyunkwan University, Suwon, Korea A copper-catalyzed multi-component reaction of alkenylborons, allylic phosphates and hydrosilanes has been developed to give the enantioenriched secondary borylalkanes. In the presence of CuC/chiral Walphos catalyst, various alkenylborons furnished the borylalkanes in good yield and with excellent enantioselectivity via hydrocupration and allylation. Alkenyl pinacolboronates and 1,8-diaminonaphthalene borons with an aryl, heteroaryl, or alkyl substituent were well tolerated to provide the correspond products. To demonstrate the utility of this method, a concise synthesis of (S)-massoialactone was carried out. 226 New Scaffold for Angiogenesis Inhibitors Discovered by Structural Modification of Natural Products Kim, S, Lee SK, Lee, S, Jeon, H, Kim, JH, Park, S, Yu, S, Li, P Presenting author’s e-mail: [email protected] Presenting author’s e-mail: [email protected] College of Pharmacy, Seoul National University, Seoul, South Korea Structural modification of natural products is an important approach to the search for new scaffolds for drug discovery. We present our efforts to create novel drug-like scaffolds with potent anti-angiogenic activity and minimized cytotoxicity by repairing the structure of wondonin. Wondonin marine natural products have novel anti-angiogenic properties without overt cytotoxicity. However, the development of this class of natural products as a new type of anti-angiogenesis agent has been hindered by the chemical instability and synthetic complexity. Our structural modification followed a medicinal chemical rationale. One of the analogues with the new scaffold exhibited excellent anti-angiogenic selectivity (efficacy vs cytotoxicity) in an in vitro study. In addition, this analogue effectively inhibited hyaloid vessel formation in diabetic retinopathy (DR)-mimic zebrafish. These results suggest that this active compound could serve as a new lead scaffold for the treatment of diseases that necessitate anti-angiogenesis agents with minimized cytotoxicity. 227 Bioactivity investigation of the extracts from porcupine phytobezoars Yew, PN1, Lim, YY1, Lee, WL1 Presenting author’s e-mail: [email protected] 1Monash University Malaysia, Subang Jaya, Selangor, Malaysia Porcupine dates are bezoar stones that are used in Traditional Chinese Medicine (TCM) treatments such as cancer, post-surgical recovery, dengue fever and etc. The medicinal values have not been scientifically investigated/reported due to availability and high pricing. This paper represents the first report on the phytochemical content, antioxidant, anticancer and anti-inflammatory properties of methanolic extracts of three porcupine dates: grassy date (GD), black date (BD) and powdery date (PD). Phenolic compounds of the porcupine dates were extracted with 100% methanol. We compared the differences between respective porcupine dates based on their (1) phytochemicals constituents, (2) antioxidant properties [Total phenolic content (TPC), Free radical scavenging (FRS), Ferric Reducing Power (FRP), Intracellular ROS scavenging assay (DCFH-DA)], and (3) cytotoxic activity on several cancer cell lines. Tannins, flavonoids, cardiac glycoside, and terpenoids were found in all porcupine dates with tannins forming the major portion in BD and PD, which contribute to its high TPC, FRS and FRP. Methanol extracts of BD and PD (200 µg/ml) demonstrated intracellular ROS scavenging activity in AAPH-induced RAW264.7 comparable to that of 1.84 µg/ml of curcumin, significant NO scavenging activity in LPS- stimulated RAW264.7, and selective cytotoxicity against colon cancer cells HT-29 and HCT-116 but not normal colon cell CCD-841-CoN . Tannins rich fractions of both BD and PD showed increased cytotoxic effects towards HT-29 and HCT-116 cells with lower IC50 (45-55 µg/ml) as compared to the crude extract (70-100 µg/ml). Overall, BD and PD exhibited promising in vitro and in vivo antioxidant, anti-inflammation and colon cancer cytotoxicity properties. 228 Bioassays-guided purification of chemical constituents from Hemigraphis alternata Wong, KM1, Cheow, YL1, Goh, JK1 [email protected]:[email protected] 1 Monash University Malaysia, Bandar Sunway, Malaysia Plants have been used to treat illness and diseases in folk medicines. Studies suggested that their therapeutic properties are attributed to bioactive compounds found within them. These compounds are candidates for drug development and extensive work have been conducted to isolate them. Previous studies suggested that leaves of Hemigraphis alternata have exhibited promising antioxidant activities, but there is no report on the isolation and identification of bioactive compounds from this plant. To our best knowledge this represents the first study to do so. In this study, methanol crude extract of H. alternata freeze dried leaves was obtained and fractionated with hexane, ethyl acetate and water to produce HA-H, HA-E and HA-W, respectively. Bioactivity studies have shown that HA-H and HA-E were excellent in the iron chelation and ferric reducing properties, IC50 of 160.4 ± 6.074 μg/mL and 0.2135 ± 0.01003 μg/mL, accordingly. Their activity was comparable to the respective standard, namely the gallic acid and ethylenediaminetetraacetate (EDTA). HA-H and HA-E were subjected to bioassays-guided purification. The purification was achieved by column chromatography using silica 60 as stationary phase and eluted with organic solvents of increasing polarity. Bioassays were then carried out to identify the active fraction. Current study have successfully identified HA-H sub-fraction 14 with highest iron chelation activity, IC50 of 34.00 ± 2.274 μg/mL. LC-MS analysis will be performed to elucidate its composition. Besides that, two crystals were purified from HA-H sub-fraction 8 and HA-E sub-fraction 7. These crystals with sufficient yield will be identified using various spectroscopic techniques. 229 Bio-inspired Energy Conversion in Nanofluidics: A Paradigm of Material Evolution Yaping Feng, Wei Guo*, and Lei Jiang* Presenting author’s e-mail: [email protected] Affiliations (Arial, 12 font Italics, Organisation, City, Country) e.g. 1 Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. 2 University of Chinese Academy of Sciences, Beijing 100049, P.R.China Well-developed structure-function relationships in living system become inspirations for the design and application of innovative materials to meet the ever-growing welfare of mankind. Recent advances in chemistry, materials science, and nanotechnology elicit considerable interest to construct ion-channel-mimetic nanofluidic systems for energy conversion and storage as effective as the electrogenic cells. Herein, three essential steps of structural and functional development in synthetic nanofluidic systems are highlighted on the viewpoint of material evolution. By adopting various design strategies from different natural inspirations, the nanofluidic devices and materials keep on evolving and gaining more functions. To acquire asymmetric ion transport functions, the solid-state nanopores transform from cylindrical to conical, and further gain versatile responsibilities via chemical modification. Towards large-scale integration and real-world applications, the structure of the nanofluidic systems experiences an evolution from one-dimensional straight channels to two-dimensional layered membrane. The research progress, challenges, and future perspectives in this growing field are discussed. 230 BIOSYNTHESIS, CHARACTERIZATION, AND ANTIPARKINSON ACTIVITY OF MAGNETITE-INDONESIAN VELVET BEANS (Mucuna pruriens L. ) NANOPARTICLES Sardjono, R.E1, Erfianty, D.D1, Khoerunnisa, F1, Musthopa, I1 1 Universitas Pendidikan Indonesia, Bandung, Indonesia ABSTRACT Biosynthesis and characterization of magnetite-Indonesian velvet bean nanoparticle (FeMPn) and its anti-Parkinson pre-clinical test have been conducted. This study consisted of several stages i.e. extraction of velvet bean seed powder, synthesis and characterization of FeMPn and anti-Parkinson pre-clinical test of FeMPn. Velvet bean seed powder was extracted by maceration using ethanol-water (1:1). FeMPn were synthesized from the aqueous solution of velvet bean seeds extract (10,000 ppm) and ferric chloride solution (0.01 M) at 1:1 ratio. The biosynthesised FeMPn were confirmed by SEM, PSA, EDX, FTIR, and TG/DTA. Pre-clinical test was conducted by catalepsy test in mice induced by haloperidol. FeMPn was administered at different doses of 5, 15 and 25 mg/kg body weight. The results showed that FeMPn have a spherical shape with the particle size 50-100 nm. Catalepsy test demonstrated that the three doses of FeMPn can decrease significantly the symptoms of Parkinson's disease such as catalepsy in mice. The optimum dose to decrease catalepsy is 15 mg/kg body weight. Keywords: Velvet bean, antiparkinson, Mucuna pruriens, nanoparticle, biosynthesis . 231 Briarenols B–E, New Polyoxygenated Briaranes from the Octocoral Briareum excavatum Su, Y-D1, Hwang, T-L2, Wen, Z-H3, Sheu, J-H3, Sung, P-J1,4 1 National Museum of Marine Biology & Aquarium, Pingtung, Taiwan 2 Graduate Institute of Natural Products, Chang Gung University, Taoyuan, Taiwan 3 Department of Marine Biotechnology & Resources, National Sun Yat-sen University, Kaohsiung, Taiwan 4 Graduate Institute of Marine Biology, National Dong Hwa University, Pingtung, Taiwan Four new polyoxygenated briarane diterpenoids, briarenols B–E (1–4), were isolated from the octocoral Briareum excavatum. The structures of briaranes 1–4 were elucidated by interpretation of spectroscopic data, and the methylenecyclohexane ring in 2 was found to exist in a twisted boat conformation. Briarenols B (1) and D (3) displayed inhibitory effect on the release of elastase by human neutrophils with an IC50 value of 3.33 and 4.65 μM. Briarenol E (4) was found to inhibit the protein expression of pro-inflammatory inducible nitric oxide synthase (iNOS) in a murine macrophage- like cell line, RAW264.7, stimulated with lipopolysaccharide (LPS). 1 2 3 4 232 Briarenols B–E, New Polyoxygenated Briaranes from the Octocoral Briareum excavatum Yin-Di Su1, Tsong-Long Hwang2, Zhi-Hong Wen3, Jyh-Horng Sheu3, Ping-Jyun Sung1,4 [email protected] 1 National Museum of Marine Biology & Aquarium, Pingtung, Taiwan 2 Graduate Institute of Natural Products, Chang Gung University, Taoyuan, Taiwan 3 Department of Marine Biotechnology & Resources, National Sun Yat-sen University, Kaohsiung, Taiwan 4 Graduate Institute of Marine Biology, National Dong Hwa University, Pingtung, Taiwan Four new polyoxygenated briarane diterpenoids, briarenols B–E (1–4), were isolated from the octocoral Briareum excavatum. The structures of briaranes 1–4 were elucidated by interpretation of spectroscopic data, and the methylenecyclohexane ring in 2 was found to exist in a twisted boat conformation. Briarenols B (1) and D (3) displayed inhibitory effect on the release of elastase by human neutrophils with an IC50 value of 3.33 and 4.65 μM. Briarenol E (4) was found to inhibit the protein expression of pro-inflammatory inducible nitric oxide synthase (iNOS) in a murine macrophage- like cell line, RAW264.7, stimulated with lipopolysaccharide (LPS). 1 2 3 4 233 Detection and Induction of Cell Death of Cancer Cells by Luminescent Iridium Complexes Having Death Receptor Binding Peptides Masum, A. A1, Hisamatsu, Y1, Suzuki, N1, Aoki, S1,2 Presenting author’s e-mail: [email protected] 1 Faculty of Pharmaceutical Sciences, Tokyo University of Science, Chiba, Japan 2 Imaging Frontier Center, Tokyo University of Science, Chiba, Japan TRAIL is a cytokine classified in TNF superfamily that triggers apoptosis in a wide variety of 1 cancer cells by complexation with death receptors (DR4 and DR5). TRAIL is a C3- symmetric protein consisting of three monomeric units.1 Cyclometalated iridium (III) complexes such as fac-Ir(tpy)3 (tpy = 2-(4-tolyl)pyridine have excellent luminescent 2 properties and possess C3-symmetric structure like TRAIL. Therefore, Ir complexes having DR binding peptide are expected to detect cancer cells and induce their cell death. Recently, Ir complexes having cationic peptides have been reported to induce Jurkat cells death and exhibit strong emission in dead cells.3 In this study, we report on the design and synthesis of luminescent Ir complex-peptide hybrids (IPHs) having DR5 binding peptide.4 IPHs are capable of binding with DR5 and detecting cancer cells such as Jurkat, K562 and Molt-4 cells. Microscopic images and flow cytometry data suggest that IPHs bind with these cancer cells in a parallel manner to the DR5 expression. Co-staining of Jurkat cells with IPHs and anti-DR5 antibody, disclose that IPH-DR5 complexes internalize into cytoplasm via endocytosis and induce necrotic type cell death of cancer cells possibly via calcium overload. To the best of our knowledge, IPHs are the first class chemical agents that detect cancer cells and induce their cell death. References: [1] Ashkenazi, A. et al. J.Clin. Oncol. 2008, 26, 3621-3630. [2] Aoki, S. et al. Inorg. Chem. 2011, 50, 806-818. [3] Hisamatsu, Y. et al. Bioconjugate Chem. 2015, 26, 857–879. [4] Pavet, V. et al. Cancer Res. 2010, 70, 1101-1110. 234 Carbazole-Containing Isoreticular MOF-5 and its Properties Jung, J.Y.1 and Choi, E.Y.1* Presenting author’s e-mail: [email protected] 1 Korea Science Academy of KAIST, Busan, South Korea Metal-Organic Frameworks (MOFs) composed of metal clusters and organic ligands that possess fine-tuning structural diversity, and offer extensive potential applications, such as gas storage, catalysis, and sensing. Recently, microporous 3D coordinated copolymers attract interests because of their improved chemical and physical properties. Carbazole- containing ligands having rigid ring structures and good electro-activities begin to be considered as building blocks in the design and synthesis of coordination networks. However, only 48 carbazole-containing coordination polymers were reported based on CSD (the Cambridge Structural Database). Moreover, carbazole-containing 3D MOFs were very rarely reported. In this study, a new carbazole-containing isoreticular MOF-5 has been synthesized via application of CZ3-acid (2,5-bis(3-(9H-carbazol-9-yl)-propoxy)benzene-1,4- dicarboxylic acid) as a partial alternative to the conventional ligand, H2BDC (benzene-1,4- dicarboxylic acid). The resulting compound, named as MBCZ3 (M: Metal cluster; B: BDC; CZ3: CZ3-acid), shows improved properties in stability, surface area, and gas adsorption ability. Especially, the rigid hydrophobic carbazole empower a dramatic enhancement in its stability which is a major barrier to practical use of MOF-5. It has not only successfully exhibited enhanced stabilities, but moreover increase in surface area and gas adsorption ability. In addition, it shows the change of optical property. 235 CARBON DIOXIDE SEPARATION AND STORAGE IN PORPHYRIN-BASED METAL- ORGANIC FRAMEWORKS Piyakeeratikul, P1, Pila, T2, Jumpathong, W1, Wannakao, S1, Kongpatpanich, K1 Presenting author’s e-mail: [email protected] 1 School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, Thailand 2 School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, Thailand Large amount of carbon dioxide emission is generated from fossil fuel combustion power plants and is considered one of the main cause of global warming. In order to lower the level of CO2, much attention has been paid in developing materials for CO2 capture. Metal- organic frameworks (MOFs) or porous coordination polymers (PCPs) are well-known as novel adsorption materials due to their large surface area, high pore volumes, and tunable structure. Thereby, MOFs can be modified by changing metal centers and organic linkers, obtain MOFs with desired structure and properties for specific application. Inspired by nature, Porphyrins have a structure similar to biomolecules related to gas sorption system such as Hemoglobin in red blood cells and Chlorophyll in plants. Besides, porphyrins have a free center site for metalation and can tailor substituted groups to be used as organic linkers in MOF structures. Here we synthesized porphyrin-based MOFs for CO2 capture, and characterized by X-ray diffraction techniques along with gas adsorption experiments. We also investigate the influences of metal nodes and metal in the center of porphyrin linkers in MOF structure, and the effects of substituted groups on porphyrin ring on CO2 adsorption and conversion. 236 Carbon Dots/NiCo2O4 Nanocomposites with Various Morphologies for Hybrid Supercapacitors Ji-Shi Wei, Peng Zhang, Huan-Ming Xiong* Presenting author’s e-mail: [email protected] Fudan University, Shanghai 200433, P. R. China ABSTRACT TEXT Carbon dots (CDs) have become a focus due to their unique properties in both physics and chemistry. Besides the widely reported fluorescence sensors or bioimaging probes, CDs can also be used as electrode materials in supercapacitors and fuel cells. For supercapacitors, high power density and excellent coulomb efficiency are their natural advantages. But the typical supercapacitors fail in the lower energy density because their energy storage is limited on the electrode surfaces in form of the double layer capacitance. To overcome this limitation, electrode materials should possess abundant reversible redox reactions to realize high energy density. For example, nickel cobalt oxides (NiCo2O4) have promising high energy densities which are based on the metal valence variations in redox reactions, while some deficiencies like volume change effects always render the short life cycles and poor rate performances of NiCo2O4 materials . To dissolve this problem, we prepared the novel CDs/NiCo2O4 nanocomposites. By adjusting the inventory rating of CDs in reactions, multi-structures of the composites were achieved from sea urchin to flower and even bayberry. The specific capacitance of the optimal sample reached 2168 F g-1 and the retention rate exceeded 75% when the current density varied from 1 to 30 A g-1. A hybrid supercapacitor was fabricated by using CDs/NiCo2O4 as positive electrode and hierarchical porous carbon as the negative electrode, respectively. Such device exhibited a high energy density of 62 Wh kg-1, and even a 99.9% capacity retention rate after 5000 cycles at a high current density of 30 A g-1. REFERENCES [1] Wei, J. S.; Ding, H.; Zhang, P.; Song, Y. F.; Chen, J.; Wang, Y. G.; Xiong, H. M. Small 2016, 12, 5927. [2] Wei, J. S.; Ding, H.; Wang, Y. G.; Xiong, H. M. ACS Appl. Mater. Interfaces 2015, 7, 5811. 237 Catalytic Asymmetric Synthesis of -Aryl--Acyloxy Propanoates Do Hyun Ryu1, Ki-Tae Kang1 and Seung Tae Kim1 1Department of Chemistry, Sungkyunkwan University, Suwon 440-746, Korea The asymmetric O-H insertion reaction of diazoesters to carboxylic acid is an ideal synthetic strategy for preparing optically active α or β-acyloxy esters, which are valuable building blocks for the construction of natural products and other biological active molecules. In this presentation, a new chiral Brønsted acid derived from carboxylic acid and chiral oxazaborolidinium ion (COBI) as activator is introduced. This acid was successfully applied as a catalyst for the highly enantioselective O-H insertion reaction of diazoesters with carboxylic acids. The reaction proceeded in good yields (up to 97%) with excellent enantioselectivities (up to 99% ee) to afford various -aryl--acyloxy propanoates. 238 Catalytic Enantioselective Hemithioacetal Isomerization: Biomimetic Access to α- Hydroxythioesters and α-Hydroxyamides[1] Park, S. Y., Song, C. E. Presenting author’s e-mail: [email protected] Sungkyunkwan University, Suwon, Korea A highly enantioselective biomimetic isomerization of hemithioacetal adducts spontaneously formed from diverse 2-oxoaldehydes and thiols, affording both enantiomers of α-hydroxy thioesters, has been achieved for the first time using artificial glyoxalase I. This reaction is exceptionally enantioselective, and the α-hydroxythioester products are of high value for multiple synthetic applications, highlighted by the coupling reagent-free synthesis of several optically pure α-hydroxyamides, highly important drug candidates in the pharmaceutical industry. Like real enzymes, the enforced proximity of the catalyst and substrates by a chiral cage in-situ formed by the incorporation of potassium salt can enhance the reactivity and efficiently transfer the stereochemical information. Our strategy will provide new scientific insight for developing biomimetic catalysts, which can achieve even more than an original enzyme. Furthermore, this work would also provide a potential starting point for developing artificial enzymes which might be used for pharmaceutical uses. [1] Park, S. Y.; Hwang, I. S.; Lee, H. J.; Song, C. E. Nat. Commun. 2017, 8, 14887. [2] Selected papers: a) Liu, Y.; Ao, J.; Paladhi, S.; Song, C. E.; Yan, H. J. Am. Chem. Soc. 2016, 138, 16486. b) Lee, J.-W.; Oliveira, M. T.; Jang, H. B.; Lee, S.; Chi, D. Y.; Kim, D. W.; Song, C. E. Chem. Soc. Rev. 2016, 45, 4638. c) Park, S. Y.; Lee, J. W.; Song, C. E. Nat. Commun. 2015, 6, 7512. d) Yan, H.; Oh, J. S.; Lee, J. W.; Song, C. E. Nat. Commun. 2012, 3, 1212. e) Yan, H.; Jang, H. B.; Lee, J.-W.; Kim, H. K.; Lee, S. W.; Yang, J. W.; C. E. Song, Angew. Chem. Int. Ed. 2010, 49, 8915. 239 Chemical Constituents and Bioactivities from the Soft Coral Sarcophyton cherbonnieri Peng, C1, Huang, C1, Hwang, T2, Sheu, J1,3 Presenting author’s e-mail: [email protected] 1 Department of Marine Biotechnology and Resources, National Sun Yat-sen University, Kaohsiung, Taiwan 2 Graduate Institute of Natural Products, College of Medicine, Chang Gung University, Taoyuan, Taiwan 3 Frontier Center for Ocean Science and Technology, National Sun Yat-sen University, Kaohsiung, Taiwan ABSTRACT TEXT Four new cembranoids, cherbonolides A–C (1–3) and bischerbolide peroxide (4), along with one known cembranoid, isosarcophine (5), have been isolated from the Formosan soft coral Sarcophyton cherbonnieri. The structures of these compounds were elucidated by detailed spectroscopic analyses, modified Mosher’s method and time-dependent density functional theory electronic circular dichroism (TDDFT ECD) calculations. Compound 4 was discovered to be the first known example of a molecular skeleton formed from two cembranoids connected by a peroxide group. Compounds 1, 3, and 4 were found to display inhibitory effects on the generation of superoxide anion in N-formyl-methionyl- leucyl-phenylalanine/ cytochalasin B (fMLP/CB)-induced neutrophils, whereas the most potent compound 4 was shown to exhibit stronger activity to inhibit the generation of superoxide anion. 240 Chloride- and sulfate-encapsulation based on metal-pyrazole complex cations Chou, C.-C., Yang, C.-C. Chang Gung University of Science and Technology, Tao-Yuan, Taiwan + + A new chloride-encapsulated digold(I) complex cation, [Cl {Au(Hpz”)2}2] (1 ), where Hpz” = 3,5-di-tertbutylpyrazole, and a new sulfate-encapsulated disilver(I) complex, [SO4 {Ag2(Hpz”)5}]·(H2O) (2) have been obtained to exist as a “host…guest…host” sandwich- type discrete entity in the solid state. The X-ray crystal structures reveal that the chloride anion engages in four hydrogen bonds only in complex cation 1+; whereas the sulfate anion engages in five hydrogen bonds besides the coordinative Ag···O interactions in complex 2. 241 Cholesterol-sensing Interactions of Islet Amyloid Polypeptide with Lipid Membranes Li, F, Li Y, Hao, R e-mail: [email protected] State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun, P.R. China Deposit of human islet amyloid polypeptide (hIAPP) at the -cells of the pancreatic islets has been associated with -cell dysfunction and death in type II diabetes mellitus. Interaction between the N-terminal domain of hIAPP (hIAPP1-19) and cellular membrane is a key step in the toxicity of hIAPP to the -cells. Cholesterol is believed to play a significant role in the peptide-membrane interaction by regulating the ordering of lipids and the formation of microdomains in cellular membranes. In this study, we monitor the interactions of hIAPP1-19 with model membranes made up of phosphatidylcholine and explore the effects of cholesterol on the binding of the peptide to the membrane, the sencondary structures of the peptide and the peptide-induced membrane damage using nuclear magnetic resonance, circular dichroism and dye leakage experiments. Our results show that the affinity of hIAPP1-19 for the zwitterionic membranes increases with increasing fraction of cholesterol in the membranes consisting of either saturated or unsaturated fatty acide chains. The presence of cholesterol facilitates the formation of -helical structure of the peptide and increases the peptide-induced membrane permeability. The promoting effect of cholesterol to the interaction between hIAPP1-19 and lipid membrane is more evident in the saturated lipid membrane than that in the unsaturated lipid membrane. Different distribution of cholesterol in the saturated and unsaturated lipid membranes may be responsible for the difference between the interactions of hIAPP1-19 with the membranes. 242 Co-assembly into the Solid Solution or Cocrystals with Optoelectronic Properties Zhen,Y1, Zhu, W1, Zhang, H1, Matsuo, Y2, Nakamura, E2, Hu, W1,3 Presenting author’s e-mail: [email protected] 1 Institute of Chemistry, CAS, Beijing, China 2 The University of Tokyo, Tokyo, Japan 3 Tianjin University, Tianjin, China ABSTRACT TEXT Organic solution solids or co-crystals formed with two or more different materials through intermolecular non-covalent interactions are gaining increasing research attention because of their applications in optoelectronics. More interestingly, their physicochemical properties are not simply the sum of molecular properties of the constituent compounds. First, A solid solution of two porphyrin derivatives was achieved by in-situ heating their soluble precusors mixture.1 Organic solar cells based on the solid solution was demonstrated for the first time, resulting in a power conversion efficiency value much higher than the devices using the single component. This increase originates largely from the suitable energy level for the solid solution state, where electronic coupling between the two porphyrins occurred. Second, an easy solution self-assembly method is reported to tailor the stoichiometric stacking of perylene-TCNQ co-crystals towards different nano/microstructures by tuning the solution concentration of donor and acceptor. Distinct molecular packing structures in these two types of co-crystals largely influence their charge transporting behavior and photoresponsivity, providing valuable insight into the rational design and controllable synthesis of organic co-crystals with desired functions.2 Last but not the least, we demonstrate the photocurrent generation of molecular heterojunction co- crystals. Theoretical calculations reveals the different charge recombination degree of these two co-crystals, indicating that molecualr stacking plays an important role in the photovoltaic effects. This work opens an avenue to develop molecular scale p-n junction cocrystals as a promising donor-acceptor contacting mode for application in organic solar cells.3 References 1. Zhen, Y.; Tanaka, H.*; Harano, K.; Okada, S.; Matsuo, Y.*; Nakamura, E.*, J. Am. Chem. Soc. 2015, 137, 2247. 2. Zhu, W.; Yi, Y.; Zhen, Y.*; Hu, W.*, Small 2015, 11, 2150. 3. Zhang, H.; Jiang, L.; Zhen, Y.*; Zhang, J.; Han, G.; Zhang, X.; Fu, X.; Yi, Y.*; Xu, W.*; Dong, H.; Chen, W.; Hu, W.*; Zhu, D., Adv. Electron. Mater. 2016, 2, 1500423. 243 Cobalt-catalyzed Synthesis of Heterocycles via C-H Bond Activation Yue L, Wenlong Y, Qiangqiang Y, Yuhong Z* e-mail: [email protected] Department of Chemistry, Zhejiang University, China Heterocycles are important structural motifs in natural products, pharmaceuticals, and functional materials. New and more efficient chemical reactions and methodologies could revolutionize the research for the preparation of heterocycles. Over the past decades, transition-metal-catalyzed C−H functionalization[1] has emerged as a powerful synthetic tool for the synthesis of a wide variety of structurally complicated heterocycles without the preactivation of starting materials. As a representative earth-abundant and less toxic transition metal, cobalt-catalyzed C-H functionalization[2] has drawn much attention for the synthesis of heterocyclic scaffolds. We have developed several cobalt-catalyzed methods for the synthesis of important heterocycles such as pyrroles,[3] quinolines,[4] indenones[5] and quinoline N-oxides[6]. These methods provide simple and efficient routes for the synthesis of diverse heterocycle compounds. Fig. 1 Cobalt‐catalyzed synthesis of heterocycles References [1] Z. Chen , B. Wang, J.Zhang, W. Yu, Z. Liu, Y. Zhang. Org. Chem. Front. 2015, 2, 1107. [2] M. Moselage, J. Li, L. Ackermann. ACS Catal. 2016, 6, 498. [3] W. Yu, W. Zhang, Y. Liu, Y. Zhou, Z. Liu, Y. Zhang. RSC Adv. 2016, 6, 24768. [4] Q. Yan, Z. Chen, Z. Liu, Y. Zhang. Org. Chem. Front. 2016, 3, 678. [5] W. Yu, W. Zhang, Z. Liu, Y. Zhang. Chem. Commun. 2016,52, 6837. [6] Y. Liu, C. Wang, N. Lv, Z. Liu, Y. Zhang. Adv. Synth. Catal. 2017,10.1002/adsc.201600834. 244 COLORIMETRIC DEMONSTRATION IN ASSESSING THE ACIDITY AND BASICITY OF AMPHIPROTIC ANIONS Punzalan, J1, Organo, V2 Presenting author’s e-mail: [email protected] 1 University of the Philippines, Manila, Philippines 2 University of the Philippines, Manila, Philippines A colorimetric demonstration using pH indicators in illustrating the acidic or basic nature of common amphiprotic anions in aqueous solutions is presented. The demonstration is simple and offers a more visually and innovative approach for educators in teaching topics such as amphoterism, acid-base conjugates, equilibrium and hydrolysis. Typically, this demonstration can be completed in less than 10 minutes making it a feasible classroom activity suitable for senior high school or undergraduate students. 245 Copper(II)-Catalyzed C-O/C-S Bond Formation between Aryl Halides and Alkanediol/Alkanedithiol: Synthesis of Phenols and Thiophenols Chae, J. e-mail: [email protected] Sungshin W. University, Seoul, Korea Carbon-heteroatom bond formation via cross-coupling reactions is among the important transformations in chemical synthesis, as the resulting products are useful in various applications in the fields such as medicine and industrial materials. We have been developing efficient and practical methods for the preparation of phenols, thiophenols, and their derivatives, using Cu (II)-catalyzed cross-coupling reactions. Here we wish to report recent progress in our research. First, an efficient copper-catalyzed C-O cross-coupling reaction between aryl bromides and ethylene glycol has been developed employing cheaper, more efficient, and easily removable copper(II) catalyst. A broad range of aryl bromides were coupled with ethylene glycol using catalytic CuCl2 and K2CO3 in the absence of any other ligands or solvents to afford the hydroxyethyl aryl ethers in good to excellent yields. In this protocol, ethylene glycol has the multilateral functions as coupling reactants, ligands, and solvents. The resulting hydroxyethyl aryl ethers were further readily converted into the corresponding phenols, presenting a valuable alternative way to phenols from aryl bromides. Similarly, aryl halides were cross-coupled with 1,2-ethanedithiol under copper(II)-catalytic conditions. In this case, the resulting coupled products were in-situ directly converted into aryl thiols via intramolecular cleavage of ArS-Calkyl bond. Thus, the newly developed protocol provides a highly efficient metal-catalyzed single-step synthesis of thiophenols from aryl halides. It features use of readily available reagents, a simple operation, and relatively mild reaction conditions. A broad substrate scope with excellent functional group compatibility was observed and a variety of thiophenols were directly prepared from aryl halides in high yields. 246 Copper-Catalyzed Arylation of Benzothiazoles with Toluene Derivatives Li, C, Jia, X Shanghai University, Shanghai, P. R. China 2-Aryl benzothiazole represents a privileged synthetic motif since many compounds containing this core structure exhibit diverse biological and pharmacologicalactivities such as antitumor, antiviral, and antimicrobial. As a consequence, many efforts have been devoted to the synthesis of such skeletons in an efficient manner. Traditionally, these compounds could be prepared from the condensation of 2-aminothiophenol with carboxylic acids or aldehydes. Nevertheless, these methods often suffered from the drawbacks including high reaction temperature, and the difficulties in synthesizing the starting materials. To overcome the drawbacks of traditional methods, there is a continuous demand for the development of efficient and environmentally benign synthetic strategies. On the other hand, toluene and its derivatives were considered to be simplest and readily available starting materials in nature, which made them highly valuable building blocks in organic synthesis. A careful literature survey revealed that reactions using toluene derivatives as benzyl precursor were very popular, thus offering a new opportunity for the formation of carbon-carbon and carbon-heteroatom bond. Additionally, using arylmethanes as acyl source was another research focus and much progress had been achieved. In this regard, we became interested in exploring novel reactions using toluene derivatives as versatile building blocks. Most recently, we have just disclosed the coupling reaction of toluene derivatives with isocyanides and carbonyl compounds, respectively. As a continuation of our previous research, herein we wish to disclose a copper-catalyzed synthesis of 2-aryl benzothiazole from benzothiazole and toluene derivatives. In this work, we have developed a novel copper-catalyzed synthesis of 2-aryl benzothiazole from readily available toluene derivatives and benzothiazole. Moreover, many mechanistic studies were also made to explain the present coupling reaction. Other features of present strategy also included the employment of simple starting materials, a broad range of substrate scope, and mild reaction conditions. As a result, the present reaction has potential to be further applied in organic synthesis. 247 Copper-Catalyzed Electrophilic Amination of Heteroarenes and Internal Alkynes with O-Benzoylhydroxylamines Yoon, H, and Lee, Y* e-mail: [email protected] Department of Chemistry, Kwangwoon University, Seoul, Korea ABSTRACT: Heteroaryl amines are important scaffolds presented in natural products, biologically active molecules and pharmaceutical targets. Various synthetic methods for formation of C(sp2)-N bonds have been developed such as Buchwald-Hartwig amination reactions, Ullman-Goldburg type amination reactions, and transition-metal-mediated oxidative coupling reactions, which involve primary or secondary amines as nucleophilic sources. As an alternative strategy, copper-catalyzed electrophilic amination of O- benzoylhydroxylamines as electrophilic sources with organometallic reagents has attracted attention. For example, a variety of organometallic reagents based on organoborons, - magnesiums, -silicons, and –zincs can be efficiently aminated using electrophilic amines promoted by Cu catalyst. In our study, we investigated an efficient and mild Cu-catalyzed electrophilic amination with organoaluminum reagents in the presence of 1-3 mol % of CuCl, affording a wide range of heteroarylamines with high efficiency. Heteroarylaluminums can be readily prepared from the direct lithiation of readily available heteroarenes, followed by transmetallation with diethylaluminum chloride. In addition, we studied electrophilic amination of alkenylaluminum reagents derived from Ni-catalyzed hydroalumination of internal alkynes with diisobutylaluminum hydride (dibal-H). A broad range of enamines and tertiary amines can be synthesized in good yields. These copper catalytic protocols are efficient and practical to prepare various amine compounds. 248 Coreactant-free and supersensitive sensing for Cu2+ by graphene oxide amplified electrochemiluminescence of graphitic carbon nitrid Binyuan Xia Institute of Materials, China Academy of Engineering Physics, Mianyang 621900, P. R. China E-mail: [email protected] Here for the first time, we present a novel electrochemiluminescence (ECL) sensor based on graphitic carbon nitride/graphene oxide (g-C3N4/GO) hybrid for the ultrasensitive 2+ detection of Cu , which is a common pollutant in environmental system. The g-C3N4/GO shows stable ECL signal in the presence of the self−produced coreactant from oxygen reduction, and the ECL signal could be effectively quenched by Cu2+, the possible ECL detection mechanism has been proposed in detail. GO can not only significantly enhance the cathodic ECL signal of g-C3N4 ( ~3.8 times), but also serve as immobilization platform for g-C3N4. After optimization of experimental conditions, the proposed protocol can offer a ultrasensitive, highly selective and recyclable method for the detection of Cu2+ with a low detection limit of 1.0 × 10−11 M and a wide linear range from 1.0 × 10−11 to 1.0 × 10−7 M. Moreover, the practicability of the ECL sensor in real wastewater samples is also tested, showing that the proposed ECL sensor could be a promising alternative method for the emergency and routine monitoring of Cu2+ in real sample. Keywords: Ultra-trace Cu2+; Graphitic carbon nitride; Graphene oxide; Electrochemiluminescence sensing 249 Correlation Between Oxidases Enzyme Activity and Total Phenolic Content Loh, ZH1, Oh, HKF1, Lim, YY1 Presenting author’s e-mail: [email protected] 1Monash University Malaysia, Bandar Sunway, Malaysia Information regarding the relationship between enzymatic oxidases (PPO) and peroxidases (POD) and degradation of phenolic contents in herbal tea leaves is scarce. Herbal tea industries mostly use drying method especially ambient air dry to prolong the shelf life of tea leaves. In the air drying method, there is a possibility that the enzymes would degrade the antioxidative phenolic compounds in herbal tea leaves. This preliminary study focuses on the correlation between enzymatic activity and the percentage decrease in the total phenolic content (TPC) in several herbal tea leaves from tropical regions. Leaves of Persea americana, Morus alba, Orthosiphon stamineus and Thunbergia laurifolia were used in this study. The leaves were subjected to ambient air drying at 24 ± 1 °C. The change in TPC was measured. PPO and POD activity were determined from fresh tea leaves. The relationship between percentage of TPC change and PPO activity was determined with a trendline of y = 3.1879x + 32.037 (R2 = 0.9174). The relationship between percentage of TPC change and POD activity was expressed as y = -0.4473x + 47.193 (R2 = 0.0298). The result suggests that there is a positive correlation between PPO activity and TPC decrease in herbal tea leaves while there is no correlation between POD activity and phenolics degradation. This study could benefit the herbal tea industry by providing the most economical drying method for the best preservation of nutraceutical properties in tea leaves. 250 Covalent bio-conjugation of hydroxyapatite for lipase immobilization Jun, M, Jung, S. Park, S. Sungshin Women’s University, Seoul, Republic of Korea Hydroxyapatite (HA) is a major component of biological bone systems. Hence, HA is regarded as a biocomparable and environmentally benign material. During bone growth, many proteins interact with and bind to HA, although the detailed mechanism of bone growth is still unclear. Researchers have used the protein adsorption property of HA in many bio-applications such as protein purification and nanomedical application. Although proteins can be physically adsorbed on HA, stronger protein binding is often required in a particular application. Recently, a few research groups have reported the covalent conjugation of HA using specific compounds (i.e. bisphosphonates) as a linker. The conjugation processes using bisphosphonates require a multi-step synthesis of linkers or a further modification of proteins. Herein, we report a facile bio-conjugation on the surface of HA. First, we have activated the surface of HA by a simple treatment with a peptide coupling reagent (for instance, N,N'-dicyclohexylcarbodiimide). Then, we directly conjugated with enhanced green fluorescent protein (EGFP) as a model protein, and the conjugation was confirmed by a fluorescent microscope. We also employed the method to the covalent immobilization of lipase. However, we found that a linker compound is required for the conjugation of lipase because of the distinct polarities of the surfaces between lipase and HA. The immobilized lipase on HA exhibited higher activity in organic solvents than free form of lipase by a factor of ~100. 251 Crack-free Colloidal Photonic Crystal films for Fluorescence Enhancement Zhijie Zhu, Su Chen E-mail: [email protected] State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing Tech University, 5 Xin Mofan Road, Nanjing 210009, P. R. China. The ability to fabricate high quality colloidal photonic crystal (CPC) films in large areas is critical in many applications, ranging from flexible displays, security devices to optical enhancement. Herein, a large-scaled CPC film with crack-free structure and uniform optical performance was prepared via a hydrogen-bond assisted method. The crack-free CPC film is ascribed to the intermolecular hydrogen bonds between carboxyl (-COOH) moieties of poly(styrene-methyl methacrylate acrylic acid) microspheres and isocyanate (-NCO-) moieties of polyurethane (PU). Furthermore, the as-prepared CPC film was applied as a Bragg reflection mirror for fluorescence enhancement. We demonstrate that a 4-fold enhancement of fluorescence signal is achieved when the stopband of CPCs overlaps with the emission wavelength of Quantum dots (QDs). This simple method of preparing large area and crack-free CPC film is promising for developing efficient optical devices. Meanwhile, this achievement might offer an available method that can highly enhance QLED lamp luminance by aid of this kind of CPC/QDs films, have a profound energy saving significance. 252 CrN Thin Films Prepared by Reactive Magnetron Sputtering for Supercapacitors Wang, Z, Wei, B Presenting author’s e-mail: [email protected] College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China Supercapacitors have been becoming indispensable energy storage devices in micro electromechanical systems and have been widely studied over the past few decades. Transition metal nitrides with excellent electrical conductivity and superior cycling stability are promising candidates as supercapacitor electrode materials. In this work, we report the fabrication of CrN thin films using reactive DC magnetron sputtering and further their applications for symmetric supercapacitors for the first time. The CrN thin film electrodes fabricated under the deposition pressure of 3.5 Pa show an areal specific capacitance of 12.8 mF cm-2 at 1.0mA cm-2 and high cycling stability with 92.1% capacitance retention after 20000 cycles in 0.5 M H2SO4 electrolyte. Furthermore, our developed CrN//CrN symmetric supercapacitor can deliver a high energy density of 8.2 mWh cm-3 at the power density of 0.7 W cm-3 along with outstanding cycling stability. Thus, the CrN thin films have great potential for application in supercapacitors and other energy storage systems. 253 Cu@MOF composite catalyst for Phenylboronic acid coupling reaction Li, Bo1, Ma, Jian-Gong1, Cheng, Peng1 1 Department of Chemistry, Nankai University, Tianjin 300071, China Transition metal-catalyzed carbon-carbon coupling reaction is one of the most important reactions in organic synthesis and the synthesis of fine chemical products. Here, for the first time, CuCl has been successfully immobilized into a metal organic framework (MIL- 101(Cr)) to obtain a series of Cu@MIL-101 catalysts by a simple simultaneous impregnation reduction (SIR) method. This type of composite catalysts demonstrate excellent catalytic activity on the aerobic homocoupling of arylboronic acids under mild reaction conditions. XRD, ICP-MS, SEM-EDS and XPS characterizations of Cu@MIL-101 showed that the active species Cu+ tends to be inside the catalyst and Cu2+ accumulates near the surface of catalyst caused by MIL-101, suggesting the contribution of a strong synergistic catalytic effect between Cu+ and Cu2+ to the high catalytic efficiency. The superior utility of such composite system was also been elucidated by the broad scope of the reactants and the excellent yields of the reaction products, together with the high stability and facile recyclability of the catalyst. [1] C. H. Liu, C.Y. Lin, J. L. Chen, N. C. Lai, C. M. Yang, J. M. Chen, K. T. Lu, J. Catal. 2016, 336, 49-57 [2] H. C. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev. 2012, 112, 673-674 [3] X. H. Liu, J. G Ma, Z. Niu, G. M. Yang, and P. Cheng, Angew. Chem. Int. Ed. 2015, 127, 1002-1005 254 Cytotoxicity diterpenoids from the cultured soft coral Lobophytum crassum Bo-Rong Peng1,2, Yi-Cheng Chou2,3, Yin-Di Su2, Mei-Chin Lu 2,3, Ping-Jyun Sung2,3,Jui-Hsin Su2,3 1Doctoral degree Program in Marine Biotechnology, National Sun Yat-sen University and Academia Sinica, Kaohsiung, Taiwan 2National Museum of Marine Biology and Aquarium, Pingtung, Taiwan 3Graduate Institute of Marine Biology, National Dong Hwa University, Pingtung, Taiwan In recent years, the aquaculture technique of soft corals has been considerably enhanced; therefore, researchers have been able to obtain larger amounts of soft corals, and thus larger amounts of bioactive metabolites, and have been able to engage in examining the various pharmacological activities. Recently, our continuing searching for bioactive agents from six cultured soft corals Briareum excavatum, Lobophytum crassum, Paralemnalia thyrsoides, Sarcophyton sp., Sinularia flexibilis and Sinularia sandensis, we found that the EtOAc extracts of one soft coral Lobophytum crassum was shown to possess significantly in vitro cytotoxicity against Molt-4 cancer cell with IC50 value of 0.46 mg/mL. The current chemical investigation of Lobophytum crassum led to the discovery of two new cembrane-based diterpenoids (1 and 2) and eight known compounds (3-10). Compound 3(13-AC) exhibited the most potent cytotoxic activity against the tested eight cancer cell lines(K562, Molt-4, U937, Sup-T1, Ca9-22, LNcap, PC3, Cal-27) with IC50 values of 1.24, 0.46, 2.47, 0.56, 1.71, 3.57, 4.42 and 3.95 µg/mL respectively for 72 h.. The results of annexin-V/PI staining assays suggested that 13-AC induced cell death in Ca9-22 cells by inducing apoptosis. As demonstrated by JC-1 staining assay, 13-AC induced apoptosis by the stimulation of reactive oxygen species (ROS) generation and the disruption of mitochondrial membrane potential (MMP). The pretreatment of Ca9-22 cells with N- acetylcysteine (NAC), an antioxidant, inhibited ROS production resulting in the attenuation of the cytotoxic activity of 13-AC. Furthermore, 13-AC inhibited the metastatic ability of Ca9- 22 cells as demonstrated by wound healing assay. 255 DEAROMATIVE [3+2] CYCLOADDITION REACTIONS TOWARDS POLYCYCLIC HETEROCYCLES Rivinoja, D.J.1, Ryan, J.H.2, Hyland C.J.T1 Presenting author’s e-mail: [email protected] 1 University of Wollongong, Wollongong, Australia 2 CSIRO, Melbourne, Australia The [3 + 2] cycloaddition reaction of nitrogen-containing 1,3-dipoles with electron deficient olefins is an efficient method for the synthesis of pyrrolidine-containing compounds.1 Less studied however, is the combination of zwitterionic 1,3-dipoles derived from vinyaziridines in combination with electron-deficient indoles in [3 + 2] dearomative cycloaddition reactions. We will present our results2 showing that palladium(0)-catalysts can reveal a zwitterionic 1,3- dipole 1' from N-tosyl-vinylaziridine 1 that can undergo a cycloaddition with highly electron- poor 3-nitro-indoles 2. This reaction generates the biologically relevant and synthetically versatile pyrrolo[2,3-b]indole 3 moiety in a single operation. The reactions proceed to give the trans diastereoisomer with high selectivity, however, when a 4-substituent is present on the indole ring a complete reversal of diatereoselectivity is observed. 1 For reviews see: (a) Adrio, J., & Carretero, J. C., Chem. Commun, 2014, 50, 12434–12446. (b) Adrio, J., & Carretero, J. C. Chem. Commun., 2011, 47, 6784–6794. (c) Stanley, L. M., & Sibi, M. P. Chem. Rev., 2008, 108, 2887–2902. (d) Pellissier, H. Tetrahedron, 2007, 63, 3235–3285. (e) Coldham, I., & Hufton, R.,Chem Rev., 2005, 105, 2765–2810. (f) Gothelf, K. V., & Jørgensen, K. A.. Chem. Rev., 1998, 98, 863–910. 2 Rivinoja, D.J., Gee, Y.S., Gardiner, M.G., Ryan, J.H., Hyland, C.J.T., ACS Catal., 2017, 7, 1053-1056. 256 Dehydrofluorination of hydrofluorocarbons to fluorine olefin over NiF2-AlF3 catalysts Wenzhi, J1, Zhengxi, D1, Mengqi, S1, Xing, L2, Zhirong, Z2 Presenting author’s e-mail: [email protected]; [email protected] 1 Hubei Polytechnic University, Huangshi, China 2 Tongji University, Shanghai, China With the discharge of greenhouse gas, the problem of global climate warming is increasingly more serious, which challenges the human’s living environment. According to the Kyoto Protocol, hydrofluorocarbon compounds (HFCs), including CF3CFH2, CF3CH3, CF2FCH3 etc., were listed in the ranks of non-CO2 greenhouse gases. Hence, the disposal and transformation of HFCs is very significant currently. Currently, among the disposal methods of HFCs, the catalytic dehydrofluorination is an ideal route. Dehydrofluorination of HFCs is thermodynamically and kinetically hindered, so the development of high efficient and stable catalysts is a difficulty for this process route. In our works, CF3CFH2 with high GWP value was served as a probe raw for model dehydrofluorination of HFCs, and the NiF2-AlF3 catalysts for dehydrofluorination of CF3CFH2 to synthesize trifluoroethylene (a useful raw material for fluoropolymer) were investigated in detail. NiF2-AlF3 catalysts as the solid acid with high activity for dehydrofluorination of CF3CFH2 were prepared, in terms of adjustment or modification on surface acidity of catalyst. In addition, the surface properties, active species and surface acidity of the catalyst were characterized by BET, XRD, Raman, UV-DRS, FT-IR, NH3-TPD, XPS, TG-DSC and TEM/SEM-EDX techniques. Furethermore, the correlation between catalyst species and surface acidity was studied that clearly disclosed the structure-activity relationship of catalyst. The issues of catalytic reaction process and deactivation mechanism were studied, reflecting in discussing the reaction techniques and catalytic stablity for the dehydrofluorination of CF3CFH2. This research will not only provide a theoretical guide, but also bring the reference of industrial application in the future. 257 DESIGN OF A GREEN POLYMER WITH VERSATILE ENVIRONMENTALLY FRIENDLY APPLICATIONS Xiao, R1, Tobin, J M2, Vilela, F2, Xu, Z1 1 City University of Hong Kong, Hong Kong S.A.R., P.R. China 2 Heriot-Watt University, Edinburgh, United Kindom A metal free synthesis of a novel polymer with rigid backbone of completely fused polycyclic rings and micro-pores was obtained. The hexaazatrinaphthylene core with electron donating nitrogens leads to interesting photocatalytic performances proved by a typical photo- oxidation of benzyamine and derivatives with full conversion and high recyclability. Moreover, we developed an organic-solvent free, environmentally friendly condition of Knoevenagel reaction catalyzed by the clean polymer itself. Contrary to normal polymers normally synthesized by C-C coupling catalyzed by heavy metals (e.g., Pd, Pt, Fe, etc.) the metal free synthesized polymer, due to the coordinative nitrogen, micropores and relatively high surface area, can pick up heavy metal (eg. Pb) from polluted water to a final concentration comparable to drinking limit. Such applications verifies the polymer for potential applications in clean energy, cleasing of water pollution and green chemistry. This work is supported by Research Grants Council of Hong Kong SAR [Project No.: 9042087 (CityU 11303414)]. 258 Desulfurization slags: from wastes to PFS coagulant by persulfate oxidation Guo Ran, Zhang Guoquan e-mail: [email protected] Key Laboratory of Industrial Ecology and Environmental Engineering, MOE, School of Environmental Science and Technology, Dalian University of Technology, Linggong road 2#, Dalian 116024, China. Abstract Desulfurization slags (DSS), which contain rich iron and sulfur resources, are the main by- product generated from industrial gas desulphurization process. The special characteristics of self-heating and even spontaneous combustion as well as release of hydrogen sulfide gas in normal temperature, impose a serious environment safety problem to industrial production and public health. Therefore, it is very important to reasonably handle DSS, especially from both the viewpoints of environmental sustainability and effective resource utilization. Herein, we report the usage of DSS as the raw material to synthesize polymeric ferric sulfate (PFS) coagulant by catalytic thermal activation of persulfate method. First, FeS in DSS was oxidized into Fe2(SO4)3 by Na2S2O8 under heating. The condition optimization was conducted in the term of different weight ratio of Na2S2O8/DSS, temperature, reaction time and stirring speed. Then, PFS was synthesized through the hydrolytic polymerization of Fe2(SO4)3, and subsequently characterized by SEM, XRD, and FTIR. Finally，the coagulation performance of PFS was evaluated via the treatment of kaolin suspensions. Results showed that (1) the activation efficiency of Na2S2O8 can be significantly improved by DSS; (2) the leaching rate of iron is up to 93.48% and no hydrogen sulfide releasing under the optimum conditions; (3) about 98% of kaolin suspensions was removed within the pH range of 5.0-11.0. In brief, the hazardous DSS can be successfully transformed into high-performance PFS coagulant through the catalytic thermal activation of persulfate. 259 DEVELOPMENT OF BACTERIAL CELLULOSE/CHITOSAN/SILVER NANOPARTICLES COMPOSITE AS WOUND DRESSING Magculang, M1,3, Balitaan, J1,3, Santiago, K1,2,3 [email protected] 1 Department of Chemistry, College of Science 2Research Center for the Natural and Applied Sciences 3University of Santo Tomas, Manila, Philippines ABSTRACT TEXT There has been an increasing interest in the use of bacterial cellulose (BC) as wound dressings due to its biocompatibility, high moisture content and unique nanofibril network morphology, mimicking the extracellular matrix. However, the applications of BC in the field of biomedicine have been delimited by to its lack of antimicrobial activity essential in promoting normal wound healing. In this study, chitosan (Ch) and silver nanoparticles (AgNPs) were used as reinforcement materials to improve the characteristics and structure of BC, and subsequently imparting antimicrobial property to it. Chitosan, an amino polysaccharide, was prepared thru deacetylation of chitin extracted from waste materials, particularly shrimp shells. On the other hand, AgNPs were green-synthesized using aqueous pineapple leaf (Ananas comosus) extract and ascorbic acid. UV-Vis spectrometry indicated the formation of AgNPs, exhibiting surface plasmon absorption at 440-460 nm. FTIR spectrum of the composite indicated the intermolecular interaction between BC and Ch. SEM images showed a well-organized three-dimensional network structure of BC/Ch/AgNPs film. BC/Ch/AgNPs composite exhibited significant inhibition against S. aureus and E. coli. Benzalkonium chloride (Bcl), a cationic surfactant widely used as topical antiseptic agent for wounds, was selected for drug release studies. It was revealed that BC/Ch/AgNPs composite has the ability to sustainably release Bcl over a period of time, critical for wound healing. Overall, the results suggest that BC/Ch/AgNPs composite could be a promising wound dressing material. 260 Development of Phosphine Oxide Catalyst Lao, Z, Toy, P Presenting author’s e-mail: [email protected] The University of Hong Kong, Hong Kong, PRC ABSTRACT In the field of organic chemistry, phosphine oxides have generally been viewed as undesirable nuisances since they are often formed as reaction by-products or result from undesired oxidation of a phosphine catalyst or ligand, and must ultimately be separated from the desired reaction product. However, recent research has shown the potential utility of phosphine oxides as catalysts in a variety of selective reactions. We have been active in this area and have focused on the development of new phosphine oxide-catalyzed reactions such as the application of triphenylphosphine oxide (TPPO) as a Lewis base catalyst in reduction reactions, and the use of 3-methyl-1-phenyl-2-phospholene 1-oxide (MPPO) as a catalyst in intra- or inter- molecular reactions. Herein, we will introduce three recently developed methods that involve phosphine oxides as catalyst: (1) TPPO-catalyzed reductive alpha-halogenation reactions, (2) MPPO-catalyzed chromatography-free amide formation reactions, and (3) Intra-molecular one-pot/three-step tandem reactions that can form pyrroline, tetrahydropyridine, and larger ring structures. 261 DEVELOPMENT OF REGIOSELECTIVE O-GLYCOSYLATION REACTION FOR SYNTHESIS OF DISACCHARIDE NUCLEOSIDES Someya, H.1; Itoh, T.1; Aoki, S.1 Presenting author’s e-mail: [email protected] 1 Tokyo University of Science, Noda, Japan Disaccharide nucleosides which contain an external sugar moiety linked to one of the hydroxyl groups of the nucleoside via an O-glycoside bond constitute an important class of natural compounds. They are found in biopolymer, such as tRNA and poly(ADP-ribose), as well as antibiotics and other biologically active compounds.1,2 Therefore, disaccharide nucleosides are expected to make good drug candidates. The synthetic methods of disaccharide nucleosides are classified into three categories: enzymatic synthesis, chemical N-glycosylation and chemical O-glycosylation. The chemical O-glycosylation would be useful because of not only application for various glycosyl donors and nucleoside acceptors but also availability of stereoselective reaction by neighboring group participation. In this context, direct O-glycosylation of 2’- deoxyribonucleosides with thioglycosides in the presence of silver triflate and p- toluenesulfenyl chloride was reported.3 In this presentation, we report on the synthesis of disaccharide nucleosides by regioselective chemical O-glycosylation of unprotected ribonucleosides by the use of boronic acids. The 2’,3’-diol of the ribonucleoside was temporary protected by the formation of cyclic boronate esters and regioselective glycosylation of 5’-hydroxyl group with thioglycosides afforded the corresponding disaccharide nucleosides in fairly good yields.4 1) Efimtseva, E. V.; Mikhailov, S. N. Russ. Chem. Rev. 2004, 73, 401–414. 2) Knapp, S. Chem. Rev. 1995, 95, 1859–1876. 3) Aoki, S.; Fukumoto, T.; Itoh, T.; Kurihara, M.; Saito, S.; Komabiki, S. Chem. Asian J. 2015, 10, 740–751. 4) Someya, H.; Aoki, S. Manuscript in preparation. 262 Diiridium (III) Complexes as Emission Probes for G-quadruplex DNA and Cell Imaging Tikum Florence Anjong, Jinheung Kim Presenting author’s e-mail: [email protected] Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea ABSTRACT TEXT DNA G-quadruplex is a four stranded structure, derived from a guanine (G) rich DNA sequence. Though G-rich sequences have been demonstrated to form G-quadruplex structure in vitro, the existence of G-quadruplex structure in vivo is still controversial. Thus detecting G-quadruplex structure has great significance for cell proliferation, cancer research and drug development. Also, imaging of small organelles in the cell such as ER is very important, in understanding the structure and function of these organelles. Herein, two new dinuclear iridium (Ir) complexes bridged by a conjugate aromatic tppz ligand, were prepared. The DNA binding properties of both complexes where studied using single, double stranded and G-quadruplex DNA. Interestingly, the Ir complex demonstrated selectivity for G-quadruplex DNA over other control DNA which was observed by an enhancement in the phosphorescent spectra of the complex. In order to understand their possible interaction with lipid-rich organelles in live cells, the phosphorescent properties of both complexes were studied using liposomes which showed an increased in phosphorescent intensity upon the addition of liposomes with the probe showing a greater enhancement. We also confirmed that the Ir complexes could be used as probes in live cells. The probes were intensely stained in HeLa cervical cancer cells. Excitation with 488 nm laser showed red emission localized in the cytosol of cells. Cellular studies showed that the probes were located inside HeLa cells, but neither complex passed through the nuclear membrane. However, the complexes possessed superior photostability, indicating their role as good luminescent agents for imaging and tracking the endoplasmic reticulum (ER) in live cells. 263 Discovery and synthesis of novel peroxisome proliferator-activated receptor δ agonists Chin, J1, Cho, SJ1, Park, KD2 [email protected] [email protected] [email protected] 1 New Drug Development Center, Daegu-Gyeongbuk Medical Innovation Foundation, 2 Center for Neuro-Medicine, Korea Institute of Science and Technology, Seoul, 02792, Korea Peroxisome Proliferator-Activated Receptor δ (PPARδ) has recently come into the focus as a re-emerging drug target for the treatment of associated diseases such as metabolic syndrome as its activation alters glucose and lipid metabolism through a transcriptional regulation and results in beneficial pharmacological actions, typically an exercise mimic. We synthesized novel PPARδ ligands and an efficient synthetic route to these analogs was also developed. Surprisingly, some of compounds were potent and selective hPPARδ agonists with 200-fold selectivity over the other two subtypes, namely, hPPAR δ and hPPARδ. Some selective PPARδ ligands showed good bioavailability and in vivo efficacy. These results suggest that our novel PPAR δ agonists could be promising candidates for inflammation and metabolic diseases. 264 Discovery of New Oxychloride Phosphors Based on Ruddlesden-Popper Structure Hasegawa, T1,2, Kim, S.W2,3, Toda, K2, Sato, M2 and Ueda, T1 Presenting author’s e-mail: [email protected] 1 Kochi University, Kochi, Japan 2 Niigata University, Niigata, Japan 3 Sejong University, Seoul, Republic of Korea White lighting emitting diodes (White-LEDs) are widely used for lighting devices, displays and head-lights of an automotive because of having much advantages, such as a long-life time, high efficiency and environmental friendless. The general white-LEDs are combined with InGaN based blue LED chips and yellow phosphors, which can be excited by blue-light from the LED chip. Since the efficacy of UV-LED chips recently enhances with remarkable development the LED technology, the new type white-LED devices using UV-light excitable phosphor materials attracts attention as next-generation lighting device. Therefore, it is necessary to newly discover the UV-light excitable phosphor materials. However, the promising host materials for the novel phosphor have limitation, and it is difficult to find the suitable host materials from databases. Thus, the discovery of new compounds is important for the development of the novel phosphor materials. We focused on the oxychlorides for searching the host materials with new phase because the interested luminescence properties have been observed in the oxyhalides matrix including oxychlorides. Eu2+ and Ce3+ show the special luminescence spectrum depended on the surrounding crystal-fields. Particular, scandate based phosphors with Ce3+ as an activator discovered to show the unique red emission in previous work. In this work, as the results of trying the search for Sr-Sc-O-Cl system, we succeeded to discover the new oxychloride, Sr3Sc2O5Cl2, which has a Ruddlesden-Popper phase. The crystal structure of Sr3Sc2O5Cl2 is composed of lamination the SrScO2Cl perovskite and SrCl rock-salt layers (Figure 1). Figure 1. Crystal structure of new Sr3Sc2O5Cl2 with Ruddlesden-Popper phase. 265 D-phenothrin biodegradation pathway in Pseudomonas sp. P31 Shaohua Chen1, Hui Zhan1, Yanmei Feng1, Jingjing Yang1, Fang Yang1 Presenting author’s e-mail: [email protected] 1 State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources, Integrative Microbiology Research Centre, South China Agricultural University, Guangzhou, China ABSTRACT TEXT D-phenothrin is a common environmental pollutant which poses increased risks to ecosystem and living organisms, yet little is known about the metabolic pathway of this chemical. This study reported a novel D-phenothrin-degrading bacterial strain, Pseudomonas sp. P31 was isolated from activated sludge by an enrichment method. Strain P31 utilized D-phenothrin as the sole carbon source for growth and completely degraded the chemical within 72 h. The high performance liquid chromatography (HPLC) and gas chromatopraphy-mass spectrometry (GC-MS) studies were conducted to monitor the degradation of D-phenothrin by strain P31. On the basis of chemical structures of D- phenothrin and the identified metabolites, a novel biodegradation pathway of D-phenothrin was proposed (Figure 1). D-phenothrin was initially hydrolyzed by cleavage of the carboxylester linkage to produce (1R,3R)-trans-2,2-dimethyl-3-(2-methyl-1- propenyl)cyclopropane-1-carboxylic acid and 3-phenoxybenzaldehyde. Then 3- phenoxybenzaldehyde was subject to diaryl bond cleavage, resulting in the formation of 1,2- benzenedicarboxylic butyl dacyl ester. Eventually, D-phenothrin was degraded by strain P31 without any persistent accumulative product. This is the first report of a pathway of degradation of D-phenothrin by hydrolysis of carboxylester linkage and cleavage of diaryl bond in a microorganism, which we propose is of vital importance in D-phenothrin biogeocycle. Figure 1 Proposed pathway for biodegradation of D-phenothrin in strain P31 266 EFFCIENT METAL-FREE SYNTHESIS OF PERFLUOROALKYLATED FLUORENES Sun, Z1, He, D1, Chen, J1, Han, J1, Zhang, H1, Cao, W*1,2 1 Department of Chemistry, Shanghai University; 2 Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences ABSTRACT TEXT Fluorene is one of the simplest motifs in polycyclic aromatic hydrocarbons, and its derivatives have found broad applications in materials science, pharmaceutical chemistry and organic synthesis[1]. In recent years, the photoelectrical potential of fluorene and related derivatives has become well recognized. Herein we report a novel and efficient metal-free method for the synthesis of perfluoroalkylated fluorene derivatives involving a reaction of 2-(2,3-dihydro- 1H-inden-1-ylidene)malononitriles[2] 1 and methyl perfluoroalk-2-ynoates 2. A series of perfluoroalkylated fluorene derivatives 3 were synthesized in good to excellent yields (Scheme 1 and Table 1). Table 1 Synthesis of perfluoroalkylated fluorene derivatives 3a b Entry R RF Product 3 Yield (%) 1 H CF3 3a 96 2 5-Br CF3 3d 92 3 H C2F5 3b 94 4 5-Br C2F5 3e 93 5 H C3F7 3c 94 6 5-Br C3F7 3f 90 a Reaction condition: 1 (1 mmol), 2 (1.2 mmol), K2CO3 (0.1 equiv) were stirred in toluene (5 mL) at 80 oC for 6 h. b Isolated yields. ACKNOWLEDGEMENT We are grateful to the National Natural Science Foundation of China (Grant Nos. 21672138, 21272152, 21542005) for the financial support. REFERENCES [1] (a) Justin Thomas, K. R.; Baheti, A. Mater. Technol. 2013, 28, 71. (b) Miyatake, K.; Bae, B.; Watanabe, M. Polym. Chem. 2011, 2, 1919. [2] Xue, D.; Chen, Y.; Cui, X.; Deng, J. J. Org. Chem. 2005, 70, 3584. 267 EFFCIENT SYNTHESIS OF TRIFLUOROMETHYLATED 5H-SPIRO[FURAN-2,3'- INDOLIN]-2'-ONES Tao, L1, Fan, Z1, Chen, J1, Han, J1, Zhang, H1, Cao, W*1,2 1 Department of Chemistry, Shanghai University; 2 Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences ABSTRACT TEXT Indolinone is an important class of heterocyclic compounds. The structural units widely present in natural products, drug molecules and functional materials[1]. Numerous studies show that, when introduction of fluorine atom(s) into the heterocyclic compound, it’s physical, chemical and physiological properties could be improved significantly[2]. Thus, here we report an efficient method for the synthesis of trifluoromethylated 5H-spiro[furan-2,3’-indolin]-2’-one derivatives 4 involving a reaction of N-substituted isatins 1, isocyanides 2 and methyl 1,1,1- trifluorobut-2-ynoate 3 (Scheme 1 and Table 1). Table 1 Synthesis of trifluoromethylated 5H-spiro[furan-2,3’-indolin]-2’-one 4a Entry R1 R2 Product 4 Yield (%)b 1 H (CH3)3C 4a 93 2 H Cyclohexyl 4b 82 3 H Ph 4c 89 4 5-Br (CH3)3C 4d 83 5 5-CH3 (CH3)3C 4e 90 a Reaction condition: 1 (1 mmol), 2 (1.5 mmol) and 3 (1.5 mmol) were stirred in toluene (5 mL) at 100 oC for 3 h. b Isolated yields. ACKNOWLEDGEMENT We are grateful to the National Natural Science Foundation of China (Grant Nos. 21672138, 21272152, 21542005) for the financial support. REFERENCES [1] Fu, W.; Zhu, M.; Zou, G.; Xu, C.; Wang, Z. Asian J. Org. Chem. 2014, 12, 1273. [2] Gu, J.; Zhang, X. Org. Lett. 2015, 17, 5384. 268 Effective Antitumor Candidates Based upon Ferrocenylselenoether Derivatives Jing, S, Xia, Q, Qu, J, Ji, W, Zhu, XF, Zhou, HY School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, China Owing to the advantages of kinetic stability, hypotoxicity, easily modification and good redox properties, a number of bioferrocene species have been found to be promising anticancer candidates, such as ferrocifen type compounds and ferrocenyl-nucleobases. Selenium has also been found to play the role of anti-carcinogenesis in two ways, as an essential nutrient providing the catalytic centers of antioxidant enzymes, or as a source that directly affect tumorigenesis. A series of ferrocenylselenoether derivatives were prepared with different structural parameters, such as chalcogen atoms, cycle and semi-rigidity. The best in vitro anticancer activity occurred with 1,5-diselena[8]ferrocenophane, which inhibited cancer cell growth at the lowest micromole concentrations. The biological studies showed that it arrested cell cycle in G1 phase and induced apoptosis by activating caspase 3/9, also inhibited endothelial cell (HUVECs) formation. The results suggest that the excellent biological activities are attributed to the synergetic effect of ferrocenophane, chalcogen atom and catechol group. Acknowledgments We gratefully acknowledge financial support from the National Natural Science Foundation of China (Grant Nos. 21671101 and 21171092) and National Basic Research Program of China (973 Program) (No. 2013CB733504). 269 Electrochemical DNA biosensing based on graphene/ molybdenum disulphide/gold nanoparticle composites Yu, Y., and Wang, Y. Presenting author’s e-mail: [email protected] Huaqiao University, Xiamen, Fujian, China ABSTRACT TEXT A sensitive thin film for the detection of DNA hybridization was established. The platform was prepared based on the modification of glass carbon electrode with graphene (Gr) and analogue graphene (molybdenum disulfide) composite (Gr/MoS2) decorated with gold nanoparticles. The composite of Gr/MoS2 was synthesized via a hydrothermal method by the use of polyethyleneimine (PEI) as the dispersant. Gold nanoparticles were in situ synthesized on the surface of the Gr/MoS2 composite, which were employed to anchor single probe DNA molecules. The electrochemical properties of the composites were investigated via CV and EIS. DNA immobilization and hybridization on the prepared functional film were studied and detected via cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under the optimized conditions, the DNA biosensor shows a good linear relationship between 0.01 pM to 100 pM with a limit of detection of 0.005 pM. The functional hybrid film displays good stability during repeated regeneration and hybridization cycles. 270 Electrochemiluminescence immunosensor for microcystin based on MoS2 nanosheets Kang T.-F.*, Zhang J.-J. E-mail: [email protected] College of Environmental and Energy Engineering, Beijing University of Technology, Beijing, P. R. China Water pollution caused by microcystins is increasing all over the world. It is important to develop new methods of determining microcystins. An electrochemiluminescence (ECL) immunosensor for microcystin-leucine- arginine (MCLR) was developed in this paper. Layered MoS2 nanosheets as the carriers of bovine serum albumin coupling MCLR (MCLR- BSA) were modified onto the surface of a glassy carbon electrode. Large amounts of CdSe quantum dots (QDs) were loaded on graphene sheets (GS) to prepare composite (QDs-GS). The composite was used to label antibody against MCLR (Ab) to obtain composites (Ab- QDs-GS) which can amplify ECL signal. The immunosensor was incubated with 5 μL Ab- QDs-GS suspension and 5 μL different concentration MCLR solution for 1 h. MCLR in solution competed with MCLR-BSA modified on the electrode surface for the limited binding sites of Ab labeled with QDs-GS to form the immune-complex. ECL experiment was performed with a MPI-A analyser, an immunosensor as working electrode, a platinum wire as counter, and a Ag/AgCl as reference electrodes. The immunosensor generated ECL signal in 0.1 M phosphate buffer solution containing of 0.1 M K2S2O8. The potential window was from 0 to -1.5 V with a scan rate of 100 mV/s. The ECL intensity of the immunosensor was decreased with the increases of MCLR concentration and was linearly dependent on the MCLR concentration from 0.0050 to 100 μg/L with a detection limit of 0.003μg/L. The immunosensor was applied in determining MCLR in real samples and satisfactory results were obtained. 271 Electro-generated ROS for the oxidative dissolution of V2O3 in alkaline solution Yudong Xue1,2, Yunting Wang1,3, Shili Zheng1, Yi Zhang1, Wei Jin1 Presenting author’s e-mail: [email protected] 1 National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 2 University of Chinese Academy of Sciences, Beijing 100049, China 3 School of Chemical and Environmental Engineering, China University of Mining and Technology of Beijing, Beijing 100083, China ABSTRACT TEXT In-situ electrochemical generated reactive oxygen species (ROS) are often used for environmental remediation in advanced oxidation process under acid conditions. In the present study, the oxidation of V(III) (vanadium oxide) to V(V) (vanadate), a critical pre- treatment process for vanadium utilization, is efficiently achieved by the reactive species produced via two-electron ORR on the N-doped carbon felt cathode in alkaline media. Nitrogen-containing functional groups appeared after N-doped treatment, which highly - enhance the hydrophilic behaviour and electro-catalytic properties of HO2 generation. In this study, novel electro-oxidation mechanism on the cathode is presented for vanadium transformation. It was determined by radical quenching experiment that 43.5% V(III) was - oxidized by HO2 and 56.5% was owning to the hydroxyl radicals generated from vanadium self-induced electro-Fenton-like reaction, respectively. The V2O3 solid particles can be well in-situ oxidized on the surface of cathode because of the V2O3 adsorbed on the carbon felt surface during the EAOPs. Therefore, this novel V2O3 electro-oxidation mechanism found for the ROS under alkaline conditions supplements the fundamentals of heavy metal transformation in electrochemical processes and serves a promising solid waste treatment method. 272 Electron penetration effect of pyrene/ semiconducting single- walled carbon nanotubes for enhanced electrochemical activity Ji,L.F.1 Presenting author’s e-mail: [email protected] 1 College of Chemistry & Material Science, Northwest University, Xi’an , China. The as-prepared single-walled carbon nanotubes (SWNTs) are always a mixture of metallic (m-) and semiconducting (s-) tubes. The amount of s-SWNTs is two times higher than the m-SWNTs, while the electrochemical activity is much lower than that of the m- SWNTs, owning to the vanishing electronic density of states (DOS) near Fermi levels. In this work, the pyrene derivatives 1-docosyloxylmethylpyrene (DomP) was used to penetrate electrons, and increase the DOS, making s-SWNTs similar performance as m- SWNTs in electrochemistry. The fluorescence and absorption spectra were investigated to verify the electron penetration process from DomP to s-SWNTs. Electrochemical impedance spectroscopy (EIS) and voltammetry curves demonstrated the enhanced electrochemical activity of s-SWNTs after electron penetration, giving rise to the increased electrocatalytic oxidation of guanine and adenine, and sensitive detection in DNA samples. 273 ELUCIDATING HUMAN HSP47 BINDING AND RELEASE BEHAVIOUR USING SITE- DIRECTED MUTAGENESIS Abdul-Wahab, MF1, Ibrahim, FH1, Zakeria, SM1, Homma, T2, Nagata, K3 Presenting author’s e-mail: [email protected] 1Faculty of Biosciences and Medical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia. 2Institute for Integrated Cell-Material Sciences, World Premier International Research Center Initiative, Kyoto University, Kyoto 606-8501 Japan. 3Faculty of Life Sciences, Kyoto Sangyo University, Kyoto 603-8555, Japan. ABSTRACT Collagen biosynthesis in the cell is assisted by many proteins acting as molecular chaperones. Abnormalities in collagen expression led to many types of diseases. Thus, thorough understanding of the specific molecular chaperone can assist novel treatment strategies for these collagen-related diseases. Heat shock protein 47 (HSP47) is a unique and important collagen-specific molecular chaperone in collagen biosynthesis. The molecular mechanisms for HSP47 binding to and release from collagen in the cells has just been proposed (Widmer et al., 2012; Oecal et al., 2016), using canine HSP47 as model. However, the mechanisms in human HSP47 is still unknown. We used human HSP47 gene cloned into an E. coli expression vector, for in vitro mutational analysis. Histidine residues are targeted, as the HSP47-collagen dissociation pH is similar to histidine dissociation constant (pKa). Homology modelling of human HSP47 using the crystal structure of canine HSP47 in complex with trimeric collagen model peptides was used to guide mutagenesis experiments. Alanine scanning mutagenesis, coupled with collagen binding assay and circular dichroism (CD) spectroscopy revealed that several His-to-Ala mutants (H220A, H335A, H368A) showed perturbed binding and/or structural integrity relative to wild-type. These suggest the potential involvement of the particular His residues in collagen binding and/or release. These mutants are currently being investigated using ELISA-based collagen binding assay to further assess their binding strength. Then, the secondary structure transition induced by pH will be thoroughly investigated using CD spectroscopy. 274 Enhanced Seebeck Coefficient of Supramolecular Thermocells and Its Theoretical Investigation Liang, Y1, Zhou, H, Yamada, T1, 2, 3, Kimizuka, N1, 2 1Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University 2Center for Molecular Systems, Kyushu University, Fukuoka, Japan. 3PRESTO, Japan Science and Technology Agency Energy harvesting from waste heat is a promising route to relieving our reliance on fossil fuels and thermo-electrical conversion has attracted much interest. Thermo-electrochemical cells (TECs), or thermocells, are an option of thermoelectric conversion, which consists of solutions of redox pairs. The key advantages of TECs are their high Seebeck coefficient (Se), which affects the efficiency of thermoelectric conversion. Past studies on TECs focused on search on redox species and electrolytes, while the methodology for enhancing Se is still demanded. − − We succeeded in enhancing Se of I / I3 TEC by introducing host–guest interaction into the TEC. A schematic illustration of the supramolecular TEC is − − shown in Figure 1. I3 is more hydrophobic than I , and α-Cyclodextrin (α-CD) can selectively encapsulate I −. α-CD is a six-membered ring of 3 glucose units that have and can reversibly Figure 1. A schematic figure of supramolecular incorporate hydrophobic guest molecules into the TEC. Red balls, purple trinuclear chains and − − − inner cavity of the ring. I3 is captured in α-CD at blue rings represents I , I3 and α-CD, cold side of the TEC, and eliminated with elevating respectively. − temperature. Hence, the local concentrations of I3 are different between hot and cold sides, which emerges additional shift of voltage and increases Seebeck coefficient. By addition of α-CD, we observed 70% increase of Seebeck coefficient.1 − We also evaluated various derivatives of CDs. Binding constant, enthalpy and entropy of I3 and CDs were evaluated by isothermal titration calorimetry at various temperature. Concentration of − uncaptured I3 was estimated according to these parameters at various temperature, and shift of equilibrium potentials were calculated according to the Nernst equation. The observed voltage profiles were in good agreements with those of calculated ones. We discussed the relation between Se and binding constant. References: 1. Zhou, H., Yamada, T., Kimizuka, N., J. Am. Chem. Soc., 2016, 138, 10502- 10507 275 ENZYME-FREE IMPEDIMETRIC GLUCOSE SENSOR BASED ON GOLD NANOPARTICLES/POLYANILINE COMPOSITE FILM Ahammad, A. J. S, Mamun, A. A, Akter, T Presenting author’s e-mail: [email protected] Department of Chemistry, Jagannath University, Dhaka 1100, Bangladesh ABSTRACT A non-enzymatic impedimetric glucose sensor was fabricated based on the adsorption of gold nanoparticles (GNPs) onto conductive polyaniline (PANI)-modified glassy carbon electrode (GCE). The modified electrode (GCE/PANI/GNPs) was characterized by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). The determination of glucose concentration was based on the measurement of EIS with the mediation of 3− 3− electron transfer by ferricyanide ([Fe(CN)6] ). The [Fe(CN)6] is reduced to ferrocyanide 4− ([Fe(CN)6] ), which in turn is oxidized at GCE/PANI/GNPs. An increase in the glucose 4− concentration results in an increase in the diffusion current density of the [Fe(CN)6] oxidation, which corresponds to a decrease in the faradaic charge transfer resistance (Rct). A wide linear concentration range from 0.3 to 10 mM with a lower detection limit of 0.1 mM for glucose was obtained. The proposed sensor shows high sensitivity, good reproducibility, and stability. In addition, the sensor exhibits no interference from common interfering substances such as ascorbic acid, acetaminophen, and uric acid. 276 Fabrication of Metal/ZnO Photocatalysts Based on Galvanic Replacement Mechanism Chunyan Zeng, Hong Wang, Presenting author’s e-mail: [email protected] Zigong, Sichuan Province, 643000 P. R. China Sichuan University of Science and Engineering Abstract: Hierarchical Metal/ZnO (Metal=Ag, Cd, Cu) nano/microstructures have been synthesized on Zn foil based on galvanic replacement mechanism. The photocatalytic properties of the products were evaluated by the degradation of RhB dye solution under UV irradiation, and the results show that all of the products exhibit significantly enhanced photocatalytic properties comparing with pure ZnO nanorods. The Ag/ZnO Heterostructures exhibit surprisingly high degradation rate for RhB dye solution (99.5%) after photocatalytic reaction for only 14 min under UV irradiation. The Schottky barrier formed at the metal-semiconductor interfaces improves the segregation of charges and prevents the charge recombination, and thus significantly enhances the photocatalytic activities of the products. On the other hand, the high stability of the Metal/ZnO hierarchical nano/microstructures can effectively prevent the aggregation of nanostructures with simultaneously preserving high photocatalytic properties due to the existence of nanosized unites. 277 Facile Synthesis of Spirooxindolyl Isoxazoline N-Oxides via [1+4] Annulation Mode He, Z1,2, Liu, Y1 1 The State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, China 2 Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, China Recently, the classical Kukhtin-Ramirez adducts, which are readily generated from trivalent phosphorus reagents and 1,2-dicarbonyl compounds, have proven to be rich in organic reactivity through their dipolar oxyphosphonium enolate species.1 Typically they undergo a variety of organic synthetic reactions acting as carbene surrogates or 1,1-dipoles.1 In 2015, our group reported a P(NMe2)3-mediated reductive [1+4] annulation of isatins with enones, leading to facile and efficient synthesis of spirooxindole-dihydrofurans.2 Presumably this reaction proceeds via Kukhtin-Ramirez zwitterions as the key active intermediate. Accordingly it unveils a simple and efficient protocol to construct five-membered carbo- and heterocycles through the [1+4] annulation mode. Most recently, Ashfeld group has developed formal [1+4] cycloaddition of 1,2-dicarbonyls and o-quinone methides by the same strategy.3 As part of our continuous efforts to develop new annulation reactions, herein we present a new P(NMe2)3-mediated reductive [1+4] annulation of isatins with nitroalkenes, leading to facile syntheses of spirooxindolyl isoxazoline N-oxides and spirooxindolyl isoxazolines. References: 1. Zhao, W.; Yan, P. K.; Radosevich, A. T. J. Am. Chem. Soc. 2015, 137, 616, and references cited therein. 2. Zhou, R.; Zhang, K.; Chen, Y.; Meng, Q.; Liu, Y.; Li, R.; He, Z. Chem. Commun. 2015, 51, 14663. 3. Rodriguez, K. X.; Vail, J. D.; Ashfeld, B. L. Org. Lett. 2016, 18, 4514. Acknowledgment: Financial support from National Natural Science Foundation of China (Grant no. 21472096) is gratefully acknowledged. 278 Facilely Synthesized Dual-emissive Carbon Dots for Ratiometric Detection Al3+ ions 1 1 1 Xiangying, S , Cunjin, W , LuLu W Presenting author’s e-mail: [email protected] 1 College of Materials Science and Engineering, Huaqiao University, China ABSTRACT Carbon dots (CDs) have widely attracted scientist’s interests due to their extraordinary optical/electric properties, including a high PL quantum yield (QY), biocompatibility and environmental friendliness. Therefore, CDs have been successfully employed in a series of applications, such as PL-based sensing. However, most of previous reports are based on the following two situations. (i) The reported CDs-based sensing systems were established on the basis of PL quenching response. (ii) Only single emissive CDs with short or long emission wavelength could be successfully prepared and employed in sensing systems. Herein, we present a green and facile approach to obtain dual-emission CDs from ascorbic acid by hydrothermal treatment for the one time, which avoids the request of tedious synthetic methodology or the use of expensive/toxic solvents and starting materials. The sensor CDs-based exhibits the dual-emissions peaked at 410 and 535 nm, respectively, under a single excitation wavelength of 355 nm. The emissions of 535 nm can be selectively enhanced by Al3+ ions, while the blue PL as an internal reference is not affected. The detection limit of this ratiometric probe is as low as 1.19 μM, which is lower than the defined limit (7.4 μM) by World Health Organization (W.H.O.). Because of the facile synthesis, attractive PL properties, and environment friendly, the dual-emissive ratiometric PL sensor could be extended to the application in the biological, chemical and environmental fields. REFERENCES [1] P. G. Luo, S. Sahu, S.-T. Yang, S. K. Sonkar, J. Wang,H. Wang, G. E. LeCroy, L. Cao and Y.-P. Sun, J. Mater.Chem. B, 2013, 1, 2116–2127. [2] Y. Yang, X. Ji, M. Jing, H. Hou, Y. Zhu, L. Fang, X. Yang,Q. Chen and C. E. Banks, J. Mater. Chem. A, 2015, 3, 5648–5655. [3] P. Ni, H. Dai, Z. Li, Y. Sun, J. Hu, S. Jiang, Y. Wang and Z. Li, Talanta, 2015, 144, 258-262. [4] Y. Liu, Y. Liu, S.-J. Park, Y. Zhang, T. Kim, S. Chae, M. Park and H.-Y. Kim, J. Mater. Chem. A, 2015, 3, 17747-17754. [5] H. Rao, W. Liu, Z. Lu, Y. Wang, H. Ge, P. Zou, X. Wang, H. He, X. Zeng and Y. Wang, Microchimica Acta, 2015, 183, 581-588. [6] X.-Y. Sun, L.-L. Wu, J.-S. Shen, X.-G. Cao, C. Wen, B. Liu and H.-Q. Wang, RSC Adv., 2016, 6, 97346- 97351. 279 Factors on machine learning performance for chemical databases Li W1, Li H1, Hu LH1*, 1School of Computer Science and Information Technology, Northeast Normal University, Changchun, China Abstract Machine learning methods are growing fast and their applications are anticipated to solve intractable problems in many areas. Usually, the performance of machine learning models is affected by many complicated factors. The accuracy and redundancy are two basic features of input descriptors and have been considered directly impacting on model performances. In regression modeling for chemical databases, how they affect models is not that straightforward. To explore these two factors on regression for chemical databases, four machine learning models are built with various input accuracies and redundancies. The results suggest that the accuracy effects on regression models are roughly related to the correlation with the target value of the dataset. If the correlation value becomes larger due to descriptor accuracies improved, the possibility of obtaining more accurate prediction is better than that with low accuracies. No tendentious effects of the descriptor redundancy on the performance of the regression model for these chemical databases are disclosed. This indicates the redundancy is an uncertain factor, which may be unnecessary to intentionally avoid in chemical database modeling. 280 Fe (III) – the Third Generation Catalyst for Regioselective Protection of Diols Dong, H, Lv, J Huazhong University of Science and Technolgy, Wuhan, P. R. China ABSTRACT Regioselective protection plays a very important role in organic synthesis, espicially in carbohydrate chemistry, for the construction of carbohydrate building blocks that are used as donors or acceptors in complex oligosaccharide synthesis.1 Stoichiometric amounts of organotin reagents had been most widely used in selective protection2 due to the high regioselectivities obtained, coupled with relatively straightforward manipulation, which uses have to be limited or banned now due to their inherent potential toxicity. The reduced amounts of organotin reagent as the first generation catalyst3 and an organoboron reagent (Taylor’s catalyst) as the second generation catalyst4 have been successfully used for the selective protection of carbohydrates recently, however only showing good selectivity for vicinal cis-diols. In the most recent, we reported an Fe(III)-based catalyst which led to high regioselectivities with very broad substrate scope in the alkylation of diols and polyols.5 The present experiments showed that Fe(III)-based catalyst was also a good catalyst for the regioselective acylation of diols and polyols (Fifure 1). Fe(III) reagent as the third generation catalyst has a great potential to be widely used in regioselective protection considering that iron is not only of low cost and high abundance but is also non-toxic and generally environmentally benign. Figure 1. Fe (III)-catalyzed regioselective acylation of diols Reference 1) S. J. Danishefsky, Y. K. Shue, M. N. Chang, C. H. Wong, Acc. Chem. Res. 2015, 48, 643-652. 2) T. B. Grindley, Adv. Carbohydr. Chem. Biochem. 1998, 53, 17-142. 3) H. F. Xu, Y. C. Lu, Y. X. Zhou, B. Ren, Y. X. Pei, H. Dong, Z. C. Pei, Adv. Synth. Catal. 2014, 356, 1735-1740. 4) a) D. Lee, C. L. Williamson, L. N. Chan, M. S. Taylor, J. Am. Chem. Soc. 2012, 134, 8260-8267; b) L. N. Chan, M. S. Taylor, Org. Lett. 2011, 13, 3090-3093. 5) a) B. Ren, O. Ramstrom, Q. Zhang, J. Ge, H. Dong, Chem. Eur. J. 2016, 22, 2481- 2486; b) B. Ren, J. Lv, Y. Zhang, J. Tian, H. Dong, ChemCatChem 2017, DOI: 10.1002/cctc.201601558 281 Fine-Tuning Coordination Environment To Regulate Magnetic Behavior of DyIII Compounds Sun, L, Chen, S,* Xie, G* E-mail: [email protected] Northwest University, Xi’an, China ABSTRACT It is crucial to understand and elucidate the slow magnetic relaxation behaviour for DyIII- based single-molecule magnets (SMMs). Herein, through fine-tuning of the anion, lattice solvents, coordinated solvent and packing arrangement, we prepared eight dysprosium compounds. Firstly, two Dy(III) single-ion magnets with a trigonal dodecahedron (D2d) for 1 and an approximately square- antiprismatic (SAP, D4d) N2O6 coordination environment for 2, formulated as [Dy(Phen)(tfmb)3](1) and [Dy(Phen)- (tfmb)3]·0.5(1,4-dioxane) (2)(tfmb =4,4,4-trifluoro-1-(4-methylphenyl)-1,3-butanedione, Phen = 1,10-phenanthroline), were obtained. The present work[1] illustrates that guest-determined notable structure change results in different barrier heights. Moreover, the reactions of formation for 3−5, [Dy(2,3′- pcad)(NO3)2(CH3OH)2] (3), [Dy(2,3′-Hpcad)2(H2O)3]·3Cl·5H2O (4), and [Dy(2,3′-pcad)(NO3)· 3 (H2O)4]·NO3·H2O (5) [2,3′-Hpcad = N -(2-pyridoyl)-3-pyridinecarboxamidrazone], are in situ thermodynamically monitored by isothermal titration calorimetry. This work[2] might offer a promising entry into the fine-tuning for the magnetic properties of DyIII-based SMMs through variations in the solvent or anion, mainly the third chemicals (pyridine) arousing the coordination competition among solvents in self-assembly reactions and realizing the oriented synthesis on the basis of thermodynamic interpretation. Finally, three carboxylate- III bridged centrosymmetric Dy dimmers, [Dy2(2,3′-pcad)2(C2H3O2)4(H2O)2] (6), [Dy2(2,3′- pcad)2(C6H5COO)4(H2O)2] (7) and [Dy2(2,4′-pcad)2(C2H3O2)4(H2O)2]·2H2O (8) (2,4′-Hpcad = N3-(2-pyridoyl)-4-pyridinecarboxamidrazone), were synthesized . 6 and 7 shows the similar packing arrangement, while 8 presenting disparate packing arrangements. Notably, the current observation represents that the packing-arrangement plays an important role in magnetic behaviour modulation for lanthanides crystalline compounds. Reference: [1] Zhang, S.; Chen, S.-P.* Inorg. Chem. 2016, 55, 3865−3871. [2] Sun, L.; Chen, S.-P.* Inorg. Chem. 2016, 55, 10587−10596. 282 Full-crystalline Hierarchical Monolithic Zeolites as Superiorly Active and Long-lived Catalysts Xie Z K1*, Liu, Z C2, Teng, J W2, Wang Y D2, Zhou J2, Yang, W M2 Presenting author’s e-mail: [email protected] 1 SINOPEC Corporation, Beijing, China; 2Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai, China Zeolite catalyst played an important role in converting methanol and/or olefins into higher valued chemicals with great market demand. However, the present zeolite catalysts often suffer from slow diffusions of reactants/products in narrow micro-channels, leading to low effectiveness and even quick deactivation. For the obvious diffusivity advance and the resulted improved catalytic performance, hierarchical zeolites have drawn more and more attentions in recent years. Actually, to satisfy necessary mechanical strength requirement in industrial applications, developing high-performance hierarchical zeolite catalyst must based on monolithic bodies rather than only the zeolite powder. However, academic studies from the view of fundamental research were widely neglected in this field. Herein, by re-crystallizing the shaped binder/zeolite body with assistance of controlled organic template steam, full-crystalline monolithic hierarchical zeolites were prepared. Obvious intra-crystalline mesopores were in-situ created while maintaining high mechanical strength in re-crystallization. A remarkable advantage of mass transfer and utilization factor was revealed in such hierarchical monolith, which means more acid sites will be accessible after re-crystallization. Due to the improvement of diffusivity, hierarchical full-zeolitic monolithic catalyst demonstrated higher propylene yield and slower deactivation rate in C4 olefin cracking (OCC) and methanol-to-propylene (MTP) reaction. Moreover, highly prolonged cycle time, which was more than 2000 h and three times as long as that of commercial catalyst, was realized in catalysing MTP under industrial condition. Such catalyst as well as its OCC and MTP process has been successfully applied in industry with advantage of high space velocity, good stability and low energy consumption. 283 Gas Adsorption in Mg-Porphyrin-based Porous Organic Frameworks: a Computational Simulation Pang Yujia, Li Wenliang and Zhang Jingping [email protected] Faculty of Chemistry, Northeast Normal University, Changchun, China ABSTRACT TEXT A novel type of porous organic frameworks, based on Mg-porphyrin, with diamond-like topology, named POF-Mgs was computationally designed, and the gas uptakes of CO2, H2, N2, and H2O in POF-Mgs were investigated by Grand canonical Monte Carlo simulations based on first-principles derived force fields (FF). The FF, which describe the interactions between POF-Mgs and gases, were fitted by dispersion corrected double-hybrid density functional theory, B2PLYP-D3. The good agreement between the obtained FF and the first- principle energies data confirmed the reliability of the FF. The results indicate that under proper conditions, [1, 2]POF-Mg are potential candidates for H2 purification. Furthermore our simulation shows that the presence of a small amount of H2O (≤ 0.01 kPa) does not much affect the adsorption quantity of CO2, but the presence of higher partial pressure of H2O (≥ 0.1 kPa) lead to the CO2 adsorption decrease significantly. The good performance of POF- Mgs in the simulations inspires us to design novel porous materials experimentally for gas adsorption and purification. 284 Generation of Natural Products-Based Screening Libraries for Drug Discovery Egbewande, F. A.1, Coster, M. J1, and Davis, R. A1. 1Griffith Institute for Drug Discovery, Griffith University, Brisbane, QLD, Australia Natural products (NPs) represent a unique source of chemical and structural diversity that exhibit a wide variety of biological activities. _ENREF_49Exploring and designing diverse compound collections using unique and under-utilized NP scaffolds increases the chances of discovering chemical probes and/or future leads that could be developed into new drugs. This project is significant as it combines knowledge from synthetic and combinatorial chemistry, and uses novel NP-templates to create smaller and smarter libraries. This study will allow for the exploration of unique chemical space and provide distinctive screening libraries containing potential drug, lead or probe molecules. To date, three unique scaffolds, valerenic acid, gibberellic acid, and thiaplakortone A have been modified to generate libraries of analogues via parallel solution-phase synthesis. The library based on the valerenic acid scaffold has recently been screened for anti- inflammatory activity at LEO Pharma’s Open Innovation platform. This library was tested in two separate anti-inflammatory in vitro assays based on IL-8 and TNF-α inhibition. Six analogues showed moderate inhibitory activity in the IL-8 assay with IC50 values of 2.8–8.3 μM, while none of the tested compounds showed any significant effect on inhibiting TNF-α release. The gibberellic acid library is undergoing high-throughput screening for anti-cancer activity against several promising targets in prostate cancer that are linked to oxidative stress, redox homeostasis, lipid metabolism and mitochondrial function; all these processes are critical for prostate cancer growth and survival. The small library based on thiaplakortone A is currently being synthesized and will be evaluated for anti-malarial activity. 285 Glucose entrapped in titania under mild environmental conditions Yu, Z，Liu,D Beijing University of Technology, Beijing, China. ABSTRACT Considerable attention has been paid to Immobilization of enzymes onto inorganic materials for direct electron transfer of metalloproteinsin recent years. The commonly used immobilization methods include physical entrapment, physical adsorption, and covalent coupling. However, these methods usually involve complicated synthetic procedures, which are often carried out under harsh experimental conditions, and with use of toxic and expensive reagents. Hence, under mild environmental conditions, development of efficient immobilization methods, which can achieve a uniform enzyme loading on the solid support, is important and highly desirable. Braun et al first reported the sol-gel encapsulation of biomolecules in 1990. The authors showed that enzymes, trapped within a porous oxide matrix, retain their biological activity. Blin describes direct one-step immobilization of glucose oxide in well-ordered mesostructured silica. There is a maximum loading of GOD, around 11wt%, that can be entrapped in the silica network and the entrapped enzyme maintains its activity. TiO2, one of inorganic support, has been used to immobilization enzymes since it is biocompatible, chemical and thermal stability. In this work, we report a facile one-step immobilization approach of enzymes mesoporous TiO2 by the unique combination of glucose oxidase, catalase and titanium precursor and subsequent aging for one week. This approach is based on our recent work on the synthesis of Protein-Mediated Synthesis of Nanostructured Titania. This is the first demonstration of an in vivo method for CGC immobilization onto inorganic materials TiO2. The CGC shows fast direct electrochemistry. . 286 GRAPHENE/POLY (BRILLIANT CRESYL BLUE)- MODIFIED ELECTRODE FOR DETECTION OF NITRITE Ahammad, A. J. S, Alam, M. K, Mozumder M. N. I, Anju, A. N, Karim, R Presenting author’s e-mail: [email protected] Department of Chemistry, Jagannath University, Dhaka 1100, Bangladesh ABSTRACT A selective and highly sensitive electrochemical method, based on a reduced graphene oxide/poly(brilliant cresyl blue) composite film-modified glassy carbon electrode, was developed for the determination nitrite. The composite film was prepared by electrochemical reduction of graphene oxide and electrochemical polymerization of brilliant cresyl blue, respectively. The modified electrode was characterized by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). The electrocatalytic activity of modified electrode toward the oxidation of nitrite was studied by cyclic voltammetry and amperometry. Cyclic voltammograms showed that nitrite undergoes irreversible oxidation at 0.77 V at modified electrode which is 0.30 V less than that of bare GCE. This shows the efficient electrocatalytic activity of the composite film. The electroanalytical application of the composite film was done by amperometric technique. The film shows a response time of less than 1 s and wide linear range of detection from 1.0 µM to 2.0 mM. The developed sensor was successfully examined for real sample analysis with tap water and it showed a stable and reliable recovery data with high reproducibility. Experimental results showed that the proposed electrode could be used as an effective and sensitive sensor for the determination of nitrite. 287 GROWTH OF MESENCHYMAL STEM CELLS ON A FREEZE-GELATED CHITOSAN- PECTIN SCAFFOLD Uygongco, GO, Chakraborty, S, Rojas, NRL Ateneo de Manila University, Department of Chemistry, School of Science and Engineering, Loyola Schools, Quezon City, Philippines ABSTRACT Cartilage and bone related injuries are both costly to treat. In addition, current methods of treatment, such as autologous grafts, are limited by the inherent differences in mechanical properties they possess when compared to the original cartilage or bone. For this study, a scaffold for potential tissue engineering applications was made from chitosan and pectin, both natural polymers. These polymers are reported to be biocompatible and viable for use as a platform for cell proliferation and implantation. The scaffold was fabricated using freeze-gelation, which is a more efficient method than most methods in use today. The scaffold was characterized, and shown to have a porous morphology and to be thermally stable. The scaffold's potential for tissue engineering was tested using human bone marrow- derived mesenchymal stem cells, which have the potential to differentiate into either cartilage or bone. An MTT cell activity assay showed the scaffold was not cytotoxic, and supported the proliferation of the mesenchymal stem cells, which is the first step towards tissue engineering for cartilage and bone. 288 Highly Luminescent and Stable Lyotropic Liquid Crystals based on Europium β– Diketonate Complex and Ionic Liquids Sijing Yi, Xiao Chen e-mail: [email protected] Key Laboratory of Colloid and Interface Chemistry, Shandong University, Jinan, 250100, China The soft lanthanide luminescent materials are impressive for their tunable and self- assembling characters, which facilitate them to be an attractive emerging materials field of research. For this aim, the novel luminescent lyotropic liquid crystals (LLC) with different mesophases have been fabricated by ionic liquids (IL) based europium β–diketonate complexes and an amphiphilic block copolymer (P123). The ILs were used both as the solvent and also as the linkage for stabilizing the doped complexes. The analyses by XRD and FTIR revealed convincingly that the IL cations had established an effective connection with both the β–diketonate ligand and the EO blocks of P123 via strong hydrogen bonding interactions. Therefore, an extremely long decay time of the excited state was obtained in complex and an excellent photostability of such luminescent LLCs could be achieved. Their long-period ordered structures had been investigated by small-angle X-ray scattering measurements and the better luminescence performance was found in the most organized mesophase. Noteworthy, the LLCs could yield an effective confining effect on the europium complex accompanied by a sizeable elongation of the excited-state lifetime and an enhancement of the energy transfer efficiency, reaching a remarkably high value. More importantly, the modulated luminescence properties observed in different mesophase structures would offer the potential and powerful possibility to allow these unique composite LLCs present for fabricating soft luminescent materials with tunable functions. We are thankful for the financial supports from the National Natural Science Foundation of China (21373127 and 21673129). 289 High-Performance Yne-Diyne Bridged Organic Dyes for Dye-Sensitized Solar Cells Hu, X, Wang, H, Xu, M, Bao, B, Fang, J.-K* Nanjing University of Science and Technology, Nanjing, China Our previous research indicated that power conversion efficiency of dye-sensitized solar cells (DSSCs) can be significantly improved by introducing a diyne unit in dye molecules. In order to further improve the light harvest ability, two novel organic dyes coded as FSD104 and FSD105 were synthesized by replacing the single-bond-bridge between electron donor (triphenylamine) and π-linker (anthracene) with triple-bond-bridge to obtain an extended conjugation. These two dyes were fully characterized by 1H NMR, 13C NMR and HRMS, etc. The photophysical and electrochemical properties and photovoltaic parameters of DSSCs sensitized by these two dyes were well investigated. The adoption of the triple- bond-bridge effectively reduces the energy gap of the dyes and broadly extends the adsorption spectra, resulting in a remarkable increase of power conversion efficiency. The results show that FSD105 with cyanoacrylic acid group has a remarkably higher electron lifetime in the TiO2 conduction band and greater dye-loading amount on TiO2 than the other dyes, which guaranteed a higher short-circuit photocurrent density and open circuit voltage. Thus, the cell based on FSD105 shows the highest power conversion efficiency of 4.14%. These results demonstrate that dyes containing a diyne unit always exhibit excellent performance and the power conversion efficiency could be further improved by extending conjugation. This work was supported by the Natural Science Foundation of Jiangsu Province (BK20140780). 290 Hollow Fe3O4 as nanoelectrocatalyst for molecule catalysis toward electrochemical immunoassay Wang, Z, Han, J, Xie, G, Chen, S E-mail: [email protected] Northwest University, Xi’an, China ABSTRACT In this work, we prepared hollow magnetic iron oxide nanoflowers (Fe3O4HNFs) as nanoelectrocatalyst to obtain a multi-functionalized redox signal tag for high-performance thionine (Thi) catalysis toward ultrasensitive protein detection. Briefly, Au-Thi-Au with good conductivity and large surface area was prepared to enhance the immobilization amount of redox molecular (Thi). Simultaneously, to improve catalytic efficiency, Au-Thi-Au (redox molecule) was further anchored on the surface of Fe3O4HNFs (nanoelectrocatalyst). Obviously, the as-prepared Au-Thi-Au@Fe3O4HNFs as signal tag combines the merits of electrochemical activity, catalytic activity, magnetic response as well as nanocarrier, which is employed in electrochemical immunoassay. Importantly, owing to the hollow structure and high activity site of Fe3O4HNFs, the signal tag of Au-Thi-Au@Fe3O4HNFs exhibits high-performance Thi catalysis even in the absence of substrate, thus, giving a highly sensitive method for electrochemical detection of alpha fetoprotein (AFP) down to the 0.033 pg mL-1. Compared with traditional enzyme-based signal amplification, the proposed immunosensor avoids the addition of any substrate in testing solution, and shows good stability, sensitivity and accuracy. 291 HYDROGEN SULFIDE GAS SENSING USING COPPER NANOPARTICLE-SENSITIZED POLYANILINE Ong, PP1, Gorospe, AEG2 and Santiago, K1,2 1Department of Chemistry, College of Science; 2Research Center for Natural and Applied Sciences, University of Santo Tomas, España 1015, Manila, Philippines Hydrogen sulfide (H2S) is one of the most common gases generated in livestock and poultry operations. Prolonged exposure to this gas, even at trace concentrations, poses a number of health risks to the surrounding community. Thus, constant monitoring of gas production from these facilities is important. However, the conventional method of detection, usually a pulsed-fluorescence analyzer, demands elaborate procedures and is usually, of high cost. This study aims to investigate the potential of developing chemically synthesized gas sensing materials based on polyaniline (PANI) doped with copper nanoparticles (CuNPs). The composites were synthesized via in situ polymerization of the aniline in the presence of copper nanoparticles. The morphological and structural properties of the composites were examined. Results show that the incorporation of CuNPs improved the sensor’s performance in terms of sensitivity to the target gas. This may be attributed to the enhanced surface area of the sensing membrane due to the presence CuNPs. The catalytic properties of CuNPs also contributed to the increased sensitivity of PANI to H2S gas. 292 Hydrophobically Directed Asymmetric Synthesis of Chiral GABAs with Quaternary Stereogenic Center Sim, J. H, Song, C. E. Presenting author’s e-mail: [email protected] Sungkyunkwan University, Suwon, Korea In nature, water is used as reaction enhancer for biosynthetic reactions to sustain life in enzymatic processes, inducing hydrophobic interactions between enzyme and substrates. From the perspective of green chemistry as well as an increased scientific effort to mimic nature, tremendous effort has recently been directed to the development of catalytic reactions in aqueous environments. In this symposium, we will present our recent discovery that water enables new catalytic reactions for otherwise unreactive substrate systems. Highly enantioselective organocatalytic Michael addition of dithiomalonates to extremely unreactive -disubstituted nitroalkenes, affording both enantiomers of highly enantioenriched Michael adducts with all carbon substituted quaternary centers, has been achieved by employing the “on water condition,” which enables enforced hydrophobic interactions between catalysts and substrates due to the hydrophobic hydration effects. The developed “on water” protocol was successfully applied for the scalable one-pot syntheses of chiral GABA analogs with all- carbon quaternary stereogenic centers at the -position, which might show highly interesting pharmaceutical properties.[1] O O O O CO2H "on water" catalysis EtS SEt NH EtS 1 SEt 1 2 R + R 2 NO 2 R R2 2 R NO2 O R1 CO2H R1,R2 H NH3 Cl NH 2 R X R2 X -disubstitued chiral GABA analogues [1] J. H. Sim, C. E. Song, Angew. Chem. Int. Ed. 2017, 56, 1835. 293 Interaction of Glycolipid S-TGA-1 with Bacteriorhodopsin and Its Functional Role Inada, M, Kinoshita, M, Matsumori, N Presenting author’s e-mail: [email protected] Kyushu University, Fukuoka, Japan It has been demonstrated that lipid molecules in biological membranes are responsible for the functionalization and structuration of membrane proteins. However, it is still unclear how the interaction of lipid molecules with membrane proteins is, correlated with the function of the membrane proteins. Here we first developed an evaluation method for the interaction between membrane proteins and lipid molecules via surface plasmon resonance (SPR) analysis. Bacteriorhodopsin (bR), which was obtained by the culture of halobacteria, was used as a membrane protein. We prepared SPR sensor chips covered with self-assembled monolayer containing mercaptocarboxylic acids, and immobilized bR onto them. Then, we evaluated the interactions with various lipids that have different structures. As a result, the halobacterium-specific glycolipid S-TGA-1 was found to have much higher affinity with bRs than other lipids. This is probably due to not only hydrophobic and electrostatic interactions but also hydrogen bonds with sugar moieties in the glycolipid. Next, we analyzed the roles of the lipid in the structuration and functionalization of bR. CD analysis showed that S-TGA-1 could promote trimerization of bR monomers more efficiently than any other lipids. Flash photolysis further indicated that bR trimers formed by S-TGA-1 reproduced the photocyclic activity of bR in purple membrane, halobacterium- membrane. These results suggest that S-TGA-1 promotes trimerization of bR through strong interactions and consequently fulfills the bR’s function efficiently. 294 IRON(III) CHLORIDE-CATALYZED CLAISEN REARRANGEMENT REACTION OF ALLYLOXYARENES UNDER MICROWAVE CONDITIONS Pramesti, I. N1, Okada, Y Presenting author’s e-mail: [email protected] 1 Ritsumeikan University, Shiga, Japan ABSTRACT Nowadays, the production of chemicals using the principles of green chemistry is extensively studied regarding to the considerable impact of the environmental problems. The Claisen rearrangement of allyloxyarenes are typically performed in a long reaction time and high temperature range 180-225oC. Recently, the microwave has been demonstrated as a powerful tool for organic syntheses since it can give significant advantages over the conventional heating, e.g., quick reaction, high chemical yield, and high selectivity. Moreover, FeCl3 as Lewis acid is considered as one of desirable catalyst due to its cheapness, easily handle and environmental friendly properties. In this study, the microwave heating effects for the Claisen rearrangement of allyloxyarenes in the presence of FeCl3 catalyst was investigated. This reaction was performed in a test tube by mixing the substrate o with FeCl3 catalyst in the various solvents. The mixture was heated at low temperature 80 C. o As a result, FeCl3 catalyst was able to initiate the rearrangement at 80 C in a short reaction time. It have been proved using 1-crotyloxynaphthalene that the reactions occur through intramolecular rearrangement not intermolecular one. The microwave heating effects were affected by the kind of solvents. The microwave heating enhanced the reaction of allyloxyarene derivatives in decalin and 1,2-dichloroethane compared with conventional heating. It was suspected that FeCl3 forms a complex with the aromatic ring of allyloxyarenes. The formed complex species was expected to efficiently absorb the microwave, so the reaction would be accelerated. The formation of the iron complex is being investigated through 1H-NMR relaxation time study. 295 ISOINDOLINE NITROXIDE-CONTAINING PORPHYRINS FOR EPR AND FLUORESCENT IMAGING PROBES Luo X, Shen Y, Liu F, Chen S, Yan, G* Presenting author’s e-mail: [email protected] School of Material Science and Engineering, Wuhan Institute of Technology, Wuhan 430074, China Some porphyrins and their metal complexes play important roles in magnetic resonance imaging (MRI), photodynamic therapy (PDT), anticancer drug and fluorescence imaging because of their preferential selective uptake and retention by the tumors. Recently, spin- labelled porphyrins have received more and more attention as potential molecular magnetic materials and EPR probes in the study of porphyrin excited states. Tetramethyl isoindoline nitroxides can display superior EPR linewidths, compared to other classes of nitroxides. In this work, isoindoline nitroxide-containing porphyrins were synthesized by the reaction of 5-phenyldipyrromethane and 5-(4'-nitrophenyl)-dipyrromethane with 5-formyl-1,1,3,3- tetramethylisoindolin-2-yloxyl using the Lindsey method. These spin-labeled porphyrins were further characterizated by MS, UV, FT-IR, cyclic voltammetry, electron paramagnetic resonance (EPR), and fluorescence spectroscopy. The electrochemical assay demonstrated that these isoindoline nitroxides-containing porphyrins had similar electrochemical and redox properties as 5-carboxy-1,1,3,3-tetramethylisoindolin-2-yloxyl. The EPR test exhibited these porphyrins possessed the hyperfine splittings and characteristic spectra of isoindoline nitroxides, with typical nitroxide g-values and nitrogen isotropic hyperfine coupling constants. Fluorescence spectroscopy revealed that these porphyrins indicated fluorescence suppression characteristic of nitroxide-fluorophore systems. Moreover, their reduced isoindoline nitroxide-containing porphyrins eliminated the fluorescence suppression and displayed strong fluorescence. Thus these isoindoline nitroxide-containing porphyrins may be considered as the potential probes for fluorescent and EPR spectroscopy. This work was supported by the National Natural Science Foundation of China (Grant No. 51373128), Key National Research and Development Program (2016YFB1101302), Wuhan Science and Technology Innovation Team of Hi-tech Industrial Project, Hubei Province (Grant No. 2015070504020217), and Innovation Fund for post-graduate education (CX2016004, CX2016012), Wuhan Institute of Technology, China. 296 Layered Double Oxide Nanocrystals for Ultrafast Removal of Toxic Pollutants Mubarak, M1,2, Islam, Md. S2, Choi, WS3, Lee, H-J1,2 Presenting author’s e-mail: [email protected] 1 Korea Basic Science Institute, Seoul, Republic of Korea 2 Ewha Womans University, Seoul, Republic of Korea 3 Hanbat National University, Daejeon, Republic of Korea Heavy metal ions existing in natural underground water and drinking water are causing environmental issues and global health concerns. Especially, arsenic [As(V)] and chromium [Cr(VI)] are hazardous pollutants, which will pose serious risks to human health, living organism, and the ecological system. Herein, flowerlike Mg/Fe layered double hydroxide (MF-LDH) nanocrystals were prepared by a simple hydrothermal method for removal of As(V) and Cr(VI) from contaminated water. After thermal treatment of MF-LDH nanocrystals, the MF-LDH was converted into their corresponding oxide, Mg/Fe layered double oxide (MF-LDO), which maintained the flowerlike structure. The crystal structure, morphology, microstructure and chemical structure were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy mapping, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The MF-LDO nanocrystals showed superb removal efficiency for both As(V) and Cr(VI), which showing over 97% removal within 5 min and providing maximum removal capacities of 178.5 mg/g [As(VI)] and 129.7 mg/g [Cr(VI)]. In addition, Au nanoparticles were successfully introduced in the MF-LDO nanocrystals and the products exhibited excellent catalytic conversion rate for reduction of 4-nitrophenol into 4-aminophenol (100% conversion in 5 min). This work provides simple, convenient and cost effective strategies to develop promising materials for water pollutant removal. 297 Lung Cancer Diagnosis via Electrochemical Strategy: From miRNA to lncRNA Xiaojun, C, Xiaoyan L, Nan J Presenting author’s e-mail: [email protected] Nanjing Tech University, Nanjing, China. Lung cancer is a global health problem for its incidence, prevalence and high mortality rate. Therefore, sensitive and specific profiling of cancer-specific miRNAs or lncRNAs is significant. Until now, there are only a very few reports about lncRNAs detection using electrochemical biosensors. Therefore, the development of sensitive electrochemical detection of lncRNAs is highly desirable. During these two years, we have fabricated three novel types of electrochemical genesensors for the detection of lung cancer related miRNAs and lncRNAs biomarkers. First, miR-21 levels were quantified as low as attomolar sensitivity by a target-triggered triple isothermal cascade amplification (3TICA) strategy with the coupling of target recycling, nicking-replication reaction and DNAzyme catalysis. Second, an H19 lncRNA electrochemical biosensor was fabricated based on a three-dimensional ordered 3+ macroporous (3DOM) graphene-AuNPs composite active interface and Ru(NH3)6 attached AuNPs@PS signal reporter. Third, a multiplexed biosensor was prepared for the simultaneous detection of two different specific sequences deduced from MEG 3, on the basis of a 3D graphene-like WS2 interface. In the presence of target specific sequence, an RNase A-aided target recycling amplification was triggered. Fc and (or) MB labelled chain reaction would subsequently generate signal enhancement, which was distinguished at different potentials. The application of these genesensors in real serum samples have also been studied, and the satisfactory results have already obtained compared with the clinical assays. Scheme 1. Schematic illustration of multiplexed and amplified electrochemical detection of two different specific sequences deduced from MEG 3. 298 Mechanistic Insights on DBU Catalyzed ß-Amination of NBS to Chalcone Driving by Water: Multiple Roles of Water Yuan, Haiyan, Zhang, jingping Presenting author’s e-mail: [email protected] Faculty of Chemistry, Northeast Normal University, Changchun, China ABSTRACT TEXT DFT calculations were conducted to pursue deeper understandings on the mechanism and the explicit role of trace water in the DBU-catalyzed ß-amination of NBS to chalcone. Being different from previously proposed by Liang et al., a cooperative participation of both DBU and water is noticed in the preferred mechanism. The preferential mechanistic scenario assisted by water undergoes three major steps: the formation of succinimide and HBrO, concerted nucleophilic addition and H-shift, and keto-enol tautomerization. Moreover, we found that DBU-HBrO is unnecessary in the third step and three-water-cluster assisted keto-enol tautomerization is the most advantageous case. It is further noted that the catalytic position of the third water molecule and the proton shift orientation to some extent affect step 3 via O···H−O and O−H···π interactions, which is confirmed by AIM analysis. The computational results suggest that water molecules play pivotal roles as reactant, catalyst, and stabilizer to promote the reaction of chalcone and NBS. The origin of the more stable transition state structure in the rate-determining step of DBU-water catalyzed mechanism is ascribed to noncovalent interactions, halogen bond, and electrostatic interactions than DBU only ones. 299 Mechanistic studies with NMR on dissolution of cellulose with CO2 Luo, H.-K.*, Lee, M. X. A., Huang S.-L. E-mail: [email protected] Institute of Materials Research and Engineering Agency for Science, Technology and Research 2 Fusionopolis Way, #08-03, Innovis, Singapore 138634 Cellulose is the most abundant natural organic polymer on earth which can be processed into fibres by wet-spinning. However, cellulose contains an ordered hydrogen bonding network, which makes it insoluble in water and common organic solvents. In commercial processes, the dissolution methods involve toxic CS2/NaOH/water system, or a greener but expensive N-methylmorpholine oxide (NMMO)/water system. Later, researchers developed more cellulose dissolution media, such as urea/NaOH/water system, ionic liquids and ionic liquid/co-solvent system. Cellulose was recently reported to be dissolved in DMSO by forming a switchable ionic 1 13 system with CO2, which is considered as a green procedure. Here we report our H and C- NMR studies on cellulose DMSO-d6 solution obtained using CO2 and 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU) as base. No signal of imine C=N was observed in the 1H-NMR spectrum of DBU, whereas in the 1H-NMR spectrum of the cellulose solution, a broad signal at 8.69 ppm was observed and attributed to C=NH of the [DBU-H]+ cation. In the 13C-NMR spectrum of DBU, the chemical shift of C=N is 159.57 ppm, whereas the signal of C=NH of [DBU-H]+ was shifted to 163.00 ppm in the 13C-NMR spectrum of the cellulose solution. In addition, a broad signal was observed at 156.09 ppm, attributing to R-OCOO- anion (R=cellulose), indicating the formation of carbonate anions. These results may suggest that DBU deprotonates the hydroxyl groups of cellulose to form [DBU-H]+ cations and R-O- - anions which reversibly react with CO2 to generate R-OCOO anions, forming a switchable ionic system and leading to the dissolution of cellulose. 300 Mechanochemical Preparation of Ru, Rh, and Ir Based Macro-metallacycles. Philjae Kang, Younghun Kim and Moon-Gun Choi Presenting author’s e-mail: [email protected] 1 Yonsei University, Seoul, Korea In these days, macro-metallacycles have attracted great attention because of a variety of structures from the diverse metal-ion coordinated environments and multifunctional ligands, and its applications. Organometallic half sandwich fragments (Rhodium, Ruthenium, or Iridium) are one of the most widely used compounds to construct macro-metallacycles on account of simple synthetic methods and high yields. A mechanochemical reaction, using kinetic energies from milling under solvent-free conditions, has been replacing diverse existing syntheses based on the solution techniques in terms of Green chemistry. A mechanochemical reaction derives higher yields, faster rates of reaction, and non-producing toxic wastes from any organic solvents. Especially, a transition metal based mechanochemistry is widely applied to the various fields like catalytic reactions, mononuclear metal complexes, and multi-dimensional networked compounds (e.g., coordination polymers or metal-organic frameworks). Nevertheless, mechanochemical syntheses of multi-nuclear metal complexes are still hardly ever investigated. Our group made an attempt to produce binuclear metal complexes by C-H activation between 5-(pyridine-3-yloxy)isophthalic acid as a ligand, and metal half sandwich fragments of [(p- cymen)Ru(OAc)2], [Cp*Ir(OAc)2] and [Cp*Rh(OAc)2]. Characterizations of binuclear metallacycles were achieved by CP/MAS 13C solid state NMR, IR, and elemental analysis. Consequently, the data was well-matched with the products from the reaction in the solution. The 3-D crystal structures were confirmed by a single crystal X-ray analysis. b) a) 301 Medical nebulizer path tracing of acute vapour inhalation Choi, KH1, Kim, HJ2, Park, BJ1 1 Department of Electrical & Biological Physics, Kwangwoon University, Seoul, Republic of Korea 2 Department of Chemistry, Chosun University, Gwangju, Republic of Korea ABSTRACT Inhalation therapy, or aerosol therapy, can be described as the inhalation of an aerosol targeted at treating diseased areas of the respiratory tract. Inhalation therapy has been practiced since ancient times, when patients were recommended to breathe the fumes carrying sulfuric vapours from the slopes of the Vesuvius. It is through the development of devices designed to aerosolize medication that inhalation therapy has become the preferred method to treat respiratory diseases. Particularly, pulmonary delivery of drugs has develop into an attractive target in the health care industry as the lung is capable of absorbing pharmaceuticals either for local deposition or for systemic delivery. In the past few years, there have been advances in the development of new nebulizers that hold the promise to improve aerosol drug delivery to patients with pulmonary diseases. However, the incident of hundreds of South Korean lost their lives is a direct example that the acute vapour inhalation toxicity is very terrible. In spite of this tragedy, it is quite regrettable that the path tracing of acute vapour inhalation toxicity is no way to ascertain. In this respect, we have synthesized novel bodipy nanogels that are newly designed and prepared by simple cross-linking and surface modification process. Microstructure and physical properties of the bodipy nanogels were investigated by transmission electron microscopy (TEM), infrared spectroscopy (IR) and steady state spectroscopic methods. This non- invasive fluorescence imaging method has the potential to provide the path tracing of acute vapour inhalation toxicity. 302 Mesalazine from Salicylic acid: Synthesis involving mild nitration conditions Khatoon, S, S, and Jahangir, S. Presenting author’s e-mail: [email protected] Department of Chemistry, Faculty of Science, Federal Urdu University of Arts, Science and Technology Gulshan-e-Iqbal, Karachi, Pakistan Mesalazine (5-aminosalicylic acid) is synthesized from Salicylic acid under mild conditions as compare to reported Mesalazine synthesis. This synthesis includes the regioselective nitration of salicylic acid with of acetic acid/ nitric acid at a lower temperature followed by reduction of nitro group into an amino group. Steps involved (two steps: nitration & reduction) in this synthesis are simple, environment friendly and high yielding. Proposed synthesis of Mesalazine can be used at the industrial level. Figure 1: Mesalazine 303 meso-Aryl Picket Calix[4]pyrroles: Tunable Receptors for Anions and Dissolved Carbon Dioxide Endale Mulugeta, Divya Sareen and Chang-Hee Lee* Presenting author’s e-mail: [email protected] A Department of Chemistry, Kangwon National University and IMSFT, Chun-Cheon 24341, Koreaa The anion recognition chemistry based on the calix[4]pyrroles has been actively studied due to the ubiquitous role of anions in various chemical and biological processes. As a result, many modified systems have been developed for enhancing affinity and selectivity for particular guest molecules. Among those model systems, the meso-aryl picket calix[4]pyrroles have been developed recently and studied for the selective recognition of guests as well as anion-templated supramolecular capsule formation. With this regards, we have developed neutral or cationic meso-aryl picket calix[4]pyrroles carrying multiple positive changes. The guest selectivity of the designed systems were greatly influenced by the nature of the picket components. For example, calix[4]pyrroles carrying cationic pyridinium picket displayed high selectivity for dipydrogen pyrophosphate anion. On the other hand, the one bearing benzimidazolium picket exhibited high selectivity toward carbonate anion. The synthesis was usually accomplished by ‘2+2’ type condensation of corresponding meso- substituted dipyrromethanes and acetone in the presence of acid catalyst. The cooperative effects of hydrogen bonding, Coulombic interaction, well-defined binding domain and anion- pi interactions were attributed to the high selectivity and binding affinity. The Fluorescence Dye Displacement Assay (FDDA) of the benzimidazolium picketed receptor showed excellent detection of dissolved bicarbonate anion at concentrations as low as 4.1 nM. Tests with various carbonated drinks revealed its ability to function as an easy-to-use sensor for dissolved CO2, as monitored through the bicarbonate anion concentration. References 1 Ion-Mediated Single-Molecular Optical Switching and Sensing Based on Fluorophore- Tethered Calix[4]pyrrole. Divya Sareen, Ji Hye Lee, Hyonseok Hwang, Soeun Yoo, and Chang-Hee Lee, Chem. Commun. 2016. 52, 5852-5855. 2 Non-Linear Allosteric Regulation of Anion Binding by Tetracationic Calix[4]pyrrole Homodimer. Indrajit Saha, Tae Sun Kim and Chang-Hee Lee, Chem. Commun. 2015, 51, 5679-5682. 3 Recent Advancements in Calix[4]pyrrole-Based Anion Receptor Chemistry, Indrajit Saha, Jeong Tae Lee, Chang-Hee Lee, Eur. J. Org. Chem. 2015, 3859-3885. (Review). 4 Receptor that can capture a discrete mono-hydrated fluoride anion, Punidha Sokkalingam, Se-Young Kee, Youngmee Kim, Sung-Jin Kim, Phil Ho Lee, Chang-Hee Lee, Org. Lett. 2012, 14, 6234-6237. 5 A dicationic calix[4]pyrrole derivative and its use for the selective recognition and displacement-based sensing of pyrophosphate, Punidha Sokkalingam, Dong Sub Kim, Hyonseok Hwang, Jonathan L. Sessler and Chang-Hee Lee, Chem. Sci., 2012, 3, 1819– 1824. 304 MICROWAVE-ASSISTED RING-OPENING COPOLYMERIZATION AND PROPERTY OF POLYCARBONATE Ouyang Y, Mei L, Liu F, Chen S, Yan, G* Presenting author’s e-mail: [email protected] School of Material Science and Engineering, Wuhan Institute of Technology, Wuhan 430074, China Recently, the microwave-assisted heating method has become a commonly used and environmentally friendly heating technology in the field of organic and polymeric synthetic chemistry. A series of poly(5,5-dimethyl trimethylene carbonate-co-2-phenyl-5,5- bis(oxymethyl) trimethylene carbonate) (P(DTC-co-PTC)) were synthesized by the microwave-assisted ring-opening polymerization of 5,5-dimethyl trimethylene carbonate (DTC) and 2-phenyl-5,5-bis(oxymethyl) trimethylene carbonate (PTC) using tin (II) 2- ethylhexanoate and aluminum isopropoxide as the catalysts. These co-polycarbonates were further reduced by a palladium-carbon catalyst (Pd/C catalyst, 10%) to make partly deprotected polycarbonates (HPDPC). These two type co-polycarbonates were characterized by gel permeation chromatography, 1H NMR, Fourier transform infrared spectroscopy, UV, differential scanning calorimetry, and automatic contact-angle measurements. The influences of the microwave irradiation time, microwave power, monomer feed molar ratio, different catalysts, and monomer/catalyst feed molar ratio on the molecular weights of copolymers were also investigated. In vitro water absorption, degradation and drug release tests indicated that partly deprotected co-polycarbonate HPDPC possessed faster degradation rate, greater hydrophilicity and faster drug release rate than corresponding P(DTC-co-PTC). This work was supported by the National Natural Science Foundation of China (Grant No. 51373128), Key National Research and Development Program (2016YFB1101302), Wuhan Science and Technology Innovation Team of Hi-tech Industrial Project, Hubei Province (Grant No. 2015070504020217), and Innovation Fund for post-graduate education (CX2016004, CX2016012), Wuhan Institute of Technology, China. 305 Mismatch duplex oligonucleotides as inhibitory agent of Bacterial Topoisomerase I Zhaoqi, Yang1, Tuoyu, Jiang1 Presenting author’s e-mail: [email protected] 1 Jiangnan University, Wuxi, China ABSTRACT TEXT Bacterial topoisomerase I (Btopo I) have been known as a potential target for therapy of anti-bacterial. A series of duplex oligonucleotides containing different length of mismatch base pairs have been designed as inhibitory agents for Btopo I in our investigation. The interactions between these newly designed oligonucleotides and Btopo I were studied and the most efficient one among them displayed an IC50 value of 18.1 nM. In addition, the results of our investigation confirm that the designed oligonucleotide would induce irreversible damages to Btopo I and without any effect for eukaryotic topoisomerase I. In consideration of the low cytotoxicity of DNA-based biopharmaceuticals and the recent development in nucleic acid based drugs, it is our hope that the results provided in these studies could benefit the future design Btopo I inhibitors with high therapeutic efficiency for the treatment of bacterial infections. 306 MODIFIED POLYSACCHARIDES AS TEMPLATE FOR THE SYNTHESIS OF POLYANILINE NANOPARTICLES Mora, E1, Balitaan, J1, and Santiago, K1,2 [email protected] 1Department of Chemistry, College of Science 2Research Center for the Natural and Applied Sciences University of Santo Tomas, España Blvd., 1015 Manila Controlled drug delivery systems are used to alter the timing and rate of release of a drug in a specific part of the body. Advances in biotechnology have had a significant impact on the development of stimuli-responsive biomaterials with tunable properties for more controlled and targeted drug delivery. Consequently, the prominent weaknesses of most systems are the cost and time associated with their fabrication. In this study, polyaniline (PANI) nanoparticles were successfully synthesized using cross-linked carboxymethyl chitin (CM-chitin)/carboxymethyl cellulose (CM-cellulose) template, as supported by their spectral and morphological analyses. The template was fabricated by converting chitin and cellulose, extracted from waste materials of squid pens and rice husks, to their respective carboxymethyl derivatives, and their subsequent cross-linking using epichlorohydrin. Release studies, using UV-Vis spectroscopy, showed that there is a sustainable release of indigo carmine by the synthesized materials. PANI nanoparticles offer a promising low-cost drug carrier material. 307 MOF biosensor for L-Cys without post-modification Gao, D1, Ma, J1, Cheng, P1 1 Department of Chemistry, Nankai University, Tianjin 300071, China ABSTRACT L-cysteine (L-Cys) is one of the most important aminoacids. It plays an important role in living systems and in various cosmetic as well as pharmaceutical preparations. Hence, the probing of L-Cys is very significant. Among all detection methods, the electrochemical techniques have been considered as the promising technique owing to the relatively low cost, simplicity, high sensitivity, and selectivity. Metal–organic frameworks (MOFs) as an ideal biosensor candidate for electrochemical reactions have attracted intensive interest because of their advantageous properties, such as their various pore sizes, high surface areas and naked active sites. Herein, We exhibited the application of an heterometal MOF II II [Fe (pz) Ni (CN)4] for the electrochemical detection of L-cysteine without further post- modification. II II To investigate the detection of L-Cys, unmodified [Fe (pz) Ni (CN)4] was coated on the surface of a gold electrode and cyclic voltammetry measurements was performed in K2HPO4–KH2PO4 buffer solution (PBS, pH 6.8). After adding the L-Cys into the buffer solution, a new anodic peak appeared at Epa = 0.895 V, which can be used as the detected signals for L-Cys. The current density of oxidation peak increased gradually with the increase of L-Cys concentration in the range of 0.10 mM to 1.0 mM. This work provides a new kind of fast and prices sensor for the detection of L-Cys. [1] Southon, P., Liu, L., Kepert, C., et al., J. Am. Chem. Soc., 2009, 131, 10998–11009. [2] Wu, X., Ma, J., Cheng, P. et al. Chem. Commun., 2015, 51, 9161—9164. 308 MONOSACCHARIDE TRANSFORMATIONS USING FLOW CHEMISTRY Mares, L.J., Baker, J.R., McCluskey, A., Simone, M.I. and Russell, C.C. The University of Newcastle, Chemistry University Drive, Callaghan, NSW, 2308, Australia ABSTRACT A number of monosaccharide transformations need prolonged reaction durations, expensive reagents and lengthy purifications. Triflation reactions can take up to 2 hours, require multiple wash steps and most often, a long purification column to isolate products (Best 2010). Triflations involve the reactive trifluoromethanesulfonic anhydride which activates primary and secondary alcohols. The esters synthesised are desirable intermediates however have limited stability at room temperature. Limiting the handling of this reagent and intermediates would be advantageous due to the in situ formation of triflic acid. Batch hydrogenations require hydrogen gas handling and pyrophoric palladium catalysts generally using Parr hydrogenators (Hizartzidis 2014). These can take up to 24 hours to go to completion and need to be recharged regularly (Best 2010). These two reactions have been transferred to flow using the Vapoutec R-4® and H-cube®. We present here novel lactone triflations using the Vapourtec R-4® and hydrogenation of a monosaccharide using the H-cube®. Triflations using flow reactors have been shown to generate benzyne precursors in aryne chemistry (Michel 2014; Yoshida 2014). No reactions have been reported using carbohydrate substrates. There are also few literature examples where flow hydrogenation has been applied to aromatic systems (Hizartzidis 2014). Here we apply for the first time a tandem azide reduction-reductive amination using hydrogenation on a monosaccharide derivative with a flow reactor. We also develop the work on flow triflation using lactone and monosaccharide derivatives. 309 Multienzymatic, One-pot Cascade Synthesis of Enantiopure Lamivudine Precursor (2R,5R)-1,3-oxathiolane Ren, Y, Hu, L, Ramström, O Presenting author’s e-mail: [email protected] KTH – Royal Institute of Technology, Stockholm, Sweden As a key precursor to anti-HIV agents, for example lamivudine, enantiopure (2R,5R)-1,3- oxathiolane was synthetized by an efficient multienzymatic one-pot cascade protocol. Starting from two achiral material, a 1,3-oxathiolane ring was formed and the absolute configuration was efficiently controlled by employing a combination of surfactant-treated subtilisin Carlsberg (STS) and Candida antarctica lipase B (CAL B). The enantioenriched 1,3-oxathiolane intermediate was generated by STS-catalyzed addition-cyclization- acetylation and subsequently resolved by adding CAL B to selectively hydrolyze the desired isomer, resulting in the (2R,5R)-2-(hydroxymethyl)-1,3-oxathiolan-5-yl acetate with an excellent ee of >99%. Since 1,3-oxathialane derivatives can be smoothly converted to lamivudine through N-glycosylation reaction, our study provides efficient access to enantiopure lamivudine as well as other nucleoside analogue agents, for instance emtricitabine and apricitabine. 310 Multi-functional Persistence Luminescence Nanoparticles for Bioimaging and Therapy Abdukayum, A, Tuerdi, A, Tursun, M Presenting author’s e-mail: [email protected] Kashgar University, Kashgar, China ABSTRACT The near-infrared (NIR) emitting Persistent luminescent nanoparticles (PLNPs) are one of the most attractive luminescence nanoparticles for biomedical application, because they have a long afterglow time and no need for in situ excitation during the biomedical imaging. PLNPs-based molecular probe not only can completely avoid tissue autofluorescence, light scattering and phototoxicity originating from the excitation source, but also have deeper tissue penetration, due to their emission wavelength located in the NIR window in biological tissue [1]. Herein, we designed a multi-functional PLNPs-based molecular probe for in vivo NIR luminescence imaging and stimuli-responsive chemotherapy. Firstly, a novel composition of NIR emitting PLNPs with superlong afterglow time was synthesised by a citrate sol−gel method. The surface of PLNPs was coated with (3- Aminopropyl)triethoxysilane, and subsequently conjugate to a pH stimuli-responsive Polyacrylic acid (PAA) polymer. The anticancer drug of Doxorubicin (Dox) was loaded into the PAA conjugated PLNPs particles for controlled drug delivery. The PAA functional PLNPs exhibit a bright NIR luminescence and sustained drug release properties. Reference [1] Abdukayum, A.; Chen, J.-T.; Zhao, Q.; Yan, X.-P., J Am Chem Soc 2013, 135 (38), 14125-14133 311 Nano-particle based microarray for facilitated phenotypic screening of natural product library in mammalian cells Bo Peng1, Changmin Yu2 and Shao Q. Yao1 Presenting author’s e-mail: [email protected] 1 Department of Chemistry, National University of Singapore, 3 Science Drive, Singapore 117543, Singapore 2 College of Materials Science & Engineering South China University of Technology Guangzhou, China ABSTRACT TEXT Traditional small molecule microarray (SMM) is not applicable for cell-based high- throughput screens (HTS). Although people has used different strategies to achieve cell phenotypic HTS, there are still many limitations, such as not controllable release, extra- chemical synthesis or limited to certain type of chemical reactions for immobilization. Mesoporous silica nanoparticles (MSNs), which has large pore size and high drug loading capacity, has been widely used in drug delivery. Herein, we report the first time the combination of microarray with MSN, to achieve controllable releasing of more than 100 member of natural product, which facilitated phenotypic HTS with several cancer cell lines by varies types of detection methods. The further application of Si-RNA BRCA1 or PARP1 knockdown combined with our MSN-natural product has identified some natural product which has synergetic effect with BRCA1 or PARP1 knockdown. Subsequent cell-based assay has confirmed our finding. This application has demonstrated our strategy has universal application in phenotypic based high-throughput drug discovery. 312 Nanosized ZSM-5 isomorphously substituted by Ga and aromatization performance Yujun F, Xiaofang S, Xuefeng B, Wei W, Xin J, Huiying W Presenting author’s e-mail: [email protected] National Center for International Research on Catalytic technology, Key Laboratory of Chemical Engineering Process＆Technology for High-efficiency Conversion, College of Heilongjiang Province, School of Chemistry and Material Sciences, Heilongjiang University, Harbin 150080, Heilongjiang, China ABSTRACT TEXT Modification with isomorphous substitution by Ga can tune the acidity and porosity properties of the ZSM-5 zeolites. In this work, the Ga isomorphously substituted nanosized ZSM-5 zeolite samples GaNZ5-1 and GaNZ5-2 with various Ga content were prepared by post-treatment method in the (NH4)3GaF6 solution with different concentrations, and the catalytic properties were evaluated in 1-hexene aromatization. After the incorporation of Ga atom, the amount of strong Lewis acid sites as well as the total ones increased along with the increasing Ga content, the amount of strong Brønsted acid sites decreased and the weak one increased, which can be ascribed to the formation of extra-framework GaO+ species contributing to strong Lewis acid sites and the insertion of Ga into the framework of zeolites, forming new weak Brønsted acid sites. Moreover, the lower B/L ratio beneficial for the aromatization was obtained. In addition, the decreasing in microporosity and enhancement in mesoporosity put down to the blockage of micropore by extraframework oxide metal species and the damage due to the acidic medium. An increasing in aromatics yield with the enhancement of Ga content was reached, and GaNZ5- 2 achieved the highest aromatics yield of 58 wt.% which can be attribute to the synergistic effect of milder Brønsted and stronger Lewis acid sites. 313 Natural Product Discovery by Activation of Silent Biosynthetic Gene Clusters LIM, Y. H.,1 Zhang, M. M.,2 Wong, F. T.,3 Lim, Y. W.,1 Qiao, Y.,2 Yeo, W. L.,2 Heng, E.,3 Ang, E. L.,2 Zhao, H.2,4 Presenting author’s e-mail: [email protected] 1 Organic Chemistry, Institute of Chemical and Engineering Sciences, A*STAR, Singapore 2 Metabolic Engineering Research Laboratory, A*STAR, Singapore 3 Molecular Engineering Laboratory, A*STAR, Singapore 4 Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana- Champaign, Urbana, United States ABSTRACT Bacteria produce a multitude of complex molecules that we have harnessed for diverse applications from medicine to agriculture and food. Yet advances in genomics reveal that we have barely scratched the surface of what microbial metabolism has to offer. The number of observed natural products is far less compared to the number of predicted biosynthetic gene clusters in bacteria genomes. One of the major hurdles is that many of these unexplored biosynthetic gene clusters, for various reasons, are transcriptionally silent under typical laboratory conditions. As such, strategies that allow us to activate expression of these gene clusters and trigger production of the encoded metabolites will enable us to tap into this valuable source of natural products and access an unexplored chemical space. Here, we present an efficient CRISPR-Cas9 based strategy to turn on the expression of silent biosynthetic gene clusters in native Streptomyces hosts. Using a one-step promoter knock-in strategy to activate silent biosynthetic gene clusters of different classes in multiple Streptomyces species, we elicited the production of distinct metabolites that were not observed in the parent strains. This presentation will disclose stories of this activation strategy to facilitate natural product discovery efforts and uncover novel compounds with desirable bioactivities. Reference: M. M. Zhang, F. T. Wong, Y. Wang, S. Luo, Y. H. Lim, E. Heng, W. L. Yeo, R. E. Cobb, B. Enghiad, E. L. Ang, H. Zhao, Nature Chem. Biol. 2017, accepted. 314 Natural Products for Drug Discovery in Bangladesh Shoeb, M, Nahar, N e-mail:[email protected] Department of Chemistry, University of Dhaka, Dhaka-1000, Bangladesh Many people in Bangladesh are suffering from different types of diseases such as diabetic, cancer, malaria, leishmaniasis, dengu, dyslipidemia, hypertension, leprosy, cardiovascular diseases (CVDs) etc. Malaria and leishmaniasis are prevalent in the hilly areas of the country. People living there cannot afford to have proper drugs for the treatment of many diseases including malaria and leishmaniasis. Diabetes is prevalent in the whole country and the number of patients is increasing day by day due to rapid urbanization and change of life style. Indigenous people are using plant materials for remedy of these ailments as modern drugs are expensive and unavailable for them. As part of our on-going research on natural products, a large number of plant extracts from Bangladesh origin were screened on normal and streptozotocin induced Type I (IDDM) & Type II (NIDDM) diabetic model rats. Extracts of Crataeva religiosa, Murray koenigie, Momordica charantia, Zizyphus rugosa, Zizyphus oenoplia, Scoparia dulcis and Coccinia indica showed significant efficacy on different animal. From the active extract of these plants, several secondary metabolites were isolated. Endophytic fungi were isolated from medicinal plants of Terminila chebula Retz, Ocimum basilicum L, O. sanctum L., Aquilaria malaccensis Lamk and Magnifera indica L., and several novel and known compounds were isolated. The parent extracts and isolated compounds of the fungal strains were tested for antibacterial, antioxidant and cytotoxicity assay against human cancer cells. Secalonic acid A and secalonic acid D showed significant cytotoxicity against human pancreatic cells with IC50 values of 7.3 and 1.6 µM, respectively. 315 New Bafilomycins Produced by a Streptomyces sp. Isolated from a Marine Sponge Theonella sp. Chen, Y-H1,2, Huang, P-C3, Lu, M-C2,3, Weng, C-F1, Su, J-H2,3, Kuo, J2,3, Sung, P-J2,3 1Department of Life Science and Graduate Institute of Biotechnology, National Dong Hwa University, Hualien, Taiwan 2National Museum of Marine Biology and Aquarium, Pingtung, Taiwan 3Graduate Institute of Marine Biology, National Dong Hwa University, Pingtung, Taiwan. ABSTRACT Three new 16-membered diene macrolides, bafilomycin M (1), N (2) and O (3), along with two known compounds JBIR-100 (4) and bafilomycin K (5) and were produced from Streptomyces sp. GIC10-1. This bacterium was isolated from a marine sponge Theonella sp. The structures of 1-5 were established by spectroscopic methods and by comparison the spectral data with known analogues. These five compounds were found to exhibit significant cytotoxicity toward MOLT-4, K-562, SUPT-1 and LNCaP tumor cells. Theonells sp. Streptomyces sp. GIC10-1 25 24 O OH 2 4 6 1 3 5 7 23 22 O OH O 8 15 13 11 21 19 12 9 20 18 16 14 10 R3 17 R2 R1 Bafilomycin M (1):R1=R2=OCH3, R3=OH H Bafilomycin N (2):R =CH , R =OH, R =OC(O)C=CC(O)OH 1 3 2 3 H Bafilomycin O (3):R =CH , R =R =OH 1 3 2 3 H JBIR-100 (4):R =OCH , R =OH, R =OC(O)C=CC(O)OH 1 3 2 3 H Bafilomycin K (5):R1=OCH3, R2=R3=OH 316 Nitromethane-Mediated, Three-Component Synthesis of β-Enaminones and Their Photochemical Properties Ding-Yah Yang e-mail: [email protected] Department of Chemistry, Tunghai University, No. 1727, Sec. 4, Taiwan Boulevard, Xitun District, Taichung City 40704, Taiwan, Republic of China β-Enaminones are widely used as a building block or synthon for the preparation of many biologically active compounds.1 Compounds featuring the β-enaminones or enamine- diketone possess many biological activities like antibacterial, anti-inflammatory, antiaggregant, antiischemic, antileukemia and other types of physiological activities. Herein we would like to report the Mn(OAc)2-catalyzed coupling of 4-hydroxycoumarin with aromatic aldehyde and primary amine in nitromethane to obtain the library of β-enaminones in good to high yields. The synthesis, substrate scope, and mechanism of this three-component reaction along with the photochemical properties of the prepared compounds will be presented.2 References 1. Ye, W.; Li, Y.; Zhou, L.; Liu, J.; Wang, C. Green Chem. 2015, 17, 188-192. 2. Manjappa, K. B., Fan, S. C, Yang, D. Y. Manuscript in preparation. 317 Noncovalent Binding of PAHs with Genetic Bases Reducing ARG Transfer Fuxing Kang1, Weijun Shou1 Presenting author’s e-mail: [email protected] 1Nanjing Agricultural University, Jiangsu, China Polycyclic aromatic hydrocarbons (PAHs) and antibiotic resistant plasmids (Arps) in the environment pose a serious threat to human health and ecological security. Combined PAH-Arp pollution has aroused much public concern. It is necessary to understand the fundamentals of PAH-Arp interactions prior to assessing their underlying environmental risks. In the present study, we assessed the effect of ampicillin resistance genes (Args) on representative PAHs phenanthrene/pyrene, revealing the noncovalent mechanism that inhibits the expression of Args in plasmid (pUC19). Results show that with plasmid exposed to the test PAHs, there is inefficient Arg expression in an E. coli host. In the absence of PAHs, the efficiency is 4.7 log units. However, the efficiency decreases to 3.72–3.14 log units with increasing phenanthrene/pyrene concentrations up to to 50 mg/L. Evidence from fluorescence titration, HPLC-MS, XPS, FTIR, and quantum computation suggests that tested PAHs physically intercalate into duplex regions of denatured DNA, combining with adenine constituents in plasmid. This physical combination damages the structure of plasmid, consequently restraining the expression of Args. Most importantly, information obtained from the study may provide a theoretical foundation for revealing the principle of combined PAH-Arp pollution, which has great significance for controlling this pollution and protecting ecological security. 318 One-Dimensional Nanomaterials for Energy Storage Mai, L*; Li, Q email: [email protected] 122 Luoshi Road, Wuhan 430070, Hubei, China Wuhan University of Technology ABSTRACT TEXT One-dimensional nanomaterials can offer large surface area, facile strain relaxation upon cycling and efficient electron transport pathway to achieve high electrochemical performance. Hence, nanowires have attracted increasing interest in energy related fields. We designed a single nanowire electrochemical device for in situ probing the direct relationship between electrical transport, structure, and electrochemical properties of the single nanowire electrode to understand intrinsic reason of capacity fading. The results show that during the electrochemical reaction, conductivity of the nanowire electrode decreased, which limits the cycle life of the devices. We have also fabricated hierarchical MnMoO4/CoMoO4 heterostructured nanowires by combining "oriented attachment" and "self- assembly". The asymmetric supercapacitors based on the hierarchical heterostructured nanowires show a high specific capacitance and good reversibility with a cycling efficiency of 98% after 1,000 cycles. Then, general synthesis of complex nanotubes was designed by gradient electrospinning, including Li3V2(PO4)3, Na0.7Fe0.7Mn0.3O2 and Co3O4 mesoporous nanotubes, which exhibit ultrastable electrochemical performance when used in lithium-ion batteries, sodium-ion batteries and supercapacitors, respectively. Recently, we have successfully fabricated a field-tuned hydrogen evolution reaction (HER) device with an individual MoS2 nanosheet to explore the impact of field effect on catalysis. We have also constructed a new-type carbon coated K0.7Fe0.5Mn0.5O2 interconnected nanowires through a simply electrospinning method. The interconnected nanowires exhibit a discharge capacity of 101 mAh g-1 after 60 cycles, when measured as a cathode for K-ion batteries. Our work presented here can inspire new thought in constructing novel one-dimensional structures and accelerate the development of energy storage applications. 319 Optimised Reactions for Thiol Probes to Detect Electrophilic Natural Products Hahn, D1, Chin, J2, Cho, SJ2, Bae, JS3, Lee, T4 1 School of Food Sciences and Biotechnology, College of Agriculture and Life Sciences, Kyungpook National University, Daegu, Korea 2 New Drug Development Center, Daegu-Gyeongbuk Medical Innovation Foundation, Daegu, Korea 3College of Pharmacy, CMRI, Research Institute of Pharmaceutical Sciences, BK21 Plus KNU Multi-Omics Based Creative Drug Research Team, Kyungpook National University, Daegu, Korea 4College of Pharmacy, Research Institute of Pharmaceutical Sciences, Kyungpook National University, Daegu, Korea New methods are urgently needed to find novel natural products as structural leads for the development of new drugs against emerging diseases like cancer and multi-resistant bacterial infections. Here, we introduce a reactivity-guided drug discovery approach for electrophilic natural products, a therapeutically-relevant class of natural products that covalently modifies their cellular targets, in crude extracts. Using carefully designed halogenated aromatic reagents, the process furnishes derivatives that are UV-active and highly conspicuous via mass spectrometry by virtue of an isotopically-unique bromine or chlorine tag. In addition to the identification of high-value metabolites, the process facilitates the difficult task of structure elucidation by providing derivatives that are primed for X-ray crystallographic analysis. We show that a cysteine probe efficiently and chemoselectively labels enone-, -lactam-, and -lactone-based electrophilic natural products (parthenolide, andrographolide, wortmannin, penicillin G, salinosporamide), whilst a thiophenol probe preferentially labels epoxide-based electrophilic natural products (triptolide, epoxomicin, eponemycin, cyclomarin, salinamide). Using the optimized method we were able to detect and isolate the epoxide-bearing natural product tirandalydigin from Salinispora and thereby link an orphan gene cluster to its gene product. Optimised reactions for thiol probes are also being developed to establish a HTS-like system. 320 PHOTOCATHODIC PROTECTION EFFECT OF TIO2 NANOTUBE FILMS ON STAINLESS STEEL Xu, L, Guan, Z C, Wang, H P, Du, R G Presenting author’s e-mail: [email protected] College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China TiO2 semiconductor films as photoanodes can provide photocathodic protection for metals, which has inviting prospects. Therefore, preparations and applications of TiO2 films have attracted considerable attention of corrosion researchers for corrosion control of metals. In this work, the TiO2 nanotube films were prepared by anodization under different conditions, and their photoelectrochemical performances were studied. TiO2 nanotube films were prepared on the cleaned Ti foils by anodization at 20 V for 30 min in a two-electrode cell with different electrolyte solutions. After the anodization, the specimens were annealed at 450°C for 2 h. Characterization of the films was accomplished by scanning electron microscopy, X-ray diffraction, and UV-vis spectroscopy. Photoelectrochemical measurements were conducted by a home-assembled photoelectrochemical measurement system, which includes a photoelectrochemical cell with a 0.5 M NaOH solution and a corrosion cell with a 0.5 M NaCl solution. The photocathodic protection effects of the films were investigated by detecting the potential change of 403 stainless steel in the cell coupled to the film in the photoelectrochemical cell. The results indicated that the electrolyte had an important effect on the morphologies and performances of the TiO2 nanotube films. A well-ordered TiO2 nanotube film was fabricated by the anodization in a glycerol solution with 40 vol% water and 0.5 wt% NH4F. When illuminated, the film made the potential of the coupled 403 stainless steel decrease by 400 mV, showing a good photocathodic protection effect. Acknowledgements This work was supported the National Natural Science Foundation of China (Nos. 21573182, and 21173177). 321 Photohydroxylated ZnS Nanobelts with High Photocatalytic Activity Ham, S, Jang, D Seoul National University, Seoul, Republic of Korea Nowadays, the environmental concern from organic pollutant have been grown. Thus, environmental remediation and energy conversion using solar light have gained extensive interest. As a part of environmental remediation, the decomposition of organic water pollutants using photocatalytic nanomaterials has been studied recently. In particular, metal sulfides have attracted significant attention in photocatalysis due to their suitable band gap and catalytic function. ZnS have been received extensive attention as photocatalyst materials because of their unique properties such as the rapid generation of electron–hole pairs by photoexcitation and the high reduction potential of conduction band. However, because ZnS is direct band-gap semiconductor material, the recombination of excited electrons and holes is very fast. To hinder the recombination of charge carriers and to increase the charge-carrier lifetime, we have formed Zn(OH)2 on the surface of the ZnS nanobelts via facile photochemical method. Hydroxyl radicals (·OH) formed by decomposition of hydrogen peroxide by UV light react with the surface of ZnS to form Zn(OH)2. Heterojunction formed between ZnS and Zn(OH)2 and surface hydroxyl functional groups separates charges effectively, and increases the lifetime of the excited charges. We have tested the photocatalytic efficiency of each sample via degradation test of 4-nitrophenol under Xenon-lamp irradiation. The optimized sample has showed 5.5 times higher photocatalytic activity compared to pristine ZnS nanobelts. Also, we have revealed the photocatalytic mechanism by monitoring reactive species using radical scavengers such as - p-benzoquinone (·O2 ) and isopropyl alcohol (·OH). 322 Piezo-like Electric Behavior of Electrospun Poly(lactic Acid) Nanoweb-Based Nanoenergy Harvester Kim, Kap Jin, Kim, Hongdoo, Ahn, Yu Jin, Yoo, Mi Kyong, Hong, Seung Kwan Presenting author’s e-mail: [email protected] Department of Advanced Materials Engineering for Information & Electronics, College of Engineering, Kyung Hee University, Yongin-si, South Korea As electrospinning has been used as a powerful and useful method for the fabrication of piezoelectric polymeric materials such as PVDF and its copolymers, poly(L-lactic acid) (PLLA) nanofiber web was prepared through electrospinning for nanoenergy harvester and pressure sensor application. Considering the shear piezoelectricity of uniaxially drawn PLLA film or fiber, the piezoelectric signal cannot be generated from a conventional capacitor structure through exerting normal pressure, because D1=d14T4 for PLLA film, i.e., piezoelectric charge (D1) can be induced only by shear stress (T4), not by normal stress (T1). Nevertheless, we could obtain a very high piezo-like electric current from electrospun PLLA nanofiber web as in case of poled PVDF or P(VDF-TrFE) film or as-electrospun PVDF and P(VDF-TrFE) nanofiber webs by external pressure. This suggests that the electrospun PLLA nanofiber web can have preferentially oriented C=O dipoles, which induced piezoelectric charge as seen from poled PVDF or P(VDF-TrFE) film. However, poled PVDF or P(VDF- o TrFE) loses piezoelectricity completely after annealing at 120 C, since oriented CF2 dipoles are randomized during annealing, whereas electrospun PLLA nanoweb showed piezo-like electricity even after annealing at 120 oC. Therefore, to identify the origin of piezoelectric charge induced by normal pressure exerted on electrospun PLLA nanofiber web, we proposed a new piezo-like electric mechanism in this study. More details are discussed in the presentation. Acknowledgement: This work was supported by Industrial Strategic Technology Development Program Founded by Ministry of Trade, Industry and Energy (MOTIE), Korea (Grant No. 10044953 and 10047976). 323 POLYANILINE-MODIFIED CARBON ELECTRODE FOR ELECTROCHEMICAL DETERMINATION OF ASCORBIC ACID Dayao, LR1, Sto. Domingo, HB2, Balitaan, JN2, Santiago, K2,3 1Department of Math and Physics, College of Science; 2Department of Chemistry, College of Science; 3Research Center for Natural and Applied Sciences, University of Santo Tomas, España 1015, Manila Abnormalities in the dosage of ascorbic acid (AA) may impose a great threat to human health. In this research, we devised an excellent electrochemical sensing unit based on polyaniline-modified carbon electrode (PANI-MCE). The sensing membrane was fabricated via in-situ polymerization process. The spectral and morphological properties of PANI-MCE were characterized using Fourier Transform Infrared (FTIR) spectrometer and Scanning Electron Microscope (SEM). The devised PANI-MCE presents good electrocatalytic properties, fast response time, and high reproducibility. Furthermore, the sensor exhibits a high sensitivity (18.713 uA mM-1) and high repeatability (RSD= 8.52%), making it a good candidate for AA determination. 324 Preparation and characterization of vinylimidazole-based polymeric monolithic capillary LC column Lin, S.-L., Fuh, M.-R. Presenting author’s e-mail: [email protected] Department of Chemistry, Soochow University, Taipei, Taiwan ABSTRACT TEXT In order to analyze polar small molecule for environmental and food safety applications, several alkylmethacrylate-based (AlMA-based) monolithic columns have been developed in our laboratory. Although the developed AlMA-based columns could efficiently separate phenylurea herbicides as well as amphenicol and sulfonamide antibiotics, these reversed- phased stationary phases are not suitable for simultaneous analysis of analytes with different physical properties such as non-polar/weak-polar and polar/charged compounds. Therefore, the development of mixed-mode stationary phases with two or more retention mechanisms becomes inevitable to enhance separation capability for analytes with different physical properties. Ionic liquids (IL) have been incorporated into liquid chromatography stationary phases by immobilization on silica or monolith to perform separation with different retention mechanisms including hydrophobic, ion-exchange, hydrophilic, and π-π interactions. In this study, we applied 1-vinylimidazole (VIM) as the functional monomer to prepare a series of VIM-based IL-monolithic columns using various dimethacrylate/diacrylate as cross-linkers. The porosity, permeability, and column efficiency of synthesized IL-monolithic columns were characterized. A mixture of phenol derivatives was employed to evaluate the applicability of the VIM-based IL-monolithic columns for separating polar small molecules. Poly(VIM-co-1,10-decanediol dimethacrylate [poly(VIM-co-DDDMA)] IL-monolithic column exhibited good retention of phenol derivatives. The retention might be attributed to the enhanced hydrophobic interactions to the long alkyl bridge in DDDMA as well as the hydrogen-bonding and π-π interactions between the phenols and the imidazolium functionality on the stationary phase. Furthermore, six phenol derivatives were well resolved by the VIM-DDDMA IL-monolithic column with isocratic elution. 325 Preparation and photocatalytic hydrogen production of Organic-inorganic hybrid materials HO-TPA/TiO2 Chen, Y1 , Liu, J1, Su, C1 *E-mail: [email protected]; 1Sun Yat-sen University, Guangzhou, China TiO2 has been widely studied as a semiconductor photocatalyst for hydrogen [1] production. However, TiO2 has narrow spectral response, fast photoelectron-hole recombination and low selective adsorption for the substrate, which limits its application in the visible-light catalysis. Calix[4]arene-based sensitizer with a cone structure has four light-harvesting units groups and anchoring groups in one molecule, which broaden the spectral response range, decrease molecule aggregation, suppress charge recombination, [2] and improve the stability. Combining the merits of both calix[4]arene and TiO2, we have manufactured new organic-inorganic hybrid materials with calixarene-based dyes and titanium dioxide by a simple sol-gel method and studied their photocatalytic hydrogen production properties.[3] In the paper, we have synthesized a calix[4]arene-based sensitizer HO-TPA, and then prepared a hybrid porous nanomaterial HO-TPA/TiO2. The mass content of HO-TPA has been optimized and the growth mechanism of HO-TPA/TiO2 has been explored. After loading the 0.5%wt Pt nanoparticles, Pt@HO-TPA/TiO2 exhibited high H2 production rate and good stability. The results show that the H2 production rate under visible light irradiation (λ ≥ 420 nm) was 3 mmol g-1 h-1 with triethanolamine as sacrifical agent and remained unchanged after 15 circle experiments. 16000 1run 2run 3run 4run 5run 6run 7run 8run 9run 10run 11run 12run 13run 14run 15run 14000 0.5% Pt@5Graph1OTPA-hybrid-300d-2h 12000 -1 10000 mol g mol / 2 8000 6000 4000 Amount of H 2000 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 Time/h (a) (b) Fig.1 (a) synthesis of HOTPA/TiO2 and (b) photocatalytic H2 production over the recyclability of Pt@HOTPA/TiO2 with 0.5 wt% Pt loading under visible light irradiation. References 326 [1] J. Schneider, M. Matsuoka, M. Takeuchi, J. Zhang,Y. Horiuchi, M. Anpo, D. W. Bahnemann, Chem. Rev., 2014, 114, 9919-9986. [2] L.-L. Tan, J.-M. Liu, S.-Y. Li, L.-M. Xiao, D.-B. Kuang, C.-Y. Su, Chemsuschem, 2015, 8, 280-287. [3] B Ghosh, K Lott, J Rirehie. Chem. Mater, 2006, 18, 504-509. 327 Properties of double layered silicone for a wearable kinesiology tape Ji, HC1, Jang, HS2, Han, JH2, Cho, NY2, Lee, JH3, Nam, KC1 1 Dongguk University College of Medicine, Goyang, Korea 2 Odoroso Co. Ltd, Seoul, Korea 3 Chung-Ang University, Seoul, Korea ABSTRACT Kinesiology tape can benefit a wide variety of musculoskeletal and sports injuries. Most of kinesiology tape is placed on skin with elastic adhesive. In this study, it is aimed to develop a clothes type kinesiology tape. For a wearable elastic therapeutic tape in cloth, a double layered silicone was developed. It is necessary for good adhesion to skin, strong property to bond fabric, and skin allergies relief. Bottom layer of the silicone is composed of liquid silicone rubber to bond fabric strongly. Top layer of the silicone consists of the mixture of a medical grade liquid silicone rubber and a pressure sensitive adhesive(PSA) for medical applications for microscopically lifting the skin. PSA was applied to compensate low viscosity and mechanical properties of top layered liquid silicone rubber. Adhesive performance to skin and bonding strength to fabric were tested. As a result, adhesive property to skin was 0.54 N/cm2 and the bonding strength to fabric was 4.2 N/cm. These results indicate that the multifunctional silicone can bond a wearable fabric and lift skin as a kinesiology taping application. 328 Quantification and Visualization of microRNA in a Nerve Cell Joon Won Park* Presenting author’s e-mail: [email protected] Department of Chemistry, Pohang University of Science and Technology, Pohang 37673, Korea MicroRNAs (miRNAs) play key roles in controlling various cellular processes, and the expression levels of individual miRNAs can be considerably changed in pathological conditions such as cancer. Accurate and precise quantification of miRNA at the single-cell level will lead to a better understanding of miRNA function. Here, we present a direct and sensitive detection method for a specific miRNA using atomic force microscopy (AFM). A hybrid binding domain (HBD)-tethering tip enabled mature miRNAs to be located individually on an adhesion force map. By scanning several sections of a micron-sized DNA spot, we were able to quantify the copy number of miR-134 from a single neuron and demonstrated that the expression was increased upon the cell activation. Additionally, we visualized individual miR-134s on fixed neurons after membrane removal and observed 2 - 4 miR-134s in the area of 1.0 x 1.0 m2 of soma. The number increased to 8 -14 in stimulated neurons, and this change matches with the ensemble-averaged increase in copy number. Moreover, mapping spines showed that miR-134s exist not at the head but at neck of spines, and the copy number is higher at the immature spines. The mapping result supports one of the previously suggested mechanisms. References 1. Hyun-Seo Koo, Ikbum Park, Yoonhee Lee, Hyun Jin Kim, Jung Hoon Jung, Joo Han Lee, Youngkyu Kim, Joung-Hun Kim, and Joon Won Park, Visualization and quantification of microRNA in a single cell by AFM, J. Am. Chem. Soc., 11664 (2016). 2. Yoonhee Lee, Youngkyu Kim, Donggyu Lee, Dhruvajyoti Roy, and Joon Won Park, Quantification of Fewer Than Ten Copies of a DNA Biomarker without Amplification or Labeling, J. Am. Chem. Soc., 7075 (2016). 3. Dae Heon Kim, Jae-Eun Lee, Zheng-Yi Xu, Kyeong Rok Geem, Yun Kwon, Joon Won Park, Inhwan Hwang, Cytosolic targeting factor AKR2A captures chloroplast outer membrane-localized client proteins at the ribosome during translation, Nature Communications, 6843 (2015). 4. Youngkyu Kim, Eung-Sam Kim, Yoonhee Lee, Joung-Hun Kim, Bong Chu Shim, Seong Moon Cho, Jeong Soo Lee, Joon Won Park, Reading Single DNA with DNA polymerase followed by Atomic Force Microscopy, J. Am. Chem. Soc., 13754 (2014). 329 Reform and exploration in the teaching of General Chemistry Jichuan Huo 1, Hong Lei 2, Juan Shen 2 Presenting author’s e-mail: [email protected]; [email protected] Affiliations (Arial, 12 font Italics, Organisation, City, Country) e.g. 1 Analytical and testing center, Southwest University of Science and Technology, Mianyang, P. R. China 2 School of Material Science and Engineering, Southwest University of Science and Technology, Miangyang, P. R. China General Chemistry is a general education course for geological engineering, civil engineering and other non-chemistry or non-chemical engineering professionals. The purpose of this course is to enable students to understand the basic theory of modern chemistry, to acquire the basic knowledge of chemistry and skills, as well as to know the application of these theories, knowledge and skills in engineering practice. It provides the necessary chemical foundation for further study and work. However, following deficiencies were found during our teaching process. Firstly, the content of General Chemistry covers the “four major chemistry courses”. Students suffer great burden of learning complicated content, fragmented knowledge, lots of concept, many formula and conclusion within short teaching hours. Secondly, some students think that many knowledge points have been learned in high school. Therefore, they are not interested in the course and not serious in class. Thirdly, the teaching object is freshman. As from different places, the students have uneven learning foundation, different agility of thinking and varying awareness of active learning [1]. The present paper analyzed the problems in the teaching process as well as the characteristics of the students combining with a number of practical teaching cases from the perspective of improving the effectiveness of General Chemistry teaching. Several reform proposals are suggested so as to increase the attraction of the course, improve the quality of chemistry teaching and cultivate students’ chemistry quality and innovation ability. 330 Regenerative Photoactive Polymer Networks by Metal-Terpyridine Interaction: Toward Sustainable Photocatalysis Jeong D-C1, Lee J1, and Song C1 Presenting author’s e-mail: [email protected] Affiliations (Arial, 12 font Italics, Organisation, City, Country) e.g. 1 Sungkyunkwan University, Gyeonggi, Korea ABSTRACT: The design and synthesis of photoactive polymeric systems are important in regard to solar energy harvesting and utilization. Although many organic photoactive systems have been developed, they suffer from their inferior long-term stability. However, Nature utilizes self-regeneration system in order to sustain photosynthesis efficiency. Here, we synthesized photoactive polymeric thin films via iterative self-assembly using reversible metal-terpyridine (M-tpy) interactions. We envisioned that the reversible M-tpy interaction can be exploited to mimic Nature’s self-repair system. In order to introduce tpy groups readily, we utilized cis-5-norbornene-exo-2,3-dicarboxylic anhydride, a norbornene derivatve, to which amine-functionalized tpy was coupled very easily. Ring-opening metathesis polymerization (ROMP) with tpy-norbornene monomers by Ru catalysts enabled the production of tpy-functionalized linear polymers and network ones. We will discuss here the several applications of tpy-functionalized polymers to photoactive thin films and regenerative photocatalytic systems. 331 REVERSIBLE NICKEL-IRON HYDROXYLPHOSPHATE CATALYSTS FOR HIGHTLY EFFICENT INTERMITTENT WATER SPLITTING Wang, z 1, Lei, Z 1, Bai, J 1, Li, Y 2, Zhao, C 1, 2 E-mail: [email protected] a Shaanxi Normal University, Xi’an, China 2 The University of New South Wales, Sydney, Australia ABSTRACT Global scale application of water splitting technology for hydrogen fuel production and storage of intermittent renewable energy sources has called for the development of oxygen and hydrogen evolution catalysts that are inexpensive, efficient, robust, and can withstand frequent power interruptions and shutdowns. Here we show controlled electrodeposition of porous nickel-iron hydroxylphosphate (NiFe-PO4) nanobelts onto the surface of macroporous nickel foams (NF) as a bifunctional composite catalyst for efficient whole cell water electrolysis. The NiFe-PO4/NF electrode exhibits high catalytic activity towards water oxidation and water reduction in alkaline solutions, and is capable of delivering current densities of 20 and 800 mA cm-2 at overpotentials of 249 and 326 mV for oxygen evolution reaction (OER), current densities of 20 and 300 mA cm-2 at overpotentials of 135 and 208 mV for hydrogen evolution reaction (HER). Further, in a two-electrode water electrolytic cell, the bifunctional NiFe-PO4/NF electrodes can achieve current densities of 20 and 100 mA cm-2 at cell voltages of only 1.68 and 1.91 V, respectively. Remarkably, the NiFe- PO4/NF catalyst also exhibits prolonged stability under both continuous and intermittent electrolysis, and can be used for oxygen evolution and hydrogen evolution reversibly without degradation.The excellent catalytic activity, stability as well as the facile and scale- up fabrication process of the NiFe hydroxyphosphate catalyst makes it promising for use as a noble-metal-free water-splitting electrode for industrial water electrolysis. 332 Rhodium(I)-Catalyzed Asymmetric Carbene Insertion Xu, M-H* State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, China Transition metal-catalyzed C-H or X-H (X = O, N, S, Si) insertion of metal carbene stands for an excellent approach for the construction of C-C or C-X bonds. Among them, catalytic asymmetric carbene insertion into C-H bonds has been well defined, while the asymmetric C-X bond formation via metal carbene intermediate were developed only recently. The Rh(II), Cu(I)/(II), Ir(III), and Fe(II) with suitable chiral ligands are the most regularly used catalysts for these transformations. On the other hand, rhodium(I) complexes with diverse chiral ligands are efficient catalysts for various asymmetric reactions, however, the related Rh(I)−carbene chemistry is far less studied. Recently, our group succeeded in performing the asymmetric metal−carbene insertion into X−H (X = B, Si) bonds using Rh(I)/diene complexes as catalysts (Figure). In this presentation, these achievements as well as recent progress will be described. 333 Screening Effects on van der Waals Interactions Li, M.1, Reimers, JR12, Gould, T3, Dobson, J3 [email protected] 3. Shanghai University, Shanghai, China 1 University of Technology Sydney, Sydney, Australia 2 Griffith University, Brisbane, Australia Van der Waals interactions are ubiquitous in the world, and have been recognized as critical to most important properties of natural matters including proteins and DNA (deoxyribonucleic acid). In chemical and biochemical environments, modern empirical approaches like Grimme’s D3 method allow for fast evaluation of these forces in electronic- structure calculations. However, this and related methods are based on London’s approximation to the van der Waals force as arising from pairwise-additive atomic fluctuations and polarizations. Recently, the Dobson classification was introduced to understand the shortcomings of such approaches, shortcomings particularly relevant for low-dimensional molecules and conductors such as graphene, C60, large aromatic molecules, and nanotubes. An important experimental characterisation of non-additive effects was the recent demonstration the placing a graphene layer between a silica substrate and silica AFM tip switches off the van der Waals interaction between tip and substrate through a Faraday-cage screening effect. We develop computational models to understand this effect, comparing the pairwise-additive D3 method to the popular many- bond dispersion (MBD) method for treating screening, and a new method developed by Gould to include and improve not only these contributions but also those from long-range fluctuations (related to the Casimir effect). 334 Separation and Determination of Clenbuterol and Ractopamine Using Field-amplified on- line Sample Stacking Method by Capillary Zone Electrophoresis Li, C, Jia, Z, Li, D, Wang,Y [email protected]; [email protected] Gansu Institute of Political Science and Law, Lanzhou, P. R. China A rapid, simple and reliable capillary zone electrophoresis method was developed for the separation and determination of clenbuterol and ractopamine. A buffer solution of KH2PO4- Na2HPO4 (50 mM ) with pH 7.20 was used as running buffer and the field-amplified sample stacking (FASS) technique was also applied to the on-line concentration of clenbuterol and ractopamine. Under the optimum conditions, clenbuterol and ractopamine were separated completely and determined with the correlation coefficient of 0.9994∼0.9996. Both of the detection ranges (S/N=3) were located from 0.1 to 50 μg mL-1. And the limit of detection was down to 20.0 ng mL-1 and 23.6 ng mL-1 for clenbuterol and ractopamine. The relative standard deviations (RSD) were less than 2.63% (run to run) and 3.73% (day to day) for peak area. Using the stacking measure, clenbuterol and ractopamine in spiked swine feed were successfully determined with the recovery of more than 95.4%. 335 Silicone Coated-Uniaxially Drawn PLA Film with Improved Piezoelectric Sensor Performance Ruthirapathi, T.S.1, Yoo, M.K.1, Ahn, Y.J.1, Kim, H.1, Kim, K.J.1 1 Kyung Hee University, Yongin, South Korea Polylactic acid (PLA) is well known as a biodegradable and biocompatible polymer with shear piezoelectric properties. The unique piezoelectricity of PLA is understood to originate from genuine chiral molecular conformation and helical structure aided by the transformation of 103 helical to 31 helical structure upon drawing film. In this study, we prepared uniaxially drawn PLA films with different draw ratios and investigated their piezoelectricity depending on draw ratio. We also measured birefringence of drawn PLA films and correlated the relationship between birefringence and piezoelectricity of ones. The film was cut in the direction of 45o angle from the draw direction and was fabricated into a rectangular sensor followed by adhering conductive fabrics to top and bottom surfaces. The observed piezoelectric voltage of PLA sensor depends on draw ratio under tensile stress. The result indicates that more drawn PLA film sensor shows higher piezoelectric voltage signal. Moreover, to improve the piezoelectric sensor performance, the PLA film sensor was coated on both sides with silicone rubber. The silicone coated- PLA film sensors are sandwiched between the two elastic textile bands along the longitudinal direction, which is designated as physiological sensing belt (PSB). The silicone coated-PLA film sensor showed higher piezoelectric signal compared with PLA film sensor itself. PLA film-based PSBs can be applied to the mattress to measure the electrical signals generated by the elongation of the sensor during heartbeat and respiration. More details will be discussed in the presentation. This work was supported by MOTIE, Korea (Grant No. 10047976 & 10044953). 336 Silver-phosphine complexes that catalyzing the photodegradation of organic pollutants Ren, Z.G.1 Lang, J.P.1 1 College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of China. Coordination polymers (CPs) are recently used in catalysing the photodegradation of organic pollutants in water. Silver compounds are known to be light-sensitive and may have good photocatalysis activities, while the silver complexes were less explored due to their relative low stability. We herein report the preparation of a series of silver complexes via the assembly of silver oxysalts (AgNO3, AgOAc, AgBz and AgSal) or silver halides with phosphine ligands, including a tetraphosphine ligand dpppda (1,4-N,N,N’,N’- tetra(diphenylphosphanylmethyl)benzene diamine) and a P-N hybrid ligand 3-bdppmapy (N,N-diphenylphosphanylmethyl-2-aminopyridine). Some water and light stable compounds were subsequently selected as catalysts and introduced in the photogradation of nitroaromatics (nitrobenzene, paranitrophenol and 2,4-dinitrophenyl) and organic dyes (RhB, MO, Amino Black, Amaranch Red, Orange I, Orange II, Orange IV, Orange G, Eriochrome + - Black T, Sunset Yellow) in water. These pollutants were fully converted to CO2, NH4 , NO3 , 2- SO4 and H2O, while the degradation mechanism was supposed to follow the ·OH radical mediated oxidation route. Photocurrent responses of some catalysts on ITO electrodes were investigated under UV irradiation, which revealed that the increase of the anodic currents fitted well with that of the rate constants in the photodegradation. 337 Simple Preparation of Tetraepoxy Compound from Anthracene revealed in Spectroscopic Study 1 1 2 1 1 1 Mohapatra, S. , Hayne, D.J. , White, J.M. , Doeven, E.H. , Adcock, J.L., Connell, T.U. , Barbante, G.J.1, Henderson, L.C.1, Francis, P.S.1 e-mail: [email protected] 1 Deakin University, Waurn Ponds, Victoria 3216, Australia 2 University of Melbourne, Melbourne 3010, Australia 2+ Tris(2,2′-bipyridine)ruthenium(II) ([Ru(bpy)3] ) has been widely used as single-electron transfer catalysts in photo-induced oxidation and reduction reactions. To explore and monitor various photoredox reactions, we designed and fabricated a reaction box equipped with a light-emitting diode (LED) as a photon source, and optical fibre connected to a charge- coupled device (CCD) spectrometer that enabled quantitative measurement of a portion of the emitted light from the reaction under progress. This provides us with insight into the activity of the photocatalyst and therefore the mechanism of the synthetic reactions. During our preliminary studies utilising this approach to explore the aerial oxidation of anthracene, we found an exceedingly simple approach to synthesise and isolate an interesting eight- electron oxidation product. The newly synthesised tetraepoxy compound has been characterised unambiguously from 1H NMR, 13C NMR, and single-crystal X-ray diffraction studies and a plausible mechanism for the reaction has been established. 338 Size control of anodic alumina membrane for aerosol therapy Nam, KC1, Choi, KH2, Ji, HC1, Park, BJ2 1 Department of Medical Engineering, Dongguk University College of Medicine, Goyang, Republic of Korea 2 Department of Electrical & Biological Physics, Kwangwoon University, Seoul, Republic of Korea ABSTRACT Inhalation therapy has played a pivotal role in the vistas of pulmonary drug delivery since ancient times, as a way of relieving respiratory diseases. Particularly, pulmonary delivery of drugs has develop into an attractive target in the health care industry as the lung is capable of absorbing pharmaceuticals either for local deposition or for systemic delivery. These drug delivery techniques has made developed rapidly in the 1950s with the development of nebulizers and pressurized metered-dose inhalers. Nebulizers transform liquid formulations and suspension into medical aerosol. In the past few years, there have been advances in the development of new nebulizers that hold the promise to improve aerosol drug delivery to patients with pulmonary diseases. In this study, a simple method is presented for the morphology and the dimension controls of the free-standing nanoporous and microporous membrane without the utilization of any elaborated instrumental works. This simple control of the nanoporous membrane is accomplished only by applying the same typical two-step anodization process of the utilized aluminum templates from the previous simple plate-type aluminum substrate. Also, the microporous membrane was synthesized by lithography process and electroforming process. Morphology and structural properties of the various porous membranes are investigated by field emission scanning electron microscopy, high resolution transmission electron microscopy, x-ray diffraction. 339 SnO2/ZnS Nanocomposites with High Photocatalytic Performances Lee, J, Ham, S, Jang, D Seoul National University, Seoul, Republic of Korea Heterojunction nanocomposites, where one semiconductor is partially coated by the other semiconductor, have received extraordinary attention as photocatalysis systems because both electrons and holes can readily participate in the redox reaction on their surfaces. Furthermore, one-dimensional (1D) nanostructures as photocatalyst substrates have been extensively used due to their unique structural and electronic properties and superior performances in the heterojunction systems. 1D nanostructures such as nanorods and nanowires/nanobelts possess several advantages as follows: large aspect ratios which can increase the capacity of light absorption; great separation efficiencies of photo-generated charge carriers due to their high mobility and straight transport pathways. In this work, we have fabricated SnO2/ZnS nanocomposites of SnO2 QDs (quantum dot)-deposited ZnS nanorods as 1D heterojunction nanostructures through a facile two-step hydrazine-assisted hydrothermal process without using any complex surface treatments to introduce new functional molecules or additional inter-connectivity. It is noteworthy that a rational synthesis of high-quality SnO2/ZnS heterojunction nanocomposites via a simple and friendly manner has not been reported yet. The photocatalytic activity and photostability of SnO2/ZnS heterojunction nanostructures are much higher than the respective ones of ZnS nanorods. The decay time, as well as the intensity, of the band-edge emission of SnO2/ZnS nanocomposites decreases progressively and rapidly with the increase of the SnO2 content, indicating that the higher photocatalytic degradation efficiencies of SnO2/ZnS nanocomposites result mainly from the increased separation rates of photogenerated charges. Our prepared SnO2/ZnS nanocomposites are considered to have great potential for photodegradation nanocatalysts in the field of waste-water treatment. 340 Stereoselective Synthesis of Alkenylboron Compounds via Copper Catalyst Jang, W. J and Yun J* [email protected] Sungkyunkwan University, Suwon, Korea Metal-catalyzed hydroboration of alkynes provides useful alkenylboron intermediates in synthetic chemistry. While the synthesis of (E)-alkenylboron via syn-addition is well-known, the synthesis of (Z)-alkenylboron via trans-addition is rarely reported. In this presentation, we report ligand controlled stereodivergent hydroboration of terminal alkynes with 1,8-napthalenediaminatoborane. NHC-Cu catalyst producued (E)-alkenylboron compounds with high stereoselectivity up to >98% for various terminal alkynes. On the other hand, (Z)-alkenylboron compounds were produced in the presence of phosphine-Cu catalyst at mild conditions via trans-addition of the borane reagent. 341 Study On CYP450 Family Based On Heterogeneous Information Networks Li Hongzhi1, Li Wenze1, Hu Lihong1 1 School of Computer Science and Information Technology, Northeast Normal University, Changchun, China ABSTRACT Cytochrome CYP450 is a large family of enzymes that are widely present in animals, plants and microbes. They are closely related to the metabolism of most exogenous and endogenous compounds, and their functions are versatile, and also related to complicated multiple reaction mechanisms, so that all the objects related to the catalytic reaction, enzymes, substrates/drugs, reaction mechanisms, tissues/organs, and diseases compose an interacting heterogeneous network. In recent years, the newly developed heterogeneous information network in data mining has established a structural analysis for various types of objects and links, which puts forward corresponding solutions to the complexity and heterogeneity of information network. Therefore, we propose to study relationships among the individual enzyme and related objects in CYP450 catalytic reactions by the heterogeneous information network, so as to understand the CYP450 reaction mechanisms and the relationships between them. Based on the establishment of heterogeneous information networks some unknown drug metabolisms and catalytic reaction mechanism may be revealed. 342 Study on the Thermal Decomposition of Tenofovir Disoproxil Fumarate You Jin-Zong, Wang Xue-Jie, Wu Cheng-Jie, [email protected] School of Science and Technology, Zhejiang International Studies University, Hangzhou, 310012, China Tenofovir disoproxil fumarate (TDF) is an antiretroviral medication used to prevent and treat HIV/AIDS and to treat chronic hepatitis B. The thermal decomposition of TDF was measured with thermogravimetry, differential scanning calorimetry, and thermogravimetric analysis coupled with Fourier transform infrared spectroscopy. The IR spectra, high-performance liquid chromatography, and liquid chromatography-mass spectrometry of TDF and the residues of its thermal decomposition at various temperatures were determined. The molecular bond orders were calculated using an ab initio method from the GAMESS program of quantum chemistry. The mode of thermal decomposition for TDF was discussed. The kinetic parameters for thermal decomposition such as activation energy Ea and the pre- exponential factor A were obtained using the Ozawa method. The prospective lifetime of TDF was estimated using the Dakin equation. The results indicated that the thermal decomposition of TDF is a three-step process, and the first stage is the decomposition of the phosphoric disoproxil section. The initial decomposition temperature in either nitrogen or air atmosphere is 138 °C. For decomposition in nitrogen, the Ea and A for the initial thermal decomposition are 92.5 kJ mol-1 and 5.01 ×109 min-1, respectively. For decomposition in air, -1 10 -1 the corresponding Ea and A are 99.3 kJ mol and 3.38 × 10 min , respectively. The thermal stability of TDF is not very good under routine temperature. 343 SYNERGISTIC OF Pseudomonas aeruginosa AND Pleurotus eryngii ON DDT BIODEGRADATION Purnomo, A.S, Ghanisari, N Presenting author’s e-mail: [email protected] Institut Teknologi Sepuluh Nopember, Surabaya, Indonesia DDT is one of the organochlorine pesticides, which dangerous for environmental and human. Thus, it is needed method that can degrade DDT effectively. Biodegradation is environment- friendly method by using fungi and bacteria to degrade organic pollutants. In this study, the ability of white-rot fungus Pleurotus eryngii to degrade DDT was investigated as well as the effect of the addition of Pseudomonas aeruginosa. The addition of P. aeruginosa was variated at 1, 3, 5, 7, and 10 mL (1 mL ≈ 1,528 x 109 cells) into P. eryngii culture which incubated for 7 days. P. eryngii degraded DDT approximately 43.21%. P. aeruginosa culture at concentration of 7 mL was the highest DDT degradation approximately 90.20% among varied addition concentration. Mix P. eryngii and P. aeruginosa degraded DDT maximally at a concentration of 10 mL of 82.37%. Metabolic products resulting from the degradation of DDT by the mixture of P. eryngii and P. aeruginosa were DDD and DDE. 344 Synthesis and Antimicrobial Activities of Novel Polymeric Cationic Dyes JJ Yang, ZR Pan Presenting author’s e-mail: [email protected] School of Environmental Science, Nanjing Xiaozhuang University, Nanjing, China ABSTRACT TEXT A number of cationic poly(acrylamide-co-vinylamine) derivatives were synthesized by using 2, 3-epoxypropyltrimethylammonium chloride as cationic reagent to react with amino groups of poly(acrylamide-co-vinylamine), and employed for the preparation of the novel polymeric cationic dyes through grafting reaction with vinyl sulfone mono-azo type reactive dye. The structures of the products were characterized by UV, FT-IR, and 1H NMR spectroscopy analysis. The antimicrobial efficacy of these novel polymeric cationic dyes against Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 29522) were evaluated by using a minimum inhibitory concentration (MIC) as an indicator. The results showed that these dyes had high antimicrobial activities on the tested bacterial strains, and all of them can inhibit visible bacterial growth at a concentration of 15.6 g/ml against both Staphylococcus aureus and Escherichia coli. 345 SYNTHESIS AND APPLICATION OF NOVEL ONE-HANDED HELICAL SUBSTITUED POLY(PHENYLACETYLENE)S Zang, Y1, Qu, Y2, Aoki, T2, Teraguchi, M2, Kaneko,T2, Ma, L1, Jia, H1 [email protected] 1 Qiqihar University, Heilongjiang, P. R. China 2 Niigata University, Niigata, Japan ABSTRACT TEXT A novel achiral phenylacetylene having an aldehyde group and two hydroxy groups was synthesized by deprotection reaction in membrane state of an one-handed helical poly(phenylacetylene) having dioxolane group by helix-sense-selective polymerization. The structures of the one-handed helical polymers and membranes were characterized by NMR, GPC, FTIR, UV and CD (Circular dichroism spectrum). The resulting polymer membranes showed good membrane forming ability which is very flexible. The enantioselectivity in permeation of the membranes from the resulting chiral polymers were examined. The polymer membranes having aldehyde group showed higher permeability and enantioselectivity than that of polymer membrane having dioxolane group in permeation of the racemate of phenylalanine (Phe). In addition, because of the introduction of aldehyde group, the permeability and enantioselectivity of the racemate of phenylethylamine of poly(phenylacetylene) membrane is much higher than that of the Phe. This result maybe cased by the reactivity between aldehyde group and chiral amine which mechanism is similar to the facilitated transport membrane. (157) 346 Synthesis and Application of a Self-Supported Polymeric Halogen Bond Donor Ma, S, Toy, P Presenting author’s e-mail: [email protected] The University of Hong Kong, Hong Kong, China ABSTRACT TEXT Halogen bonds (XBs), which was defined by IUPAC as the non-covalent interactions between an electrophilic halogen substituent R-X and a Lewis base LB, have gained increasing attention since the mid-1990s, especially as catalysts in organic synthesis In this regard we have synthesized a self-supported polymeric XB donor functionalized with 2-iodobenzimidazolium groups. In the presence of 0.5 mol% of our polymeric XB donor, a variety of 2-arylquinolines were reduced to the corresponding tetrahydroquinolines with Hantzsch ester, and the catalyst was successfully recovered and reused several times. Aldimines were also successfully reduced with high yields. Our catalyst was then applied to Diels-Alder reactions of aldimines with Danishefsky’s diene. Finally, our catalyst was also successfully applied in Friedel-Crafts reactions. 347 SYNTHESIS AND BIOLUMINESCENCE OF HETEROCYCLIC ANALOGUES OF FIREFLY LUCIFERIN Obata, R1, Kitada, N2, Maki, A.S2 Presenting author’s e-mail: [email protected] 1 Keio University, Yokohama, Kanagawa, Japan 2 The University of Electro-Communications Chofu, Tokyo, Japan ABSTRACT TEXT The several firefly luciferin analogues were synthesized by the solid-phase technique. Firefly luciferase catalyzes the oxidation of its substrate firefly luciferin (DLH2) in the presence of oxygen, magnesium ion and adenosine triphosphate, resulting in the production of light. This light emission phenomenon, so called bioluminescence is widely utilized for biomedical research and drug development, such as in vitro cell based reporter gene assay and also for in vivo optical imaging. Recently, several synthetic luciferin analogues as new substrate for firefly luciferase have been reported. We also developed red-shifted luciferin analogues suitable for in vivo bioluminescence imaging. However, DLH2 is a highly specific substrate for firefly luciferase, therefore, observed light outputs from modified luciferin analogues were commonly lower than those from native DLH2. To investigate the light producing mechanism of luciferase and to obtain higher light output from modified luciferin substrates, several luciferin analogues were synthesized. The structure of DLH2 consists with benzothiazole and thiazoline ring units. From our previous structure activity relationship study of synthetic luciferin analogues, thiazoline moiety was found to be the critical part to work as substrate. So in this study, benzothiazole moiety was substituted to heterocyclic structures, such as benzofuran, benzothiophene and indole. The protected cysteine bound resin was adopted for the solid-phase synthesis, and thiazoline ring was constructed in situ to obtain the target compounds. Compare to previous liquid phase synthesis of luciferin analogues in our lab, solid-phase method was suitable to obtain small scale products. Chemi-/bioluminescence property of synthesized luciferin analogues will be present. 348 Synthesis and characterization of Fe-Beta catalyst with high isomerization performance Xiaomeng, W, Wei, W, Jianwei, Z, Xuemei, S, Yang, Z, Zhaolu, F, Guozhi, J Presenting author’s e-mail: [email protected] International Joint research center of Catalytic technology, Key Laboratory of Chemical Engineering Process and Technology for High-efficiency Conversion, College of Heilongjiang Province, School of Chemistry and Material Sciences Heilongjiang University, Harbin, Heilongjiang, China ABSTRACT TEXT Conversion of vegetable oils into renewable hydrocarbon-based fuel can be achieved by catalytic hydrotreating to biodiesel products via decarboxylation or hydrodeoxygenation processes to obtain mainly n-alkanes. Furthermore, hydroisomerization of n-alkanes can be also significant depending on the characteristic of the catalysts and these reactions can contribute to upgrade the fuel properties that can be fed directly into unmodified engines because they are composed by hydrocarbons in the range of diesel and jet fuel [1, 2]. Metal/acid bifunctional catalysts, especially the Pt or Pd supported on zeolite molecular sieves showed good catalytic performance in hydroisomerization of n-alkanes, but the excess acidity of zeolites had been found to be responsible for the cracking of long carbon chains. Therefore, in this study a series of partially Fe-incorporated Beta-x (x was the ratio of Al(NO3)3/ Fe(NO3)3, x = 4.00, 1.50, 0.67, 0.25) zeolites were synthesized, and based on the Beta-x molecular sieve, a series of 0.5Pd/ Beta-x bifunctional catalysts were prepared. Their catalytic performance was investigated in n-hexadecane hydroisomerization using a fixed-bed flow reactor system. The highest iso-hexadecane yield of 69% was obtained at an n-hexadecane conversion of 82% over the 0.5Pd/Beta-1.50 catalyst, which can be attributed to the suitable amount and strength of the Brönsted acid sites. 349 Synthesis And Characterization Of Modified Urea Formaldehyde Resin Mehedi, M2, Sultana, S1, Nur, H P1, Abedin, M J1, Samaddar P R2 Presenting author’s e-mail: [email protected] 1 Fiber & Polymer Research Division, BCSIR Laboratories, Dhaka, Bangladesh 2 Department of Chemistry, Eden Mohilla College, Dhaka, Bangladesh ABSTRACT Thermosetting polymer, urea formaldehyde resin is the most widely used adhesive for the production of wood based panels. Adhesive grade thermoformable Urea Formaldehyde (UF) resin has been synthesized in this piece of research work. To improve the mechanical properties of the synthesized UF resin, it was modified with thermoplastic polymer polyvinyl alcohol (PVA) during the reaction process. Optimum condition for the reaction was selected by changing the parameters such as time, temperature, pH, concentration of PVA and molar ratio of urea and formaldehyde. FT-IR spectroscopic analyses were done for synthesized UF resin and modified UF resin. Physical properties of both the liquid UF and modified UF resins were measured and reported. Polymer films of the synthesized UF resin and modified UF resin were made by solution casting method. Mechanical and thermal properties of both the unmodified and modified UF resin films were measured and studied to examine the effect on the amount of PVA incorporation in modified UF resin. Thermal properties of both UF resins exhibited almost the same glass transition temperature (Tg) and melting point (Tm) but improved tensile properties were obtained for modified UF resin than unmodified UF resin. The modified UF resin with 2% incorporation of PVA showed significantly higher tensile properties than other modified UF resins. 350 SYNTHESIS AND SYSTEMATIC STUDY OF PORPHYRIN METAL-ORGANIC FRAMEWORKS Pila, T1, Jumpathong, W2, Piyakeeratikul, P2, Wannakao, S2, Kongpatpanich, K2 Presenting author’s e-mail: [email protected] 1 School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, Thailand 2 School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, Thailand Metal organic frameworks (MOFs) are novel microcrystalline materials comprised of metal cluster as a coordinator and organic ligand as a linker. MOFs have emerged as promising materials due to their remarkable features such as ultra-high porosity, flexibility and tunable properties. In this work, porphyrin is chosen as the organic linker because of its rigid structure, variety of peripheral substituents and the available center site for metalation, which makes it superior to other ligands. Consequently, the topological diversity of MOFs can be intelligently designed by manipulating porphyrin peripheral functional groups as well as several choices of metalation, resulting in versatile properties of MOFs that can meet the desired application. Despite the challenge posed by the preparation of porphyrin-based MOFs, we can synthesize porphyrin-MOFs which have new properties and can be used in a wide range of applications. 351 SYNTHESIS OF CHIRAL COVALENT ORGANIC FRAMEWORKS USING (+)-MENTHOL AS CHIRAL SOURCE Xu, L1 , Zang, Y1, Chen, Q1, Lei, T1, Tong, X1, Ma, L1, Jia, H1 1 Qiqihar University, Heilongjiang, P. R. China ABSTRACT TEXT Novel chiral covalent organic frameworks (CCOFs) having different size of pores were synthesized by using (+)-menthol as chiral source. Three kinds of linkages were used in the synthesis of CCOFs, such as, boroxine, alkynyl group and imines. The resulting CCOFs were characterized by infrared spectroscopy (IR), scanning electron microscope (SEM), transmission electron microscope (TEM), power X-ray diffraction (PXRD), circular dichroism (CD), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC) and Brunauer-Emmett-Teller (BET). The crystallinities and porosities of boroxine linked CCOFs were higher than that of linked by alkynyl group and imines. However, the stability of CCOFs having alkynyl group and imines as linkages were higher than that of boroxine linkage in the presence of water or protic solvents because of the decomposition of its boroxine bonds. The CCOFs were used as preliminary enantioseparation materials for 2-butanol racemate. 352 Synthesis of Metal Complexes of N-Heterocyclic Carbenes and Their Catalysis Wanzhi Chen and Xiaofei Department of Chemistry, Zhejiang University, Hangzhou, China ABSTRACT The coordination and organometallic chemistry of N-Heterocyclic carbenes (NHCs) have been developed quickly, and NHCs have been widely used for the preparation of transition metal-based catalysts. Metal NHCs complexes have been found extensive applications in C-C and C-N formation reactions. Transition metal complexes of NHCs are normally obtained through reactions of free carbenes and corresponding metal salts, transmetallation of Ag-NHC complexes, or reactions of imidazolium salts with basic metal salts. We present more direct and convenient synthetic methodologies for the preparation of metal NHC complexes. A number of metal-NHC complexes have been obtained in moderate to excellent yields through reactions of commercially available metal powder with imidazolium salts. The copper and nickel NHC complexes were used as carbene transfer reagents for the preparation of other noble metal complexes such as palladium, platinum, and rhodium complexes. A few C-C and C-N formation reactions will also be presented by using these metal NHC complexes. 353 Synthesis of nano Zn-substituted ZSM-5 zeolites and their aromatization performance Su, X1, Bai, X1,3,*, Wu, W2,*, Fang, Y2, Jiang, X2 Presenting author’s e-mail: [email protected] 1 College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin, China 2 National Center for International Research on Catalytic technology, School of Chemistry and Material Sciences, Heilongjiang University, Harbin, China 3 Institute of Petrochemistry, Heilongjiang Academy of Sciences, Harbin, China ABSTRACT TEXT In today's society, the fuel consumption increased greatly with the rapid development of automotive transportation, as a sequence, exhaust pollution becomes more and more serious. In China, approximately 80% of gasoline comes from FCC processes in which the olefin content is usually as high as 45–65 vol.%. Therefore, it is crucial to decrease the olefins and sulfur contents in FCC gasoline. Many studies have shown that olefins aromatization is greatly favored over bifunctional Zn incorporated ZSM-5 zeolites[1].The incorporation method of isomorphous substitution effectively avoid the blocking of the micropore and the loss of active component compared with impregnation method. Moreover, microwave-irradiated heating (MW) provides distinct advantages such as rapid heating, homogeneous nucleation as well as a shorter crystallization time. Hence, this research was undertaken to study the influence of heating methods both conventional electric heating (CE) and microwave irradiation (MW) in the seed preparation and crystallization process of synthesis of nanosized ZnZSM-5 zeolite via organic structure-directing agent-free method on the physicochemical properties and catalytic performance in the 1-hexene aromatization. The results show that combine of microwave irradiation heating with conventional hydrothermal method can not only promote the nucleation and growth rate but also modulated the size and arrangement as well as the acid strength and density of the ZnZSM- 5 nanocrystals. ZnNZ5-MW/CE sample exhibited the highest aromatics yield due to the intact micropore structure, higher concentration of Brønsted acid site as well as the promoted synergistic effect between Brønsted and Lewis acid sites. References [1] S.M.T. Almutairi, B. Mezari, P.C.M.M. Magusin. ACS Catal. 2012, 2, 71–83. 354 Synthesis of Novel peroxisome proliferator-activated receptor δ agonists Chin, J1, Cho, SJ1 [email protected] [email protected] 1 New Drug Development Center, Daegu-Gyeongbuk Medical Innovation Foundation, Daegu, Korea Peroxisome Proliferator-Activated Receptor δ (PPARδ) has recently come into the focus as a re-emerging drug target for the treatment of associated diseases such as metabolic syndrome as its activation alters glucose and lipid metabolism through a transcriptional regulation and results in beneficial pharmacological actions, typically an exercise mimic. We synthesized novel PPARδ ligands and an efficient synthetic route to these analogs was also developed. Surprisingly, some of compounds were potent and selective hPPARδ agonists with 200-fold selectivity over the other two subtypes, namely, hPPAR δ and hPPARδ. Some selective PPARδ ligands showed good bioavailability and in vivo efficacy. These results suggest that our novel PPAR δ agonists could be promising candidates for inflammation and metabolic diseases. 355 Synthesis of Silver Nanoclusters in DNA Nanostructures Yahui Guo1, Yao Zhang1, Renjun Pei2, Weirong Yao1, He Qian1* Presenting author’s e-mail: [email protected] 1 School of Food Science and Technology, Jiangnan University, Wuxi, China 2 Suzhou Institute of NanoTech and NanoBionics, Chinese Academy of Sciences, Suzhou, China ABSTRACT Noble metal nanoclusters (NCs) have been emerged as a class of intriguing materials as luminescent chromophores. An increasing number of works have been carried out to synthesize fluorescent silver nanoclusters, and the many reported works demonstrated that the properties of silver nanoclusters heavily depend on their protection groups. Ag nanoclusters that use DNA as template showed not only excellent biocompatibility for their employment of naturally occurring biomolecule DNA, but also intrinsic role as a probe, which saved trouble of functionalization. Different DNA scaffolds including hairpin, i-motif, G-quadruplex, triplex, D’-DNA, C-rich DNA etc. were employed to cap the fluorescent dots with specific optical properties respectively. Based on our experimental data, we found that, besides the sequences of the capping DNA, a hydrophobic environment also makes important contributions to the brightness of DNA-AgNCs. REFERENCES 4. S. Choi, R. M. Dickson and J. Yu, Chem. Soc. Rev., 2012, 41, 1867-1891. 5. I. Diez, M. Pusa, S. Kulmala, H. Jiang, A. Walther, A. S. Goldmann, A. H. Muller, O. Ikkala and R. H. Ras, Angew. Chem. Int. Ed., 2009, 48, 2122-2125 6. X. Yuan, T. J. Yeow, Q. Zhang, J. Y. Lee and J. Xie, Nanoscale, 2012, 4, 1968-1971. 7. H. C. Yeh, J. Sharma, J. J. Han, J. S. Martinez and J. H. Werner, Nano Lett., 2010, 10, 3106-3110 356 Synthesis of Three-connected Periodic Mesoporous Organic silicate Fan, X1, Zhuoying Xie,1* Zhongze Gu1,2,* Email: [email protected] 1State Key Laboratory of Bioelectronics, School of Biological Science and Medical Engineering, Southeast University, Nanjing, China 2Suzhou Key Laboratory of Environment and Biosafety, Research Institute of Southeast University in Suzhou, Suzhou, China “Co-condensation” is one of the most common and convenient methods to incorporate organic groups onto periodic mesoporous silicas（PMSs）surface. However, the stability of traditional PMSs is predicated upon the existence of a robust, four-connected network of tetrahedral SiO4 building blocks, once the three connected RSiO3 organic units over the 25% of total, the open framework will collapses. Therefore, the incorporation of modified functional groups by co-condensation are very limited, lower than 25% of total, generally .In this study, we gained inspiration from the new-type PMSs called periodic mesoporous hydridosilica (meso-HSiO1.5), which possess a three- connected network structure but still present ordered channels, synthesized a three- connected periodic mesoporous organic silicate by co-condensation pathway. Since the mechanical stability of meso-HSiO1.5 is attribute to the small amount of Si-OH•••H-Si hydrogen bonding and the small steric demand of Si-H groups，except these Si-H bonds which used to maintain structure, the rest of them provide the active sites for functional modification, which enhance the degree of functionalization greatly. Our method，which synthesize mesoporous organic silicate by co-condensation with triethoxysilane and different organosilicon coupling agents, enhances breaks the 25% limit of organic functionalization of PMSs by co-condensation, and provides an effective approach to gain functionalized mesoporous silica with a higher functionalized degree. 357 SYNTHESIS, SPECTROSCOPIC, ANTIOXIDANT AND ENZYME INHIBITION STUDIES OF TITANIUM((IV) COMPLEXES Ashiq, U1 , Shaikh, Z1, Jamal, RA1, Mahroof-Tahir, M2 [email protected] 1Department of Chemistry, University of Karachi, Karachi, Pakistan 2Department of Chemistry and Earth Sciences, Qatar University, Doha, Qatar 2Department of Chemistry and Biochemistry, St. Cloud State University, St. Cloud, MN 56304, USA ABSTRACT The present study explores the synthesis and inhibitory potential of Titanium(IV) complexes of hydrazides against lipoxygenase oxidative enzyme. In addition, non-enzymatic radical scavenging activities of these complexes were also determined. The complexes were characterized by spectroscopic methods (IR, 1H NMR and 13C NMR), elemental analysis and conductivity studies. These studies suggest bidentate coordination of the ligands through carbonyl oxygen and primary amine nitrogen, resulting in octahedral geometries. Hydrazides with pyridyl substituents displayed 1:2 metal- to-ligand ratio, and hydrazides with imino substituents exhibited 1:3 metal-to-ligand ratio resulting in an outer sphere complex. The remaining complexes displayed inner sphere coordination with 1:1 metal-to-ligand ratio. Results showed that hydrazide ligands and their respective Titanium(IV) complexes posses scavenging and inhibition potential against DPPH and lipoxygenase, respectively. However, contrary to that uncoordinated ligands showed no activity against nitric oxide and superoxide whereas their complexes showed varying degrees of radical scavenging properties against DPPH, superoxide and nitric oxide free radicals. These studies indicate that geometry of complex, nature and position of substituent groups play a vital role in scavenging and inhibition potential of these compounds. The structure–activity relationships of the complexes are discussed. 358 THE ANESTHETIC PROPERTY OF LEAF EXTRACT FROM Datura metel (Talampunay) LEAVES Villahermosa, M1, Lirazan, M1 [email protected] 1University of the Philippines Manila, Manila City, Philippines Datura metel, a shrub-like perennial herb commonly known as devil's trumpet and metel grown in tropical to temperate areas of the world is a popular traditional medicine despite its narcotic property and high toxicity. It is used by some indigenous people in the Philippines for relieve of asthma, rheumatism, cold symptoms and excessive sneezing associated with hay fever. This study aims to evaluate the anesthetic property of the leaf extract of Datura metel using the modified Mouse Tail-flick Test of Grant (Grant 1993) and Beam Balance Test on male and female Swiss Webster mice. The numbness to heat and pain observed in mice immediately after injection of leaf extract confirms its anesthetic effect. The negative controls 99% ethyl alcohol, ethyl acetate (analytical grade) and 0.9% NaCl solution did not show the same effect. The minimum effective dose of the extract was observed to be 1.425 mg/kg mouse, a dose which is within the range of admissible anesthetics administration, 1- 5 mg/kg of mouse (Becker 2006). The onset of effect had a mean value of 1 second, significantly different (p<0.00027) from that of equal dose of Lidocaine HCl, the positive control used in the experiment. However, there was no significant difference on the duration of their effects (p=0.31134). The plot of duration of effect against different doses of leaf extract was found to be linear with pearson correlation coefficient of 0.9761, indicating direct proportionality. Moreover, the results of the Beam Balance test suggest that the anesthetic effect of the leaf extract is probably localized or on the site of injection. 359 The effects of intramolecular hydrogen bonding in unsymmetrical squaraines on photovoltaic performance Lin Yang1, Youqin Zhu,2 Suling Zhao,2 Yan Huang*1 1 Key Laboratory of Green Chemistry and Technology (Ministry of Education), College of Chemistry, Sichuan University, Chengdu 610064, P. R. China. 2 Key Laboratory of Luminescence and Optical Information (Ministry of Education), Institute of Optoelectronics Technology, Beijing Jiaotong University, Beijing 100044, P. R. China. ABSTRACT TEXT (Arial, 12 font, left aligned, maximum 250 words) Three unsymmetrical squaraines (USQs) with different number of hydroxyl groups (BIISQ bearing two hydroxyl substituents, BIISQ-MOH bearing mono-one, and BIISQ-NOH bearing none) have been synthesized for understanding of the molecular structure-property relationship of photovoltaic materials. Their solar cells based on BIISQ have obtained the best performance, which is approximately three times higher than that of BIISQ-NOH. Our research show that the introduction of strong intramolecular hydrogen bonding interactions in squaraines can affect the whole π-conjugated properties, such as deepening the HOMO energy level and thus enhancing the open-circuit voltage, increasing the dipole moment and then improving hole mobility, weakening the electron-withdrawing ability of centric four- membered rings (as A unit in squaraine molecule) and thus improving the compatibilities between USQs and PC71BM. This work reveals that the introduction of intramolecular HB interactions in π-conjugated systems could be a promising strategy in tailoring molecular properties, film morphology, and photovoltaic performance. Interestingly, our research also finds that when the molecular skeletons of donor materials are relatively similar, thin layer chromatography (TLC) analysis might be a simple, cheap, and rapid way to preliminarily forecast the compatibility between donor materials and PCBM. 360 The Mechanism and the Kinetics of Thermal Decomposition of Gemcitabine Xue-Jie Wang， Jin-Zong You School of Science and Technology, Zhejiang International Studies University, Hangzhou, 310012, China Gemcitabine (GTB) is a nucleoside analog used in chemotherapy for various carcinomas. The thermal decomposition of GTB was measured with thermogravimetry, differential scanning calorimetry, and thermogravimetric analysis coupled with Fourier transform infrared spectroscopy. The IR spectra, high-performance liquid chromatography, and liquid chromatography-mass spectrometry of GTB and the residues of its thermal decomposition at various temperatures were determined. The molecular bond orders were calculated using an ab initio method from the GAMESS program of quantum chemistry. The mode of thermal decomposition for GTB was discussed. The kinetic parameters for thermal decomposition such as activation energy Ea and the pre-exponential factor A were obtained using the Ozawa method. The prospective lifetime of GTB was estimated using the Dakin equation. The results indicated that the thermal decomposition of GTB is a three- step process and the first mass loss stage mainly is to lost furan ring. The initial decomposition temperature in either nitrogen or air is 225 °C. For decomposition in nitrogen, the Ea and A for the initial thermal decomposition are 122.0 kJ mol-1 and 2.75 × 1010 min-1, respectively. For decomposition in air, the corresponding Ea and A are 133.8 kJ mol-1 and 4.37 × 1011 min-1, respectively. The thermal stability of GTB is good under routine temperature. 361 The mole: the unit of counting quantity but not measuring quantity Huang, R1, Huang, H1, Li, D2, Zhu E1 [email protected] 1The College of Chemistry and Chemical Engineering, 2The College of Physics and Technology, Xiamen University, Xiamen, Fujian, China There are seven base quantities in ISQ with base units. Mass can be generalized as amount of matter in object, which is easily confused with amount of substance. the other six quantities may be measured directly with instrumentations, but amount of substance may be not obtained directly, because it is a counting quantity. It is not correct to consider amount of substance as physical quantity. Quantities can be compared by assigning a numerical value in terms of a unit of measuring or counting. Two basic divisions of quantity imply distinction between continuity and discontinuity. The two principal types of quantities are divided as physical(measuring) and mathematical(counting). All measurements contain three elements: a number of magnitude, units providing basis for comparing, and uncertainty or error. Some counting quantity can be expressed as accurate number without error. Mass is a physical quantity, but amount of substance is defined in the unit of mole that contains as many entities, as there are atoms in exactly 12 g of 12C. So that, the amount of substance is counting quantity. One can determine chemical entities, in moles, by dividing sample’s mass by the substance’s molar mass. Other methods include use of molar volume or electric charge. The number of particles in a mole is known as Avogadro’s number, which value is 6.022140857(74)ⅹ1023, with the error deriving from physical measurements of mass or volume or electric charge. Therefore, mole, just like dozen, is a unit of mathematical quantity but not physical quantity. 362 Thioether Modified Zr-MOFs: Enhanced Stability, Hg (II) Removal and Post-synthetic Modification HOU Y.-L., XU Z. E-mail: [email protected] City University of Hong Kong, Hong Kong Metal-organic framework, as one of the most promising well-defined porous materials, have attracted numerous attention from all research areas. Thousands of MOF materials have been prepared and reported by chemists now, among which Zirconium-based MOFs (such as UiO-66, PCN-606, NU-1000) are widely explored due to their high stability. Various methods already discovered for the effective and efficient preparation (solvothermal one-step synthesis, post-synthetic modification, post-synthetic exchange and microwave synthesis, etc.) and application of MOF-based porous materials. So far, the MOFs with both high chemical stability and efficient metal uptake capability have been pay less attention. Based on our previous research of MOF materials modified with thioether groups, we combine multifunctional flexible thioalkyl side chains with the stable and well-defined structure of Zirconium-based MOFs with UiO-68 or NU-1100 topology, respectively. Here, we report several Zirconium-based MOF sorbents, which are highly stable in both air and water, readily utilized for the effective heavy metal removal from aqueous solution. Enhanced air-stability of Zr-MOFs was achieved by the concise design and synthesis of the ligands, where both backbone and sidechain of the organic linkers pay important roles. Thiol-modified Zr-MOFs show excellent Hg(II) removal capability approaching commercial available materials, and the one with NU-1100 structure performs best for the removal of Hg(II) ions from aqueous solution with Kd value of 2.4×104 mL g−1 and the maximum absorption capability(qmax) of 322mg/g based on Langmium model. Furthermore, the thioalkyl sidechains are further crosslinked inside the crystalline solid for the readily construction of hydrophilic MOFs and polymer@MOF composites. 363 TIN OXIDE GROWH MEASUREMENT AT INDOOR ENVIRONMENT Saito, H1, Kumakura, M 1 1 Tokyo Denki University, Tokyo, Japan We measured tin oxide growth rate at Indoor environment with electrochemical methods. Mainly used methods are Sequential Electrochemical Reduction Analysis (SERA) and Quarts Crystal Microbalance (QCM). The surface oxide thickness affects tin soldering. This is because that the melting point of tin oxide is higher than that of tin itself. Since the oxide layer forms at indoor environment, engineer need to estimate the oxide thickness for better soldering. This work shows the tin oxide growth. We obtained that two oxides SnO and SnO2 are formed on the tin surface and found that SnO2 grows at indoor environment. 364 Transition metal complexes with 3,3’-diphenyldicarboxylate and 1,4-bis(1,2,4-triazol- 1-yl)butane): Structure and luminescence Mei-Na Zhang, Ting-Ting Fan, Xia Li* E-mail: [email protected] Deparment of Chemistry, Capital Normal University, Beijing, China Abstract Three metal–organic frameworks (MOFs), [M(3,3΄-dpdc)(btb)1/2]n (M = Zn 1, Cd 2; 3,3΄-dpdc = 3,3’-diphenyldicarboxylate and btb = 1,4-bis(1,2,4-triazol-1-yl)butane) and [Cu3(3,3΄-dpdc)3(btb)2]n (3), were prepared and structurally determined. The semi-rigid 3,3΄- dpdc is a V-shaped aromatic multicarboxylate species, which make it a good candidate for constructing diverse structures MOFs with good stability and luminescence property. The flexible btb ligand can adopt different conformations and is usually introduced in the synthesis of MOFs, leading to novel topologies or entanglements. The Zn(II), Cd(II) and Cu(II) centers as nodes have different coordination geometry, which results in MOFs with different structures and functions. Complex 1 is a 2D structure with the uninodal [ZnO4N]. The net with topology of {33.47.54.6} is constructed from the Zn- COO-Zn-btb- handed helices by long linear spacer 3,3’-dpdc ligands. Complex 2 possesses a 3D framework with 12 29 14 the uninodal [CdO4N2] and topology of {3 .4 .5 }, consisting of Cd-3,3’-dpdc- and Cd- 3,3’-dpdc –Cd-btb- handed helices. Complex 3 is a 3D framework with 2-nodal 15 35 5 6 8 12 [Cu1O5]/[Cu2O4N2] and topology of {3 .4 .5 }2{3 .4 .5 .6.7}, there are helical chains consisting of the mixing Cu1, Cu2, btb, COO, 3,3΄-dpdc. The three anhydrous MOFs are thermally stable. Complexes 1-2 exhibit intense ligand-based blue luminescence and high sensitivity to detect Fe3+ in aqueous solution through fluorescence quenching. Furthermore, the 2D network structure (1) is more effective in sensing Fe3+ than that of the 3D structure (2). 365 Transition-Metal-Free Oxidation of Allylic Alcohols to α,β-Unsaturated Carboxylic Acids Yang, J W E-mail: [email protected] Sungkyunkwan University, Suwon, South Korea Green chemistry, also known as sustainable chemistry, is the design of chemical products and processes that reduce or eliminate the use or generation of hazardous substances. From the perspective of green chemistry, we recently addressed our efforts to the design and t development of transition-metal-free oxidation using NaO Bu-O2 system. As a result, allylic alcohol can be readily converted to the corresponding α,β-unsaturated carboxylic acid under mild conditions. The present protocol is an eco-friendly alternative to a conventional transition metal-based method. This new strategy allows large-scale production with non- chromatographic purification, while also suppressing competitive reaction pathway. 366 Triple-Stimuli-Responsive Fluorescence Molecular Controls with Novel Near IR- BODIPY Functionalized [2]Rotaxane Arumugaperumal, R1, Venkatesan, P2, Shukla, T1, Raghunath, P3, Singh, R1, Wu, SP2, Lin, MC3, Lin, HC1* E-mail: [email protected] 1 Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu, Taiwan 2 Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan 3 Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, Taiwan ABSTRACT A novel near IR fluorescent switchable NIR4 [2]rotaxane composed of two different molecular stations and rotaxane arms terminated with near IR borondipyrromethene (BODIPY) fluorophores and its derivatives were synthesized for the first time by CuAAC click chemistry. The molecular shuttling motion could be addressed by the fluorescence signal transduction via distance dependent photo-induced electron transfer process of NIR4 [2]rotaxane triggered by external chemical stimuli (acid/base). The construction and efficient synthesis of NIR4 [2]rotaxane with a high level of the structural complexity design always has a more challenging task of selective anion sensing. Conspicuously, the key design of molecular architecture involved the embedded flexible arms of both NIR4 and NIR2 triazolium groups acted as molecular stations and H-bonded donors, which exhibited impressive selectivity and sensitivity toward complementary anionic guest species. The specific mechanical molecular motions and host-guest interactions of mechanically interlocked machines (MIMs) were also further explored by quantum mechanical calculations. Accordingly, the host systems of NIR2 and NIR4 could be applied in vivo imaging and clarify the distribution of - H2PO4 at subcellular levels. 367 Tuning Tilt Angle of Si Nanostructures by Metal-Assisted Chemical Etching Teng, F, Li, N, Xu, D, Xiao, D, Yang, X, Lyu, N Presenting author’s e-mail: [email protected] Jilin University, Changchun, China Si nanostructures have been widely applied in the field of nanoelectronics, opto-electronics, energy conversion and storage, as well as biosensors and chemical sensors. Metal-assisted chemical etching (MaCE), a wet etching method, has attracted considerable attention due to its accessibility and cost-efficiency. It is known that the morphology of Si nanostructures affects the performance of Si based photoelectric devices. However, it is difficult to control the tilt angle of Si nanostructures with MaCE, which limits the applications of MaCE in Si nanofabrication. Herein we demonstrate a facile method to precisely regulate the tilt angle of nanocones with MaCE in a one-step process. With Au nanohole arrays as templates, the tilt angles of Si nanocones can be tuned from 69.2 ° to 88.6 ° by varying the composition of etchant. The reflectivity of Si nanocone arrays with the same height (2.2 μm) decreases with the decreasing of the tilt angle. When the tilt angle is 83.0 °, the average reflectivity is lower to 1.37% at 250-1000 nm band. This method can be applied for the fabrication of Si nanocones over large area (as large as 2 cm × 2 cm). This chemical method should be applicable to other Si nanostructures, which may promote the applications of MaCE in semiconductor manufacturing. 368 ULTRABRIGHT AMP PROTECTED GOLD NANOCLUSTERS AND ORIGINATION OF HIGH LUMINESCENCE Liu, J1, Li, H-W1, Wang,W-X1, Wu Y1* [email protected] 1State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, Jilin University, No. 2699 Qianjin Street, Changchun 130012, China. ABSTRACT In the present study, the adenosine monophosphate (AMP) protected gold nanoclusters (AuNCs@AMP) are prepared by using a newly developed heating method in a short time ( 60 min), which show a strong and stable luminescence in a relative high QY (14.5%). The in-depth study by employing Infrared, 1H and 31P NMR spectra as well as Mass spectrometry supply possible binding model and ratio of AMP to the gold cluster, which reveal the origination of such a high luminescence to both the binding of either purine ring and/or phosphate moiety of AMP as well as their orientations at the gold surface. In addition, the electron-rich atoms as nitrogen and oxygen, or group moiety as -NH2 in ligands can largely promote the luminescence emission of the AuNCs. The present study revel the intriguing generation of ultrabright luminescence from metal nanoclusters, and it will stimulate more researches both on the fabrication and practical applications of luminescent AuNCs. ACKNOWLEDGEMENTS. We greatly appreciate the financial support from the projects of NSFC (Nos. 21373101, 21003061 and 91027027) and the Innovation Program of the State Key Laboratory of Supramolecular Structure and Materials, Jilin University. 369 Virtual Screening of Inhibitors against Mtb Fatty Acyl-AMP Ligase FadD32 Gazmen JD1, Billones J1 1University of the Philippines Manila, Manila, Philippines The emergence of drug-resistant tuberculosis (TB) has spurred interest in the development of new antitubercular drugs. One druggable target in M. tuberculosis (Mtb) is fatty acyl- AMP ligase (FAAL) FadD32, an essential enzyme involved in the mycolic acid biosynthesis. The absence of backup mechanisms in Mtb and the proven essentiality of FadD32 for the survival of the pathogen, make it an attractive drug target. In this study, virtual screening has been performed based on a pharmacophore generated from the homology model of FadD32. The high-scoring hits were docked to the target and rank- ordered based on calculated binding energies. The top 10 hits, with better binding affinity than the substrate, were further elaborated by De Novo Evolution technique. The hit compounds and their variants were then evaluated in silico for their ADME-Tox properties. Gratifyingly, 2 of the top hits and 2 hit variants exhibited superior binding affinity and desirable drug-like properties. 370