P-301:Tribological studies of Halogen-free quinolinium based bis(salicylato)borate ionic liquidasEco-Friendly antiwear lubricant additive
Vinay Jaiswal, Kalyaniand Rashmi B. Rastogi* E-mail: [email protected] Department of Chemistry, Indian Institute of Technology(Banaras Hindu University), Varanasi-221005, India Abstract Halogen-free quinolinium based bis(salicylato)borate ionic liquid has beensynthesized by metathesis of lithium bis(salicylato)borate anion with substituted quinoliniumhalide as cation and characterized by various spectroscopic techniques. The tribological performance of synthesized ionic liquid in base lube has been evaluated on Four-ball lubricant testing machineby varying load for 30 min duration and varying test durations at 392N load. Studied ionic liquid shows excellent friction and wear reducing behavior due to the formation of in-situthin tribofilm at the steel-steel interface.The surface morphology of the wear track has been investigated by contact mode Atomic Force Microscopy and Scanning Electron Microscopy which show drastic decrease in surface roughness in presence of studied ionic liquid. In addition to this,the interactions of individual cation, anion and ionic liquid with the surface of iron have been studied by density functional theory method which strongly favors the observed tribological results. Keywords:Halogen-free ionic liquid, Antiwear lubricant additives, Surface characterization: AFM, SEM and Theoretical calculations. Corresponding Author:Prof. RashmiBalaRastogi E-mail:[email protected] Fax No.: +91 542 2368428
P-302: Exceptional Large Stokes Shift Flourophores: Design, Synthesis and Rationalization of Photophysical Properties of Novel Heterocyclic Dyes R.Rakesh,1K.G.Sreejalekshmi*1 1Department of Chemistry, Indian Institute of Space Science and Technology, Thiruvananthapuram695547, India *E-mail: [email protected]
Molecular engineering of organic push-pull dyes demands judicious assortment of π-conjugated segments which bridge the electron donors and acceptors [1]. Heterocyclic systems with π-conjugated skeleton offer multiple advantages as fragments in designing of push-pull dyes where ease of synthesis and tunable reaction sites are preferred attributes. The widely adopted synthetic strategy in the construction of heterocyclic push-pull dyes is Pd-assisted couplings [2] whereas we envisaged a design based on thiazole ring formationemploying aroylthioureas [3] bearing variable donor units and halomethylthiophene with strong electron acceptor groups.These novel 4-aryl-2-N,N-dialkylamino-5-(2-thienyl)thiazolesaccessed through a facile synthetic procedure exhibit excellent photo physical propertiesboth in the solid form and in a range of solvents and possess exceptionally large stoke shifts (>150nm) and were sensitive to perturbations in the solvent environment. DFT/TDDFT calculations indicated significant geometric relaxations upon photoexcitation [4] and provided rationalization of the observed large stokes shift.Solvent effects were taken in to considerations using integral equation formalism polarizable continuum model (IEF-PCM).The versatility of synthesis extend the possibility of development of diverse fluorophores with fine-tuned photophysical properties for applications in luminescent devices, biological imaging and for photodynamic therapy (PDT).
Fig.1: Rationalization of the large Stokes shift: MOs of ground (left) and excited (right) optimized states
References 1. W.Yongzhen et al.,Chemical Society Reviews42, 2039-2058, 2013. 2. D. J. Schipper et al.,Chemistry of Materials, 23, 1594-1600, 2011. 3. A.Saeed et al., Journal of Sulfur Chemistry35, 318-355, 2014. 4. C.Yinghui et al.,The Journal of Organic Chemistry77, 2192-2206, 2012. P-303: Copper–Catalyzed C–H Functionalization of Pyridinesfor the Synthesis of ImidazoHeterocycles D. Ramachandra Reddy, S. Adimurthy* Academy of Scientific & Innovative Research, CSIR–Central Salt & Marine Chemicals Research Institute, G.B. Marg, Bhavnagar-364 002. Gujarat (INDIA) Fax: +91-278- 2471686, Ph. No.+919427148497,[email protected]
Over the past decade, the development of efficient strategies for the syntheses of azaheterocycles through C–H functionalization using transition-metal catalysts is of considerable interest. Direct C–N bond formations by the loss of H2, N2 or H2O to build complex nitrogen heterocycles enriched organic synthesis greatly. In particular, the synthesis of imidazo[1,2–a]pyridines received much attention due to their diverse and enhanced biological activities[1]. In this context, significant contributions have been made by various groups including our group[2]. Reported synthetic routes to imidazo[1,2–a]pyridines rely on 2– aminopyridine derivatives with various oxidative coupling partners[2]. In the present study we reportcopper(I) iodide catalyzed oxidative C(sp2)–H functionalization of pyridines for the synthesis of imidazo[1,2–a]pyridines. The same strategy has been extended for 2– phenylimidazo[2,1–a]isoquinolines from isoquinolines[3]. Good selectivity for 3-substituted pyridines and single isomer formation with isoquinoline were observed. Mechanistic studies revealed that the reaction proceeds both ionic as well as radical pathway. References 1. C.Enguehard-Gueiffier et al., Mini-Rev. Med. Chem., 7, 888,2007. 2. a) K. C.Chunavala et al.,Synthesis, 635. 2011.b) A. K.Bagdi et al., Adv. Synth. Catal.,355, 1741,2013. 3. D. Ramachandra, Reddy et al.,J. Org. Chem., DOI: 10.1021/jo5021618,2014.
P-304: Design and synthesis of 11α-functionalized bile acid derivatives as potential anticancer and anti-tuberculosis agents. Jaisingh M. Divse, Chaitanya R. Charolkar, Vijay M. Khedkar, Dhiman Sarkar, Vandana S. Pore* Organic Division, National Chemical Laboratory, Pune 411008, India *E-mail: [email protected]
Abstract :
Steroids with C-11 functionality are well-known for biological activity and are obtained in a number of naturally occurring molecules such as cortisone, hydrocortisone, and corticosterone. Here, synthesis of C- 11 azido functionalized cholic acid derivative 2 has been achieved in excellent yields from cholic acid 1 [1,2], from which a series of novel 11α-triazoyl bile acid derivatives 3 was achieved. In addition, we also have synthesized N-alkyl and N-acyl derivatives of C- 11 amino bile acid esters 4 by reduction of 11 azido compound 2 by Staudinger reaction. All the newly synthesized compounds showed selective anticancer activity against HeLa (Human Cervix epithelioid carcinoma cell line) among 4 cell lines tested. Few Compounds were found to be very active against Mycobacterium tuberculosis H37Ra (Dormant Stage). Inactivity of all the new compounds against all the tested bacterial strains indicates the specificity of these molecules. To probe the physico-chemical properties influencing the structure activity relationship for this class of molecules, classification models based on a binary QSAR approach termed recursive partitioning (RP) analysis have been generated [3,4]. The decision tree could highlight structural characteristics that discriminate the active from inactive which can serve as guide to design molecules with improved activity. In silico ADME predictions were also performed to gauge their pharmacokinetic, safety and druglikeness profile.
Fig.1: Novel C-11 functionalized bile acid derivatives.
Reference 1. V. S. Pore et al., J. Med. Chem., 49, 2652, 2006. 2. Marples et al., Tetrahedron, 54, 11907, 1998. 3. C. Strobl, J. Malley, G. Tutz Psychol Methods, 14, 323, 2009. 4. S. Y. Choi, J. H. Shin, C. K. Ryu, K. Y. Nam, K. T. No, H. Y. Park Bioorg Med Chem, 14b, 1608, 2006.
P-305: Design and Synthesis of Coumarinoyl-1,3-thiazole Conjugated PAMAM as Multifunctional Fluorescent Dendritic Nanoprobes Sarah Titus, 1 K.G. Sreejalekshmi *1 1Department of Chemistry, Indian Institute of Space Science and Technology, Thiruvananthapuram, Kerala 695547, India. *E-mail: [email protected]
The development of highly fluorescent agents has paramount significance in different fields especially in biological and medical diagnostic applications. The need for improving the sensitivity and specificity of fluorophores continue to motivate researchers in exploring new materials with desired properties. Ideal fluorescent probes should have the control over the functionalisation stoichiometry, together with less potential toxicity effects to implement them in to real world applications. Due to their globular shape, modular structure and monodispersity dendrimers became the most attractive material for developing fluorescent nanoprobes and are reported to be excellent scaffolds for biological delivery agents and diagnostic probes [1]. The high functional group density at the chain ends coupled with control over molecular structure make these synthetic moieties extremely useful as materials with tunable properties. Recently many research groups such as Kim et al [2], Gonçalves et al [3] Yordanova et al [4] have developed dendrimer conjugated with organic dyes as fluorescent sensors for different applications. Being interested in the design and development of potential bioactive heterocyclic systems and their conjugation to PAMAM dendrimer periphery for therapeutic and imaging applications in cancer treatment, we have designed and synthesized a novel biocompatible thiourea conjugated PAMAM (PAMAM-TU), which can be used as a precursor for the development of a number of heterocyclic-PAMAM conjugates. The PAMAM-TU was obtained by transferring thiocarbamoyl amidine unit to the terminal amino groups of PAMAM G0 containing ethylenediamine core using 1-(N-arylthiocarbamoyl)amidino-3,5- dimethylpyrazole as amidine transfer agent under mild conditions. In the present work we focus the synthesis of coumarinoyl-1,3-thiazole conjugated PAMAM employing PAMAM-TU for the development of fluorescent dendritic nanoprobes. The novel conjugates exhibit solvent dependent fluorescence emission and the details are presented.
Fig.1: Structure of coumarinoyl-1,3-thiazole conjugated PAMAM dendrimer and fluorescence solvatochromism Reference 1. B. Noriega-Luna et al., Journal of Nanomaterials, 2014. 2. Y. Kim et al., Biophys. J., 104, 1566, 2013. 3. M. Gonçalves et al., Biomacromolecules, 15, 492, 2014. 4. S.Yordanova et al., J. Photochem. Photobiol., A.,283,1,2014. P-306: Amphiphilic Fluorescent well-defined Living Polymer from Indole-3-carboxaldehyde and 4-Bromo-1, 8-naphthalic anhydride: Synthesis and Characterization Ambika Srivastava1, Divya Singh1, Ashok Kumar1, Rajesh Kumar*1 and Arti Srivastava2 1 Department of Chemistry, Centre of Advance Studies in Chemistry, Faculty of Science, Banaras Hindu University, Varanasi-221005, UP, India. *E-mail: [email protected]
2 Department of Chemistry, School of Physical Sciences, Guru GhasidasVishwavidyalaya, Bilaspur-495009 (CG), India
In this work, fluorescent amphiphilic polymer bearing indole repeating units with naphthalimide pendants was obtained by ATRP followed by chemical modification. The polymer showed a specific fluorescence emission maximum at 538 nm excited at 435 nm in aqueous solution. The amphiphilic nature of the polymer was investigated using two spectroscopic methods viz. absorption and emission spectroscopy. The two methods revealed critical micelle concentration of PAIHN solution to be 0.015 and 0.013 mg/ml respectively thus, the results of these two methods have evidenced fair agreement with each other. TEM studies also supported self-assembled micelles of PAIHN in water. These results demonstrate the possibility of preparing modified amphiphilic polymers with tunable fluorescence.
P-307: Green Approach for The Synthesis of ((Z)-N’-(2-oxoindoline-3- ylidene) isonicotinohydrazide Executing Hydrogen Transfer Complexion Ability WithNitro-aromatic Acceptors Devendra S, Raghuvanshia, Jyotsna S. Meshramb* aSchool of Chemical Sciences, North Maharshtra University, Jalgaon- 425 001 (MS) bHead, Department of Organic Chemistry, School of Chemical Sciences, North Maharshtra University, Jalgaon- 425 001 (MS) [email protected] Abstract: Herewith, we have modified fly ash (a industrial waste, collected from Dipnagar power plant near Bhusawal) by hydrothermal treatment to prepare zeolite type porous material. The synthesized material is well characterized by IR, XRD, FESEM, TGA analysis. The modified fly ash is found to be an efficient heterogeneous catalyst for the synthesis of some isonicotinohydrazide derivatives. The synthesized isonicotinohydrazide derivatives showing excellent binding ability with some high energy nitro-compounds to form some charge transfer complexes. The synthesized compounds were well characterized by IR, H1 NMR, C13 NMR and Mass analysis. The binding study of these charge transferredcomplexeshas been studied on UV-Vis spectrophotometer, it shows isobestic points in the spectra implicating the proper binding executed, complex geometry and binding constant. The study shows that these compounds can be utilized as chemical sensors for the high energy nitro-compounds. key words: Fly ash, CT complex, UV-Visible study, Nitro compounds, Isonicotinohydrazides
Nitro aromatics
P-308: Ruthenium catalysed alkylation of Aroylbenzofurans with acrylates via C-H activation Kolluru Srinivas,Yadagiri Kommagalla and Chepuri V. Ramana* Division Of Organic Chemistry, CSIR-National Chemical Laboratory, Pune-411008,India [email protected] Abstract: 2/3 Aroylbenzofurans are important structural motifs of natural products and pharmaceutically important compounds. Drugs like budiodarone, amiodarone, benzbromarone, dronedarone contains aroylbenzofuran moiety, which acts as antiarrhythmicagents, uricosuricagent, anti-inflammatory agents etc.[1] Despite of such importance of Aroylbenzofurans till now there are only few reports available for the functionalization at C2 position and there are no reports available for C3 position. Recently ruthenium catalyzed alkenylation with acrylates has been reported by the groups of Ackermann, Wang, Miura, Jeganmohan and Prabhu.[2]In this poster, we present some of our recent inventions that deal with the ruthenium catalysed carbonyl-directed C3-H activation and alkylation of 2-aroylbenzo[b]furans with acrylates with an option for linear or branched selectivity.[3]
References
1. S. E. Velu, C. H. Luan, L. J. DeLucas, C. G.Brouillette, W. J. Brouillette.,J. Comb. Chem,7, 898, 2005. 2. [a] K. Graczyk, W. Ma, L. Ackermann.,Org. Lett,14, 4110, 2012; [b] K. Padala, M. Jeganmohan.,Org. Lett,14, 1134, 2012; [c] V. Lanke, K. R. Prabhu.,Org. Lett,15, 2818, 2013. 3. Y. Kommagalla, K. Srinivas, C.V. Ramana, Chem. Eur. J, 20, 7884, 2014.
P-309: A new pyridoxal based fluorogenic sensor for detection of Zn(II) − and its applications for in vitro detection of Zn(II) and H2PO4 by Fluorescence imaging of cells: X-ray crystal structure, DNA binding studies and DFT calculations of the Zn(II) complex Satyajit Mondala, Bipinbihari Ghosha, Bholanath Pakhiraa, Subhra Kanti Mukhopadhyayb, Avishek Banikb, Partha Mitrac, Shyamal Kumar Chattopadhyaya* aDepartment of Chemistry, Indian Institute of Engineering Science and Technology , Shibpur, Howrah 711103, India. E mail: [email protected] bDepartment of Microbiology, The University of Burdwan, Burdwan, West Bengal, India cDepartment of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India
A tridentate Schiff base ligand, (E)-4-((2-(dimethylamino)ethylimino)methyl)-5-(hydroxymethyl)-2- methylpyridin-3-ol, which is highly selective for detection of Zn(II), by fluorescence or UV-Vis spectroscopy, has been synthesized. Mononuclear, highly fluorescent, zinc (II) complex (1) has been prepared by an easy “one pot” method, in which the Schiff base ligand is generated in situ. The complex was characterized by various spectroscopic techniques and its structure was determined by single crystal X- ray diffraction technique. DFT and TD-DFT calculations were used to understand the electronic structures of the ligand and the complex and the natures of the electronic transitions observed in their UV-Vis spectra. In the complex Zn(II) is found to be pentacoordinated, with one azide ligand, one neutral aquo ligand and a monoanionic tridentate N,N,O donor ligand. In aqueous solution, at physiological pH (0.01 M Tris-HCl buffer, pH 7.4), compound 1 exhibits an intense greenish blue fluorescence (λex 385 nm, λem 469 nm,). The − − − 2− 2− − − complex was tested with several anions, such as F , Br , AcO , CO3 , SO4 , NO3 and H2PO4 in Methanol-Water mixture (in aqueous buffer of pH 7.4). The monozinc species was found to act as a highly − selective sensor for H2PO4 , detected by UV-Vis and fluorescence spectroscopy as ON-OFF signaling. Both the fluorometric and UV-Vis titration results suggest that compound 1 is a highly selective sensor for phosphate ions. Compound 1 is also found to show significant DNA binding activity.
P-310: Micellar Interaction and Catalytic Activity of Polymers Containing Carboxylate, Oximate and Hydroxamate Functional Groups Sunita Dhritlahre*1, Manmohan L. Satnami1 1School of Studies in Chemistry, Pt. Ravishankar Shukla University, Raipur (C.G.), 492010, India *E-mail: [email protected]
Abstract:
Polymers cantiaining different functional group was synthesised. Thermodynamics of the micellization of alkyltrimethylammonium halide and alkyl pyridinium halides in the presence of these polymers have been investigated [1]. Surface properties and interaction parameters were determined by using conductivity and surface tension measurements. The micellar mediated hydrolysis of the carboxylate and phosphate esters by the polymers exhibited multifunctional catalytic activity [2]. The effect of micellization, pH of the medium and surfactant concentrations on the catalytic activities of polymers has been discussed.
Keywords: Poly hydroxamic acid, cationic surfactant, polymer, nucleophiles
References
1..Md.Jelas Haron,Wan Md .Zin WanYunus,Pergamon, 41 ,805, 1994 2. Renata S.Mello ,Faruk Nome, Langmuir, 27, 15112, 2011
P-311: A Double-Duty Nucleoside Probe for Studying RNA Structure and Function by Fluorescence and NMR Spectroscopy Sudeshna Manna and Seergazhi G. Srivatsan * Indian Institute of Science Education and Research, Dr. Homi Bhabha Road, Pashan, Pune-411008 E-mail: [email protected]
Abstract: Various biophysical tools have been developed to study structure, function and dynamics of RNA. Among the techniques fluorescence-base methods have been extensively used due to its high sensitivity and real time analysis.[1] Apart from fluorescence, NMR is another attractive tool which can provide structural information of biomolecules at the atomic level. In particular, 19F NMR is advantageous because of its (i) high natural abundance, (ii) environment sensitivity and (iii) long range of chemical shift.[2] There are very few reports where NMR and fluorescence has been used as complementary techniques to study the structure, function and dynamics of biomolecules using a single probe.[3] In this context, I will present the synthesis, photophysical characterization and NMR study of 5-(5- fluorobenzofuran-2-yl)uridine analogue, which acts as a dual sensitive probe for both fluorescence and 19F NMR spectroscopy techniques. This nucleoside shows emission in visible region with a reasonable quantum yield and it displays very good solvatochromism. Its 19F chemical shift is also sensitive to changes in solvent polarity and viscosity. The corresponding triphosphate of this nucleoside analogue has been incorporated into RNA oligonucleotides by in vitro transcription reactions using T7 RNA polymerase. Characterization of the labeled RNA by fluorescence and 19F NMR spectroscopy will be also discussed.
References: 1. Srivatsan, S. G.; Sawant, A. A. Pure Appl. Chem. 2011, 1, 213−232. 2. Chen, H.; Viel, S.; Ziarelli, F.; Peng, L. Chem. Soc. Rev. 2013, 42, 7971−7982. 3. Riedl, J.; Pohl, R.; Rulísek, L.; Hocek, M. J. Org. Chem. 2012, 77, 1026−1044.
P-312: Diphenylether based derivatives as Fe (III) chemosensors: Spectrofluorimetry, Electrochemical and Theoretical studies Rashmi Sharma, Manmohan Chhibber and Susheel K. Mittal* School of chemistry and Biochemistry, Thapar University, Patiala-147004 Email: - [email protected]
Abstract: 4-(2,4-dinitrophenoxy)-3-methoxybenzaldehyde (DPE-I) and (4-(2,4-dinitrophenoxy)-3- methoxyphenyl) methanol (DPE-II) were synthesized with high yield [1] and characterized by spectroscopic techniques. Both the receptors showed high selectivity for Fe3+ over other cations. Receptors showed 1:1 complexation with Fe3+ in correlation with theoretical studies (Fig. 1). DPE-I showed fluorescence quenching on complexation with Fe3+ ion at 350nm due to PET (photon induced transfer) mechanism between Fe3+ and the large π electron conjugate system of ligand, while DPE-II displayed emission band at 314 nm which underwent fluorescence quenching selectively on gradual addition of Fe3+ at 314nm and simultaneously a new band at 424 nm emerged with isobestic point at 355 nm which increases with increase in Fe3+ conc. Electrochemically, DPE-I due to presence of electron donating group (aldehydic) facilitates reduction of nitro group on benzene ring of the molecule so, peak potentials of the two curves obtained for DPE-I appear at -1.16 V (Epc1) and -1.39 V (Epc2) respectively, while in DPE-II (methanolic group) due to its electron donating character makes the reduction of nitro group a little difficult due to which peak potentials occur at higher potential as compared to DPE-I i.e. at -1.30 V (Epc1) and -1.43 V(Epc2)respectively.
DPE-I+Fe3+ DPE-II+Fe3+
Fig.1: The DFT optimized structures of complexes of receptors DPE-I and DPE-II with Fe3+calculated at the B3LYP/6-31G/LanL2DZ level respectively.
Reference [1] M. Chhibber, G. Kumar, P. Parasuraman, T.N.C. Ramya, N.Surolia , A. Surolia, Bioorg. Med. Chem., 14, 2006, 8086–8098.
P-313: Cu2+ and F- detection by a fluorescent chemosensor: Dansyl- antipyrine dyad
Akul Sen Gupta and Vijay Luxami* School of chemistry and Biochemistry, Thapar University, Patiala-147004 Email: - [email protected]
Abstract: These days fluorescent chemosensors for the detection of copper and fluoride ions have received wide attention due to their harmful effect on biological and environmental processes, also these in excess are responsible for gastrointestinal disease, hypoglycemia and environment pollution etc. Thus, we synthesised Dansyl-antipyrene dyad (Fig.1) and its absorbance and emission properties was studied towards different cations and anions. It was observed that dyad binds selectively with Cu2+ ions among all other cations and selectively with F- ions amongst all other biological relevant anions. Two new absorption channels open at 470 nm and 310 nm in the presence of Cu2+ and F- ions respectively. The fluorescence intensity of dyad at 528 nm quenched in the presence of Cu2+ ions whereas F- ions shows ratiometric response and opens new emission channel at 420 nm. The emission changes induced in the presence of Cu2+ and F- ions leads to the miniaturization of sequential XNOR logic operation.
CH3 N N O
CH3 HN
O S O
N H3C CH3
Fig.1: Dansyl-antipyrine dyad
P-314: Theoretical Studies on the Reducing Properties of Closo- Monothiaboranes Elambalassery G. Jayasree *, Chinthu Sukumar Department of Chemistry, School of Physical and Mathemetical Sciences, University of Kerala, Trivandrum, INDIA.
Keywords- disulfide bonds, reduction, drug delivery
Ph: 9746790202, Mail id: [email protected]
Abstract The reversible thiol-disulfide exchange reaction is a very important biochemical reaction affecting the protein folding. Incorporation of this dynamic reversible disulfide bonds offers great potential for synthesizing the macromolecular cages[1]. In the current study, redox couple were explored for various isomers of closo-monothiaboranes. Structure, stability and reducing properties of sulphur substituted single cage closo- boranes and fused cage systems were investigated using various theoretical tools. On the basis of geometry optimization and Natural Atomic Orbital Analysis, the structure and stability of closo-monothiaboranes have been analyzed. In order to calculate the reducing properties of these monothia systems, one electron added radicals have been computed correspondingly which showed that B-S and B-B bonds are weakened making the system more relaxed indicating the viability of the cage towards rupturing upon reduction. Addition of one more electron makes the structure break down completely. This property can be exploited in constructing potential systems for drug delivery. Detailed qualitative and quantitative studies of the monothiaboranes as well as fused polyhedral structures will be presented.
Reference 1. J. D. Hartgerink, Curr. Opin. Chem. Biol. 2004, 8, 604–609.
P-315: Studies in the PAHs Sensing by Calix[4]arene Derivative Capped CdSe Quantum Dots: Effect of Calix[4]arene Conformation Rabindra Kumar, A. K. Jain and J. N. Babu* Centre for Environmental Science & Technology, Central University of Punjab, Bathinda 151001, India E-mail: [email protected]
Calixarenes are a versatile class of container molecules with various conformation the molecule can adopt. The Calix[4]arene nitrile derivatives [1 & 2] in cone (1) and 1,3-alternate (2) conformation are capped to the CdSe Quantum Dot [3]. CdSe QDs, Calix[4]arene and its complex were synthesized and confirmed with 1H NMR, 13C NMR, FTIR, EDX, FESEM, UV-Spectrophotometer, and PL Spectra. The Calix(1-2)@CdSe were studied for solution based fluorogenic sensing of PAHs namely acenaphthene, anthracene, fluorine, naphthalene and pyrene. The studies show a selective recognition of anthracene by 1@CdSe whereas 2@CdSe showed a selectivity for anthracene and fluorene. The inclusion based recognition of the PAH has been investigated and established by 1H NMR. The results of the findings would be discussed in detail.
Key words: Calix[4]arene, cone conformation, 1,3-alternate, CdSe QDs, PAHs.
Reference 1. E. M. Collin et al. 1997 J. Chem Soc. Perkin Trans, 1, 3137, 1991 2. M. Kumar et al., Dalton Transactions, 39, 10116, 2010. 3. W. W. Yu and X. Peng, Angew Chem Int Edit., 41, 2368, 2002.
P-316: Experimental and Theoretical Investigations of The Charge Transfer Complexes of Imidazo[1,2-a]pyridines with DMAD Pooja Maheshwari1, Raakhi Gupta1, R. K. Bansal1*, Susanta Das2 and Sourav Pal2 1Department of Chemistry, The IIS University, Mansarovar, Jaipur 302 020, India 2Department of Chemistry, National Chemical Laboratory, Pune 411 008, India *E-mail: [email protected]
Keywords: Charge transfer complexes, Imidazo[1,2-a]pyridines, DMAD, TDDFT, CT transition energy
Abstract: Charge transfer (CT) complexes are currently of great importance because of their diverse applications such as in drug activity, non-linear optical activity, surface chemistry and micro-emulsion. They are also used as semiconductors, dendrimers and photocatalysts [1]. In certain organic molecules, it is possible to alter the availability of electrons by introducing an appropriate substituent group, making it an electron donor or an electron acceptor. Such molecules on coming in contact with an appropriate donor or acceptor molecule induce molecular interactions resulting in the formation of CT complexes evinced by the appearance of an intense colour [2]. In the present study, we investigated CT complexation of differently substituted imidazo[1,2-a]pyridines (1, R= H, Ph, p-OMeC6H4, p-NO2C6H4, p-FC6H4) with DMAD. On mixing the two reactants in dichloromethane at room temperature (~25ºC), CT complex is formed with the appearance of a pink colour confirmed by an absorbance band in the visible region (λmax=480~510 nm). The experimental value of the CT transition energy for unsubstituted imidazo[1,2-a]pyridine was found to be 2.43 eV.
N N N
R R R N N N CH2Cl2 rt
MeO2C CC CO2Me MeO2C CC CO2Me MeO2C CC CO2Me
R= H, Ph, p-OMeC6H4, p-NO2C6H4, p-FC6H4 Scheme 1
A model CT complex of unsubstituted imidazo[1,2-a]pyridine with DMAD was investigated theoretically in the gas phase using TDDFT method [3]. Frontier molecular orbital calculations reveal electron transport phenomena from imidazo[1,2-a]pyridine (Donor) to DMAD (Acceptor) in the CT complex, the interacting site being bridge-head N-atom of imidazo[1,2-a]pyridine and -C≡C- bond centre of DMAD moiety. However, the calculated values of the λmax, 401 nm and the CT transition energy, 3.09 eV showed much variance from the experimental ones.
References [1] S. Bhattacharya, M. Banerjee and A. K. Mukherjee, Spectrochimica Acta Part A, 57, 2409-2416, 2001. [2] B. Prabitha, S. Periandy and K. Govindan, Asian J. Chem., 11(4), 1205-1210, 1999. [3] T. Stein, L. Kronik and R. Baer, J. Am. Chem. Soc., 131, 2818-2820, 2009.
P-317: Chromogenic Signaling of Water Content in Acetonitrile by a Deprotonated Schiff base K. Tiwari, M. Mishra, S. R. Gupta, R. Dwivedi and Vinod P. Singh* Department of Chemistry, Banaras Hindu University, Varanasi-221005, India Keywords: Chromogenic signaling, UV-Visible, LOD, X-ray crystallography Corresponding author. Tel.: +91 9455227374. E-mail address: [email protected] (K. Tiwari)
The solvatochromism is an important property of a solute because most chemical reactions and all biochemical reactions in the human body occur in solution.1 As water is the most common impurity in organic solvents, determination and control of water content in organic solvents or chemical products are highly important in laboratory chemistry and industrial processes.2,3 Herein, a simple, cost effective (E)-4-[{2-(2,4-dinitrophenyl)hydrazono}methyl]benzene-1,3-diol (DBH) is synthesized and characterized by elemental analysis and spectroscopic tools along with single crystal X-ray crystallography. The solvatochromism of DBH in solution and naked eye detectable chromogenic signaling behavior of the deprotonated DBH for the determination of water content in acetonitrile through UV-Visible absorption spectra is investigated. The signaling is based on effect of water content on deprotonation of DBH. Prominent color changes are observed up to 2% water content and limit of detection (LOD) of the deprotonated DBH for determination of water content in acetonitrile is calculated as 0.012%.
References
1. C. Reichardt,, Pure & Appl. Chem., 76, 1903, 2004. 2. R. A. Timm, M. P. H. Falla, M. F. G. Huila, H. E. M. Peres, F. J. Ramirez-Fernandez, K. Araki and H.E. Toma, Sensors & Actuators B, 146, 61-68, 2010. 3. W. K. O’Keefe, F. T. T. Ng, and G. L. Rempel, J. Chromatography. A, 1182, 113, 2008.
P-318: Preparation of superhydrophobic polypropylene membrane for oil-water and organic-water separations Ankit M. Kansara, 1Sanjay G. Chaudhri, 1 P. S. Singh*1 1RO Division, Central Salt and Marine Chemical Research Institute, Bhavnagar 364021, India *E-mail: [email protected]
Abstract: Oil–water separation is a global challenge because of tougher regulations concerning oily industrial wastewater discharges, the need for water recycling and reuse, as well as frequent crude oil leakages. For that it is necessary to develop hydrophobic membranes to solve the problems. A simple and inexpensive one-step immersion method is reported here to prepare superhydrophobic polypropylene membrane. The membrane surface with high roughness ranging from micro- to nano-scale having water contact angles greater than 150° was created by functionalization of polypropylene fabric with poly(alkoxysiloxane). The membranes were tested for separation some selected oil-water and organic-water mixtures under gravity-induced separation system. The results indicated excellent separation efficiency of the prepared membranes.
Water CA= 153°
Silica- poly(alkoxysilane) functionalized PP fabric
Fig.1: Graphical representation of oil-water separation system
Reference 1. Xiaoyu Li et al., J. Mater. Chem. A, 2014, 2, 11830–11838. 2. Yao Lu et al., J. Mater. Chem. A, 2014, 2, 11628–11634. 3. Aikifa Raza et al., J. Mater. Chem. A, 2014, 2, 10137–10145
P-319: Novel CdO/BiOBr Heterostructures: Synthesis, Characterization, Photoinduced Charge-Transfer Property and Enhanced Visible-Light Photocatalytic Activity Bilal Masood Pirzada and Suhail Sabir* Department of Chemistry, Aligarh Muslim University, Aligarh, India-202002 Email: [email protected] Novel CdO/BiOBr heterostructures were synthesized by a facile chemical bath method under ambient conditions [1]. A series of CdO/BiOBr heterostructures were obtained by tuning the Bi/Cd molar ratios. The resulting heterostructures were characterized by the XRD, SEM, TEM, TGA/DTA and FTIR. Optical properties of the heterostructures were studied by Photoluminiscence, PL and UV-Visible spectroscopy. The CdO/BiOBr nanocomposites exhibited high photocatalytic activity in the degradation of Rhodamine B under visible-light irradiation. The enhanced photocatalytic activity under visible light can be attributed to the high surface area and the formation of the heterojunction which inhibits the charge recombination [2]. Surface Photovoltage Spectroscopy and Transient Photovoltage Spectroscopy depict that the photoinduced charge transfer property of p-type BiOBr can be well enhanced by coupling with n- type CdO [1]. This study hence reveals that the heterojunction constructed between the interfaces of CdO and BiOBr play an important role in determining the dynamics of charge carriers and their photocatalytic activity.
Figure 1: Overlay showing decrease in absorption intensity of Rhodamine B at its λmax 554 nm at different irradiation time intervals in the presence of 1:1CdO/BiOBr composite under constant stirring and bubbling of atmospheric oxygen. Keywords: Bismuth oxy bromide, Heterostructures, Photo-induced charge transfer, Photocatalytic activity Reference 1. Jing Jiang et al., J. Phys. Chem. C 2011, 115, 20555–20564. 2. Wenquan Cui et al., Appl. Surf. Sci. 2014, 319, 298–305.
Correspondence: Dr. Suhail Sabir, Department Of Chemistry, Aligarh Muslim University, Aligarh, India, 202002. Email: [email protected] Phone: +91-571-2700920-ext-3366
P-320: Self-Assembly in Comb Polymers for Improved Charge Carrier Mobility Dr. Asha S. K Polymer Science & Engineering Division, National Chemical Laboratory (NCL), Dr. Homi Bhabha Road, Pune 411008, Maharashtra, INDIA E-mail: [email protected]
Donor-Acceptor combination in organic semiconducting materials is a versatile design strategy for improved device efficiency in organic photovoltaic applications. The self assembly approach to bring together D-A units in the domain range (5-10 nm) required for the efficient charge separation has been much explored for small pi conjugated organic molecules. While this approach has resulted in beautiful hierarchical architectures, unfortunately photovoltaic performance of devices based on self assembled donor-acceptor small molecules has not always been very encouraging. On the other hand, their polymeric counterparts seems to hold better promise with the multiple self- assembly sites along the polymer backbone ensuring good nanoscale D-A interaction along with better processability. In this context, we attempted self assembly of pi conjugated organic molecules with pre formed high molecular weight polymers like poly(4-vinyl pyridine) (P4VP) whereby the crystallinity of the small molecule could be retained at the same time processability as well as improved charge carrier mobility was also achieved.1,2 Furthermore, we extended this approach to self assembled donor- acceptor pi conjugated small molecules, which were further polymerized so as to translate the self-assembly of small molecules to processable polymers. The 1:1 D-A complex as well as the supramolecular polymer complex showed uniform lamellar structures in the domain range < 10 nm. The complex also exhibited space charge limited current (SCLC) with a bulk mobility estimate which was an order of magnitude higher accompanied by a higher photoconductivity yield compared to the pristine acceptor molecule.3
References: 1. Rekha Narayan et al., J. Mater. Chem. C, 2, 6511, 2014. 2. Rekha Narayan et al., Adv. Funct. Mater. 23, 2033, 2013. 3. B. Saibal et al., ACS Applied Mater. Interfaces. 2014, ASAP, DOI: 10.1021/am5055542 P-321: Steam and Dry reforming of methane on Ni intercalated Ruddlesden-Popper strontium titanate
Srikanth Dama, Richa Bobde, Satyanarayana Chilukuri*. Catalysis Division, CSIR-National Chemical Laboratory, Pune-411008, India *Corresponding author; Phone No. 020-25902019, [email protected].
Srn+1Tin-x NixO3n+1 (n = 1) phase and the higher-order of Ruddlesden-Popper phases [1] Srn+1Tin-x NixO3n+1 (n = 2, 3 and∞) has been synthesized by citrate gel method. The present studies are aimed at incorporation of Ni in the B site of Srn+1TinO3n+1 lattice. These perovskites were characterized by using various physico-chemical techniques to find the structure-activity relationships. From XRD and Raman spectra studies, it was found that Ni is successfully substituted in the B site and as n is increased a structural phase transition is observed from tetragonal I4/mmm in the Srn+1Tin-x NixO3n+1 (n = 1,2 and 3) to cubic Pm3m in the SrTi1-xNixO3 phase. The catalytic activity of Ni intercalated Ruddlesden-Popper strontium titanate was checked for steam and dry reforming of CH4.
Keywords: Srn+1Tin-x NixO3n+1,CH4.
Fig.1: XRD of Srn+1TinO3n+1 Perovskites. Fig.2: Dry reforming of Srn+1Tin-xNixO3n+1 Perovskites.
Reference 1. S. N. Ruddlesden,. P. Popper, Acta Crystallogr. 10, 538, 1957.
P-322: Self-templated Chemically Stable Hollow Spherical Covalent Organic Framework Sharath Kandambeth, Digambar Balaji Shinde and Dr. Rahul Banerjee. 1Physical Chemistry Division, National Chemical Laboratory, Pune 411008, India *E-mail: E [email protected]
AA hollow spherical covalent organic framework (COF) with mesoporous walls has been synthesized by the single step template free method. A detailed time dependent study of hollow sphere formation reveals that an inside-out Ostwald ripening process is responsible for the hollow sphere formation. The synthesized COF hollow spheres are highly porous (surface area ~1500 m2g-1), crystalline and chemically stable, due to the presence of strong intramolecular H-bonding. The presence of intramolecular hydrogen bond brings structural rigidity and planarity to the 2D COF, and also protects imine bonds from nucleophilic attack. The synthesized hollow spheres COFs were fully characterized through PXRD, FT-IR, 13C solid-state NMR, TEM, SEM and AFM. These mesoporous hollow sphere COFs were used for the trypsin immobilization studies, which shows an uptake of 15.5 µmol/g of trypsin by the COF-DhaTab hollow sphere.
Fig.1: Synthesis of COF DhaTph hollow spheres for enzyme adsorption.
Reference 1. Kandambeth, S.; Mallick, A.; Lukose, B.; Mane, V. M.; Heine, T.; Banerjee, R. J. Am. Chem. Soc. 2012, 134, 19524. 2. Kandambeth, S.; Shinde, D. B.; Panda, M. K.; Lukose, B.; Heine, T.; Banerjee, R. Angew. Chem. Int. Ed., 2013, 52, 13052.
P-323: Synthesis, Characterization of Metal (II) complexes Bearing Tridentate NNO Functionalized Ligand: Density Functional Theory, DNA Interaction and Cytotoxicity Sellamuthu Kathiresana, J. Ranjanib, J. Rajendharanb, Jamespandi Annaraja* aDepartment of Materials Science, School of Chemistry, Madurai Kamaraj University, Madurai-625 021, India. bDepartment of Genetics, School of biological science, Madurai Kamaraj University, Madurai-625 021, India. Email: [email protected]
Abstract: A series of Cu(II), Ni(II) and Zn(II) complexes have been synthesized using a tridentate (N, N, O donor) Schiff base ligand system. These complexes were characterized by various physicochemical techniques, namely FT-IR, UV-Vis, ESI-MS, 1H NMR, EPR and CV. The density functional theory calculations are used to investigate the electronic structures and the electronic properties of ligand and complexes. Their interaction with herring sperm DNA was examined with the help of absorption, circular dichroism (CD) and fluorescence spectroscopic techniques [2] at pH 7.1. The observed hyperchromism along with binding constant (Kb) were fallen in the order of Cu > Ni > Zn. The addition of increasing concentration of complexes with DNA, both positive and negative bands at 275 and 245 nm respectively undergo decrease in elipticity [1]. All spectroscopy results indicate that complexes show good binding affinity to HS- DNA possibly through intercalation or partial intercalation. In vitro cytotoxic effect of the complexes was carried out in human lung cancer cell line (A549) and cell imaging studies were also performed.
Key words: NNO donor ligand; DFT; DNA interaction; binding constant; Anticancer activity
(a) (b)
Fig.1: (a) Circular dichroism spectra of HS-DNA in the absence and presence of complexes in Tris-HCl (pH 7.1) at room temperature. [complex]= 30 µM, [DNA] = 100 µM. (b) Emission spectra of EB bound to DNA in the presence of Nickel complex. Arrows indicate the intensity changes upon increasing concentration of the complexes.
Reference 1. Pankaj Kumar et al., Dalton Trans., 2012, 41, 7573–7581 | 7575. 2. Yan-Cheng Liu et al., Dalton Trans., 2009, 10813–10823.
P-324: Mechanosynthesis of Covalent Organic Frameworks (COFs) B. P. Biswal, 1 S. Chandra, 1 S. Kandambeth,1 R. Banerjee *1 1Physical/Materials Chemistry Division, National Chemical Laboratory, Pune 411008, India *E-mail: [email protected], [email protected]
Construction of bonds through the simple, economical, and environmentally friendly mechanochemical (MC) route is of considerable interest in modern synthetic chemistry. Recently mechanochemistry has been efficiently employed to carry out various organic and inorganic transformations, nanostructure formation, construction of metal−organic frameworks (MOFs) and thus has become a good alternative to classical solution-based synthesis. A class of thermally and chemically stable isoreticular covalent organic frameworks (COFs) were synthesized for the first time via room-temperature solvent-free mechanochemical grinding. All these COFs were successfully compared with their solvothermally synthesized counterparts in all aspects. These solvent-free mechanochemically synthesized COFs have moderate crystallinity with remarkable stability in boiling water, acid (9 N HCl), and base (3 N NaOH). Exfoliation of COF layers was simultaneously observed with COF formation during mechanochemical synthesis. The microscopic structures thus obtained seemed to have a graphene-like layered morphology (exfoliated layers), unlike the parent COFs synthesized solvothermally.
Fig.1: Mechanochemical synthesis of isoreticular covalent organic frameworks.
Reference 1. Friš . ić, T. Chem. Soc. Rev. 2012, 41, 3493. 2. Kandambeth, S.; Mallick, A.; Lukose, B.; Mane, V. M.; Heine, T.; Banerjee, R. J. Am. Chem. Soc. 2012, 134, 19524. 3. Biswal, B. P.; Chandra, S.; Kandambeth, S.; Lukose, B.; Heine, T.; Banerjee, R. J. Am. Chem. Soc. 2013, 135, 5328.
P-325: C-H Bond Activation by FeV=O Complex at Room Temperature
Munmun Ghosh, Kundan Kr. Singh Sagar, Chakadola Panda, Andrew Weitz, Michael P Hendrich, Terrence J Collins, Basab B. Dhar, Sayam Sen Gupta
CEPD Division, National Chemical Laboratory, Pune 411008, Maharashtra, India e-mail: [email protected]
High valent iron-oxo intermediates have been proposed to play a very important role in many biological reactions and catalytic cycles. In the heme enzyme CytP50, the high valent FeIV(oxo) cation radical that is isoelectronic with FeV=O, has been characterized as the reactive intermediate for the hydroxylation of camphor. Similarly FeV=O as the active intermediate has also been postulated for non heme Rieske dioxygenase family of enzyme. Therefore chemists have synthesized several functional models of both heme and non-heme iron-complexes with the goal that they may function as catalysts to perform selective oxidation reactions such as C-H hydroxylation in an environmentally benign manner. The FeIV=O intermediates of non-heme complexes have been isolated, structurally characterized and their reactivity towards hydroxylation of C- H bonds have been studied in detail. There are very few reports of FeV=O which includes TAML (stable at -40 oC). But the activity towards unactivated C-H bond at room temperature still remained a challenge. Recently FeV=O species of [FeIII(biuret-TAML)], made by equimolar amount of meta-chloroperbenzoic acid (m-CPBA) in acetonitrile at 25 °C has been reported from our group1. The green coloured solution formed was characterized by UV-vis, EPR, HR-MS and Mossbauer. At 25 oC the rate constant for the V IV -5 -1 decay (k5/4, decay from Fe =O to Fe =O) was determined (4.45 × 10 s ). This stability value encouraged us to study C-H bond activation by this FeV=O complex. A series of alkanes having C-H BDE ranging from 99.3 kcal mol-1 (cyclohexane) to 84.5 kcal mol-1 (cumene) had been studied by both UV-Vis spectroscopy. Significant kinetic isotope o effect (KIE) of 9 for toluene/d8-toluene at 25 C and linear Bell-Evans-Polayni graph support the r.d.s involved abstraction of the H atom from the C-H bond by the FeV=O1. Realizing this extraordinary potential of activating sp3 C-H bonds we have studied selective hydroxylation with complex molecules containing multiple 3o centers. We find that our complex can catalyze selective hydroxylation of TON aliphatic 3o C-H bonds with TON of ~50-100.
Reference:
1. Ghosh et al. J. Am. Chem. Soc., 2014, 136 (27), pp 9524–9527
P-326: Synthesis and Characterization of Lanthanide(III) Complexes with a Mesogenic Schiff-base having [1, 2, 3]‐Triazole Moiety
M Karunakar , Rajasekhar Yerrasani and T. R. Rao*
Department of Chemistry, Banaras Hindu University, Varanasi-221005, India
Email:[email protected] & [email protected] Abstract:
Heterocyclic liquid crystalline Schiff’s base with [1,2,3]-triazole ring at the terminal position was synthesized through Cu(I)-catalyzed 1,3-dipolar cycloaddition of 1-azido-4- nitro benzene with terminal octyne; a series of lanthanide(III) complexes of the type [Ln(LH)3 (NO3)3] (Ln = La, Pr, Nd, Sm, Eu, Tb and Dy; LH = N-(4-(4''-hexyl-1H-1,2,3- triazol)-4-(4'-dodecyloxy) salicylaldimine have also been synthesized and characterized by FT-IR, 1H & 13C NMR, UV/Vis, and Mass spectral techniques. The ligand exists as zwitterion in the complexes, binding to the metal in a mono dentate fashion through the phenolate oxygen and the nitrato groups chelating to the metal to complete nine coordination around the lanthanide ion. Their mesophases were characterized by a combination of differential scanning calorimetry and polarising optical microscopy. The ligand exhibited a meso phase over a wide temperature range
References: 1. S. Sharma, D. Lacey, P. Wilson, Liq. Cryst. 30 (2003) pp.451-461. 2. Y.D. Zhang, K.G. Jespersen, M. Kempe, J.A. Kornfield, S. Barlow, B. Kippelen, S.R. Marder, Langmuir 19 (2003) pp.6534-6536. 3. R. Mcdonald, D. Lacey, P. Watson, S. Cowling, P. Wilson, Liq. Cryst. 32 (2005) pp.319-330. 4. A. Mori, A. Sekiguchi, K. Masui, T. Shimada, M. Horie, K. Osakada, M. Kawamoto, T. Ikeda, J. Am. Chem. Soc. 125 (2003) pp.1700-1701. 5. V.F. Petrov, V.I. Yashkichev, Mol. Cryst. Liq. Cryst. 518 (2010) pp.12-39. 6. R. Cristiano, D.M. Pereira De Oliveira Santos, G. Conte, H. Gallardo, Liq. Cryst.33 (2006) pp.997-1003. 7. G. Conte, F. Ely, H. Gallardo, Liq. Cryst. 32 (2005) pp.1213-1312. 8. D. Srividhya, S. Manjunathan, S. Thirumaran, E-J. Chem. 6 (2009) pp.958-960. 9. D. Srividhya, S. Manjunathan, S. Thirumaran, C. Saravanan, S. Senthil, J. Mol.Struct. 927 (2009) pp.7-13.
P-327: Efficient titanium dioxide for oxidation of aliphatic, allylic and benzylic alcohols by molecular oxygen under visible light irradiation Raji Vadakkekara, Subhash Chandra Ghosh, Asit Baran Panda* Discipline of Inorganic Materials and Catalysis, Central Salt and Marine Chemicals Research Institute (CSIR), G.B. Marg, Bhavnagar-364002, Gujarat, India. *E-mail adress: [email protected]; [email protected]
Titanium dioxides (TiO2) is widely used in photochemical applications such as H2 production by water splitting, the degradation of volatile organic compounds (VOCs), organic synthesis, and dye-sensitized solar cells so on. TiO2 prepared using aqueous solution of titanium peroxo carbonate (TPC) complex, also modified with zirconium carbonate, polyethylene glycol, and orthophosphoric acid (H3PO4). The photocatalytic oxidation of alcohols into aldehydes proceeded with excellent conversion and selectivity on TiO2 by O2 under visible light irradiation (40 W CFL) at room temperature. TiO2 prepared at 150 C̊ using TPC followed by vacuum dried at 70 C̊ showed 100% conversion towards benzaldehyde, also all catalysts showed 100% selectivity. Allylic, benzylic and aliphatic alcohols also showed very good conversion and selectivity toward aldehydes. The oxidation of benzyl alcohol was subjected to detailed investigations to study the effect of parameters such as time, temperature, amount of catalysts and solvent, different substrate, solvents and facets of TiO2.
Reference
1. L. Liu et al., J. Phys. Chem. C, 117, 18578, 2013.
2. N. Sutradhar et al., Chem. Commun., 47, 7731, 2011.
P-328: Palladium (II) Catalyzed Efficient C-3 Functionalization of Indoles with Various Electrophiles Swapna Sarita Mohapatraa, Debjit Dasb and Sujit Roya* aOrganometallics & Catalysis Laboratory, School of Basic Sciences, Indian Institute of Technology, Bhubaneswar – 751013, India bCentre for Applied Chemistry, Central University of Jharkhand, Brambe, Ranchi- 835205, Jharkhand, India *E-mail: [email protected]
Functionalization of indoles via selective, bench- and eco-friendly strategies has captured wide attention since structural motifs bearing the ‘indole core’ are frequently found in pharmaceuticals, natural products, and other functional synthetics [1].In this context, recent work from our group has established that palladium(II) complex namely, PdCl2(MeCN)2,efficiently catalyzes the regioselective alkylation of indoles with various electrophiles like allyl alcohols, benzyl alcohols, carbonyls and enones under conditions insensitive to moisture and air [2]. Notably, the reaction does not require any other co-catalyst, acid, base, additive, or external ligand. The easy handling of the catalyst makes the reaction more attractive, simple and practical. In this presentation, highlights of recent developments in our work will be emphasized.
Reference 1. Bandini, M.; Eichholzer, A. Angew. Chem. Int. Ed., 48, 9608, 2009. 2. Das, D.; Roy, S. Advanced Synthesis & Catalysis, 355, 1308, 2013.
P-329: Sulphur promoted C(sp3)-C(sp2) cross dehydrogenative cyclisation of acetophenone hydrazones with aldehydes: an efficient synthesis of 3, 4, 5-trisubstituted 1H-pyrazoles Rajeshwer Vanjari, Tirumaleswararao Guntreddi and Krishna Nand Singh* Department of Chemistry (Centre of Advanced Study), Faculty of Science, Banaras Hindu University, Varanasi-221005, India. *E-mail: [email protected], [email protected].
A novel strategy for the cross dehydrogenative coupling (CDC) of acetophenone hydrazones and aldehydes has been developed for the synthesis of highly substituted pyrazoles. The report makes first-time use of elemental sulfur as a promoter as well as a hydrogen acceptor in effecting Csp3-Csp2 bond formation via C-H activation.
Fig.1: Sulphur promoted C-H activation.
Reference 1. R. Vanjari, T. Guntreddi, S. Kumar and K. N. Singh, Chem. Commun., 2014, DOI: 10.1039/C4CC08210A
P-330: Synthesis, Characterization, DNA Binding/Cleavage properties of Cobalt(III) Complexes and their Antimicrobial activities
D. Ezhilarasan1 M. Murali Krishnan2 and M.N. Arumugham2* 1E.S Matriculation Higher Secondary School, Villupuram – 605 602, Tamilnadu, India. 2Department of Chemistry, Thiruvalluvar University, Serkadu, Vellore – 632 115. INDIA
Abstract: A ternary water soluble Cobalt(III) complexes [Co(trien)(X)]Cl3 (trien = triethylenetetramine, X= Semicarbazide 1, Thiosemicarbazide 2) has been synthesized and characterized by elemental analysis, Infra-red spectra, molar conductance and NMR methods. The interaction of complex with Calf Thymus DNA was investigated by Absorption spectroscopy, Emission spectroscopy, Viscosity measurement and Cyclic Voltammetry measurements. The complexes were shown excellent bind with DNA. The complexes were screened for their in vitro antibacterial activity
Keywords: Triethylenetetramine, DNA binding, Antimicrobial Activity e-mail:[email protected] Cell: 9443291583
P-331: Estimation of iron (ferroin) using different Ion exchangers through a Nonlinear Chemical Reaction
Sna Rashid1, Nadeem Bashir1,2, Shagufta Rashid1, Shafia Lateef1, Nisar Ahmad Farhad1, G. M. Peerzada1* 1Department of chemistry, University of Kashmir, Srinagar-190006, J&K India 2Department of Chemistry, Govt. College for Women Nawakadal Srinagar 190002 J&K Email: [email protected], *[email protected], [email protected]
Ion exchange resins comprise one of the most important scientific developments of the 20th century. Their applicability to water softening, environmental remediation, wastewater treatment, hydrometallurgy, chromatography, catalysis etc was recognized in numerous publications. The present investigation pertains to the interaction of different ion exchangers with a nonlinear chemical reaction (Belousov Zhabotinsky reaction) and this reaction has been used for the first time for the estimation of iron (ferroin) using different ion exchangers like Amberlite irc86, Dowex marathon C Na and Dowex m4195 through Phloroglucinol-bromate-ferroin based system. It is found that estimations of ferroin scales upto 0.005 mol L-1 from a very minimal concentration on varying weights of Amberlite irc-86 from 0.02 g to 0.30 g, Dowex marathon C Na from 0.1 g to 1.3 g and Dowex m-4195 from 0.002 g to 0.055 g. The results from potentiometry have been supported by UV visible Spectrophotometry. Besides, some interactions between different reagents have been explored using cyclic voltammetry.
Keywords: Nonlinear chemical reaction, Belousov-Zhabotinsky reaction, ion exchange resin, capacity, selectivity, chelation, voltammogram, Amberlite IRC86, Dowex m4195, Dowex marathon C Na.
-1 1000 1000 0.0002 mol L ferroin 0.02 g amberlite and loaded ferroin 0.10 g amberlite and loaded ferroin 900 900 0.22 g amberlite and loaded ferroin
800 A 800 B
1 700 700
600 600 0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
1000 1000
900 900 Absorbance
800 C 800 D Redox PotentialRedox (mV)
700 700 0 600 600 0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200 400 500 600 Time (s) Wavelength(nm) Fig. 1 Fig. 2
0.00020 Loading time 45 minutes
0.00018 R2=0.999
0.00016
0.00014
0.00012
Absorbance 0.00010
0.00008
0.00006 0.00 0.05 0.10 0.15 0.20 0.25 Weight of Amberlite (g) Fig. 3
Fig 1: Variation of oscillatory parameters with change in the amount of Amberlite loaded with ferroin for 45 minutes while keeping concentration of other reagents constant at [Phloroglucinol] 1 1 1 = 0.013 mol L⁻ , [BrO3⁻] = 0.13 mol L⁻ and [sulfuric acid] = 1.5 mol L⁻ . Fig 2: Effect of varying amounts of Amberlite irc86 loaded with 0.005 molL-1on the absorption spectrum of ferroin. Fig 3: Variation in absorbance of ferroin loaded with different amounts of Amberlite IRC86. References: [1] Maselko, J.; Showalter, K. Physica D 1991, 49, 21. [2] Yoshikawa, K.; Aihara, R.; Agladze, K.J.phys.chem.A 1998,102, 7649-7652 [3] Maselko, J.; Reckley, J. S.; Showalter, K. J. Phys. Chem. 1989,93, 2774. [4] Huh, D. S.; Choe, S. J.; Kim, M. S. React. Kinet. Catal.Lett. 2001 [5] Field, R. J.; Körös, E.; Noyes, R. L. J. Am. Chem. Soc.1972, 94, 8649. [6] Maselko, J.;Reckley,J.S.;Showalter,K. J. Phys. Chem. 1989, 93, 2114-2180. [7] Usma Gull, Nadeem Bashir, G. M. Peerzada, N. A. Dar. 2013 Bull. Chem. Soc. Japan, 86(2), 266-272.
P-332: Synthesis of isoxazole tethered diarylheptanoids towards drug like Curcumin analogs. aSandeep Bhosale and Debnath Bhuniya* aDepartment of Organic Chemistry & FDW, Andhra University, Visakhapatnam, 530003 Department of Chemistry, Drug Discovery Facility, Advinus Therapeutics Limited, Quantum Towers, Plot No. 9, Rajiv Gandhi Infotech Park, Phase-I, Hinjewadi, Pune 411057, India
Abstract: Diarylheptanoids are plant metabolites that have been isolated from various genera, including
Zingiberaceae (Ginger family).1 In general, diarylheptanoids (for example, Curcumin, Compounds A and B) have medicinal values due to their antioxidant, hepatoprotective, antiproliferative and anti-inflammatory activities.2
B Curcumin B IC50: 1-3 mg/mL (cancer cell lines) IC50: 13 µg/mL (Leukemia cell line)
We present here an efficient and enantiospecific synthesis of a new class of isoxazole tethered of 1,3-syn and 1,3-anti diarylheptanoids 4-7 and 10-12 starting from D-glucose. For synthesis of these compounds, we have successfully applied a general synthetic strategy developed for synthesis of diarylheptanoids3a combining with the invention of MagtrieveTM methodology for synthesis of isoxazole and isoxazoline heterocycles.3b We hope that these diarylheptanoid analogs, along with their synthetic strategy, will serve as a valuable starting point to pursue medicinal chemistry of these new hybrid class of compounds.3c
3 steps 2 steps
For R = H (93%, 4 steps 2 76%, 78%. 3 62% 4 R = H, R1 = F (85%, 83%); 5 R = H, R1 = OMe (87%, 82%); 6 R = OMe, R1 = OMe (91%, 85%); 7 R = OMe, R1 = Cl (89%, 86%).
1 5 steps α−D-glucofuranose 70% 3 steps (83%, 79%, 83%. 2 steps
8 9 10 R2 = H, R3 = F (92%, 82%); 11 R2 = H, R3 = OMe (85%, 83%); 12 R2 = OMe, R3 = H (93%, 82%).
Reference: (a) Lv. H, She, G. Nat. Prod. Commun. 2010, 5, 1687-1708; (b) Lv. H, She, G. Rec. Nat. Prod. 2012, 6, 321-333. (a) Chattopadhyay, I.; Biswas, K.; Bandyopadhyay, U.; Banerjee, R. K. Current Science 2004, 87, 44-54 and references cited herein; (b) Lee, K-H. et al J. Med. Chem, 2002, 45, 5037–5042; (b) Ishida, J.; Ohtsu, H.; Tachibana, Y.; Nakanishi, Y.; Bastow, K.; Nagai, M.; Wang, H.-K.; Itokawa, H.; Lee, K.-H. Bioorg. Med. Chem. 2002, 10, 3481-3487; (c) Ohtsu, H.; Xiao, Z.; Ishida, J.; Nagai, M.; Wang, H.-K.; Itokawa, H.; Su, C.-Y.; Shih, C.; Chiang, T.; Chang, E.; Lee, Y.; Tsai, M.-Y.; Chang, C.; Lee, K.-H. J. Med. Chem. 2002, 45, 5037-5042; (d) Narasimhulu, M.; Reddy, T. S.; Mahesh, K. C.; Krishna, A. S.; Rao, J. V.; Venkateswarlu, Y. Bioorg. Med. Chem. Lett. 2009, 19, 3125-3127. (a) Bhosale, S.; Vyavahare, V. P.; Prasad, U. V.; Palle, V. P.; Bhuniya, D. Tetrahedron Lett. 2011, 52, 3397-3400; (b) Bhosale, S.; Kurhade, S.; Prasad, U. V.; Palle, V. P.; Bhuniya, D. Tetrahedron Lett. 2009, 50, 3948-3951. (c) Sandeep Bhosale, PhD Thesis Ref. T(2)/7354/2013, Andhra University, Visakhapatnam.
P-333: Sequential Synthesis of Substituted Furans from Aryl Alkynes and Ketones Involving a Cerium(iv) Ammonium Nitrate (CAN)-Mediated Oxidative Cyclization Sridhar Undeela, Joshi P. Ramchandra, Rajeev S. Menon*
Medicinal Chemistry and Pharmacology Division, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500 007, India and Academy of Scientific and Innovative Research, New Delhi-110025
E-mail address: [email protected]
Furans constitute a ubiquitous class of heterocycles widely found in a variety of biologically active natural products and man-made molecules alike.1 Thus, the synthesis of substituted furans has attracted a lot of attention. Paal-Knorr synthesis2 and various transition metal mediated cycloisomerizations3 represent classical and modern methods of furan synthesis respectively. Here, a convenient, two-step synthesis of substituted furans from readily available aryl alkynes and ketones is presented. Aryl alkynes and ketones first undergo a superbase mediated addition to afford β,γ-unsaturated ketones.4 The latter on oxidative cyclization, mediated by the combination of cerium(IV) ammonium nitrate (CAN) and potassium bromide,5 furnish substituted furans. When sufficiently electron rich arene rings are present in the substrates, they undergo site-selective bromination under the conditions.6 The cyclization can be conveniently carried out in a biphasic medium in an open flask.
(1) Wong, H. N. C.; Hou, X. L.; Yeung, K. S.; Huang, H. in Five- Membered Heterocycles: Furan, Vol. 1; Alvarez-Builla, J., Vaquero, J. J., Barluenga, J., Eds.; Wiley-VCH: Weinheim, 2011; pp 533-692.
(2) (a) Stauffer, F.; Neier, R. Org. Lett., 2000, 2, 3535 (b) Rao, H. S. P.; Jothilingam, S. J. Org. Chem., 2003, 68, 5392.
(3) (a). Egi, M.; Azechi, K.; Akai, S. Org. Lett., 2009, 11, 5002. (b) Blanc, A.; Tenbrink, K.; Weibel, J.-M.; Pale, P. J. Org. Chem., 2009, 74, 4360. (c) Zhang, J.; Schmalz, H.-G. Angew. Chem. Int. Ed., 2006, 45, 6704.
(4) (a) Trofimov, B. A.; Schmidt, E. Y.; Zorina, N. V.; Ivanova, E. V.; Ushakov, I. A. J. Org. Chem. 2012, 77, 6880. (b) Trofimov, B. A.; Schmidt, E. Y.; Ushakov, I. A.; Zorina, N. V.; Skitalt’tseva, E. V.; Protsuk, N. I.; Mikhaleva, A. Chem. Eur. J. 2010, 16, 8516.
(5) Nair, V.; Panicker, S, B.; Augustine, A.; George, T. G.; Thomas, S.; Vairamani, M. Tetrahedron 2001, 57, 7417.
(6) Sridhar, U.; Ramchandra, J. P.; Menon, R. S. Tetrahedron Lett. 2014, 55, 5667. P-334: Enantioselective NHC-Catalyzed Annulations of 2-Bromoenals with 1,3-Dicarbonyl Compounds, Enamines and Enolizable Aldehydes, Heterocyclic C-H acids
Santhivardhana Reddy Yetra, Trinadh Kaicharla, Anup Bhunia, Tony Roy and Akkattu T. Biju*
E-mail: [email protected]
ABSTRACT: The N-Heterocyclic carbene (NHC)-catalyzed generation of α,β-unsaturated acyl azoliums followed by its interception with various nucleophiles, the formal [3+3] annulation reaction is well documented.1 Intriguingly, however, the NHC-catalyzed generation of chiral α,β-unsaturated acyl azoliums is rare. Recently we reported the enantioselective NHC-catalyzed annulations of 2-bromoenals with 1,3-dicarbonyl compounds and enamines via chiral α,β-unsaturated acyl azoliums. The reaction resulted in the asymmetric synthesis of synthetically and medicinally important dihydropyranones and dihydropyridinones, and the reaction tolerates a wide range of functional groups.2 Moreover, very recently, we demonstrated that enolizable aldehydes and heterocyclic C-H acids as nucleophilic partners for chiral α,β-unsaturated acyl azoliums, and the reaction furnished dihydropyranone derivatives.3 In addition, based on DFT calculations, a mechanistic scenario involving the attack of nucleophile from the below the plane of the α,β-unsaturated acyl Azoliums, and the mode of enantioinduction is presented. The details of this work will be presented.
References
1. For selected recent reviews on NHC organocatalysis, see: (a) De Sarkar, S.; Biswas, A.; Samanta, R. C.; Studer, A. Chem. Eur. J. 2013, 19, 4664. (b) Ryan, S. J.; Candish, L.; Lupton, D. W. Chem. Soc. Rev. 2013, 42, 4906. (c) Bugaut, X.; Glorius, F. Chem. Soc. Rev. 2012, 41, 351. (d) Nair, V.; Menon, R. S.; Biju, A. T.; Sinu, C. R.; Paul, R. R.; Jose, A.; Vellalath, S. Chem. Soc. Rev. 2011, 40, 5336. 2. Yetra, S. R.; Bhunia, A.; Patra, A.; Mane, M. V.; Vanka, K.; Biju, A. T. Adv. Synth. Catal. 2013, 355, 1089. 3. (a)Yetra, S. R.; Kaicharla, T.; Kunte, S. S.; Gonnade, R. G.; Biju, A. T. Org. Lett. 2013, 15, 5202; (b) Yetra, S. R.; Roy, T.; Bhunia, A.; Porwal, D.; Biju, A. T. J. Org. Chem., 2014, 79, 4245.
P-335: NHC Based Fluorescent Chemodosimeter for Selective Recognition of Cyanide Ions in Aqueous Medium
Mambattakkara Viji,1 Akhil K. Nair,1 Paramjyothi C. Nandajan1 and Danaboyina Ramaiah*1,2 1Photosciences and Photonics, CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Thiruvananthapuram-695019, Kerala. 2CSIR-North East Institute of Science and Technology (CSIR-NEIST), Jorhat-785006. *E-mail: [email protected] or [email protected]
The hazardous impact of the cyanide ions on both physiological and environmental conditions, has led to an intensive research efforts for the design and development of efficient probes for their detection. [1] The probes involving the displacement approach utilize the affinity of the CN- ions towards various n- metal ions to form stable [M(CN)x] complexes.[2] In this context, we have synthesized two novel N- heterocyclic carbene (NHC) based mono- and dinuclear silver complexes bearing optically active anthracene chromophore for the selective and sensitive detection of the cyanide ions in aqueous medium. The uniqueness of these probes is that they recognize the cyanide ions through visible changes in fluorescence intensity with a sensitivity of ca. 50 ppb, which is far more sensitive than the maximum contaminant level as prescribed by the US-EPA. Interestingly, our NHC probe can be used for the accurate quantification of cyanide ions in aqueous medium. As far as we know this is the first report, which describes NHC based complexes that can be used for the recognition of the cyanide ions in the aqueous medium and signal the event through visible enhancement in fluorescence intensity.[3]
Fig.1: Possible mechanism for the detection of CN- ions using the NHC probe.
References
1. R. Badugu et al., J. Am. Chem. Soc., 127, 3635, 2005. 2. Z. Xu, et al., Chem. Soc. Rev., 39, 127, 2010. 3. M. Viji et al., RSC Adv., 4, 47982, 2014.
P-336: 1,1-DPE and Itaconate Diester Arylation using Pd(OAc)2 and AgOAc co-catalysis Mizoroki-Heck reaction with aryl iodides and diazonium salts Priyanka R. Jawalkar, Swapnil R. Dumbre, Suresh Iyer * Organic Chemistry Division, National Chemical Laboratory, Pune 411008, India *E-mail: [email protected]
1,1-disubstituted olefins are excellent partners for Heck arylation to provide cis-stilbenes and precursors for Tamoxifen analogues (anti-breast cancer drug). The use of PdOAc2 as catalysts and AgOAc as co-catalyst gives very high yield of the Heck arylation products. Itaconate diesters also provide arylidene succinates in high yields. Aryl diazonium salts are alternative substrates for arylation of 1,1-DPE and itaconate diester, using PdOAc2 as catalyst without the requirement of AgOAc and give high yield of the desired substituted arylation product.
Fig.1: Mizoroki-Heck arylation of 1,1-DPE and Itaconate diester
Reference
1. D. Xu, C. Lu, W. Chen., Tetrahedron, 68, 1466, 2012. 2. M. A. Schmidt, J. J. Talley., Chem. Ind. (Dekker – Catalysis of Org. Reactions), 62, 105, 1995 3. F-X. Felpin, K. Miqueu, J-M. Sotiropoulos, E. Fouquet, O. Ibarguren, J. Laudieu., Chem. Eur. J., 16, 5191, 2010 P-337: A rhodamine based probe with Visible and NIR output signaling for respective Hg(II) and Cu(II) ion detection Ajoy Pal1,2 and Bamaprasad Bag*2 1Organic Chemistry Division, National Chemical Laboratory, Pune 411008, India 2Colloids and Materials Chemistry Department, Academy for Scientific and Innovative Research, CSIR-Institute of Minerals and Materials Technology, P.O.: R.R.L., Bhubaneswar-751 013, Odisha, India. *E-mail: [email protected]
Metal ion toxicity in physiological functionalities lead to dysfunction of cells and many health hazards[1], therefore, desirably presets their on-site, real time, selective analysis for biological, environmental and clinical monitoring perspective. Rhodamine based signaling probes[2] for selective detection of metal ion have been of enormous interest because of their ability to evaluate critical concentrations of such environmental pollutant and physiological hazardous substances; apart from their advantages as dual channel signaling module, a straight forward structure-function correlation protocol, and ability to modulate signal in aqueous media. Methodological design of these probes owe to modulation of various parameters such as operational conditions, solvent medium, electronic decoupling etc. to address selectivity, sensitivity, response time, reproducibility/reversibility of signaling operation and reusability issues in detection of various ions at sub-micromolar level with monitoring window of dual chromogenic and fluorogenic signaling. However, advantageous are those which detect multi-analytes as a function of operational conditions[3] and output signals. In a modular approach, the 2-amino-3-pyridyl methylamino- functionalized rhodamine hydrazide derivative L (Fig. 1a) was demonstrated to exhibit chromogenic signals with Hg(II) ion in a aq.-organic binary mixture medium through 557nm output window whereas rendered an Cu(II) specific NIR-absorption signal at 713nm (Fig.1b). The limit of Hg(II) ion detection with this probe was found to be 0.05 µM (spectroscopic) and 0.1µM(naked eye) respectively in aqueous acetonitrile medium The focus of this investigation is centered on tuning role of solvent medium in inducing an altered selectivity with a theoretical support.
Fig.1: Schematic structure of molecular probe L (a) and absorption spectral changes of L after addition with various metal ions. Inset: the fluorescence colour of probe (a) and after addition of Hg(II) (b) upon UV light irradiation.
References 1. (a) Sullivan, J. B.; Kriger, G. R. (eds.) Clinical Environmental Health and Toxic Exposure, 2nd edn., Lippincott Williams and Wilkins, Philadephia, 2001. (b) Harada, M. Crit. Rev. Toxicol., 25, 1, 1995. 2. (a) Beija, M.; Afonso, C. A. M.; Martinho, J. M. G. Chem. Soc. Rev., 38, 2410,2009; (b) Chen, X; Pradhan, T.; Wang, F.; Kim, J. S.; Yoon, Y. Chem. Rev., 112, 1910, 2012. 3. (a) Bag, B.; Pal. A. Org. Biomol. Chem. 9, 4467,2011; (b) Pal, A.; Bag, B. RSC Adv., 4, 10118, 2014; (c) Pal, A.; Bag, B.; Thirunavoukkarasu, M.; Pattanaik, S.; Mishra, B. K. RSC Adv., 3, 18263, 2013. P-338: Synthetic Utility of Carbon Dioxide as a C1- Synthon in Aryne Multicomponent Reactions: A Facile Synthesis of Phthalimides Trinadh Kaicharla, Manikandan Thangaraj, and Akkattu T. Biju*
Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Dr. Homi Bhabha Road, Pune - 411008, India Email address: [email protected]
The synthesis of value-added products by the efficient utilization of CO2 as a one- carbon source has been an imperative subject in organic chemistry because it is a cheap, 1 non-toxic and always available basic compound. Intriguingly, the incorporation of CO2 in aryne reactions has received only limited attention. In this context, we have recently reported the operationally simple and transition-metal-free multicomponent reaction
(MCR) involving arynes and isocyanides with CO2 as the third component to afford the N-substituted phthalimides in moderate to excellent yields (38-87%). The desired product was formed by the construction of two new C-C bonds and a new C-N bond.
Additionally, the incorporation of water as the third component instead of CO2 resulted in the formation of biologically important benzamide derivatives in moderate to good yields (26-92%).2,3
References Cokoja, M.; Bruckmeier, C.; Rieger, B.; Herrmann, W. A.; Kühn, F. E. Angew. Chem., Int. Ed. 2011, 50, 8510. 1. Carey, J. S.; Laffan, D.; Thomson, C.; Williams, M. T. Org. Biomol. Chem. 2006, 4, 2337. Kaicharla, T.; Thangaraj, M.; Biju, A. T. Org. Lett. 2014, 16, 1728.
P-339: Design and synthesis of new Zn(II) nalidixic acid−DACH based Topo−II inhibiting molecular entity: Chemotherapeutic potential validated by its in vitro binding profile, pBR322 cleavage activity and molecular docking studies with DNA and RNA targets Imtiyaz Yousuf, Farukh Arjmand* Department of Chemistry, Aligarh Muslim University, Aligarh–202002, India. E–mail address: [email protected]. *Corresponding author. Tel.: +91 5712703893.
Nalidixic acid−DACH based Zn(II) molecular (1) entity was synthesized and thoroughly characterized by spectroscopic techniques (FT−IR, 1H and 13C NMR, ESI−MS) and single crystal X–ray crystallography as a potential chemotherapeutic drug candidate. The comparative invitro binding studies of complex with targets like CT−DNA and yeast tRNA were carried out by employing UV−vis, emission spectroscopy, circular dichroism and viscosity which revealed higher binding affinity ofcomplextowards yeast tRNA as compared to CT−DNA. Complex 1 cleaves pBR322 plasmid via hydrolytic pathway (validated by T4 religation assay); in addition, 1 also exhibited significant inhibitory effects on the catalytic activity ofTopo– II at a concentration of 30 μM. Further, validation of the interaction studies was accomplished by carrying out molecular docking studies with DNA, RNA and Topo−II targets. This work also advances our knowledge for the development and design of small RNA targeted therapeutic molecules which were relatively under exploited drug targets [1].
Fig. 1Diagram showing a single asymmetric unit of complex 1.
Reference 1. F. Arjmand, I. Yousuf, M. Afzal, L. Toupet Inorg. Chim. Acta 421 (2014) 26–37.
P-340: Synthesis of New 4-Thiazolidinones Bearing Nitrogen and or Sulphur Five Membered Heterocyclic Scaffolds Mahendra B. Bhalerao, Amarsinh R. Deshmukh, Anusaya S. Chavan Ramrao A. Mane*a Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad-431 004, Maharashtra, India Email: [email protected]
Abstract:
Type I and Type II diabetes mellitus (DMs) are now recognized as serious global health problem and growing rapidly worldwide. Owing to the seriousness of Type II DM various pharmacological agents have been developed. 4- Thiazolidinones is a group of pharmacological agents. Pyrazoles are also emerged as potential antihyperglycemic agents. A number of pyrazolyl compounds have been cited in the literature and are found to display antihyperglycemic activity.
Literature survey reveals that, there is scanty information on the molecules having pyrazole, thiazole, and 4-thiazolidinone rings in one molecular frame. Considering the seriousness of diabetic disease and limitations of present antidiabetic agents, here it was thought worthwhile to synthesize the titled heterocycles bearing 4-thiazolidinone, thiazole, and pyrazolyl pharmacophores with hope to obtain the therapeutic agents with better antidiabetic activity. A series of N-phenyl-2-(1-(4-(4-fluorophenyl) thiazole-2-yl)-3-(4-methyl-5- phenylthiazol-2-yl)-1H-pyrazol-4-yl)-3-phenylthiazolidin-4-ones has been synthesized via multistep starting from 1-(4-methyl-2-phenylthiazol-5-yl) ethanone. The details of synthetic route, developed for the entitled products will be provided in the presentation.
O S N N N S S N N R O S N (1)
F (6a-l)
References:
[1] Jawale D. V., Pratap U. R., Rahuja N., Srivastava A. K., Mane R. A., Bio Org Med Chem Lett., 2012, 22, 436. [2] Beckman, J. A.; Creager, M. A.; Libby, P.J. Am. Med. Assoc. 2002,287, 2570. [3] Gregory, R.; Greg, A.; Beverly, B.; Christine, B.; Bork, B.; Bryan, F. B.; Michele, E. G.; Jiaping, D. J. Med. Chem. 2001,44, 2601.
P-341: One poteco-friendly synthesis of new N-phenyl-3-(2’methyl/phenyl-4’- methylthiazole-5’-yl)-4(3’-aryl-thiazolidin-4’-on-2’-yl)pyrazoles)as anti- inflammatory agents Lalit D. Khillare, Sambhaji T. Dhumal, Manisha R. Bhosle and Ramrao A. Mane*a Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad-431 004, Maharashtra, India Email: [email protected]
Abstract: Non-steroidal anti-inflammatory drugs (NSAIDs) are amongst the most widely used therapeutic agents for the treatment of severe pain and inflammation. Most of the effective painkillers,including opioids and non-steroidal anti-inflammatory drugs, aregenerally not selective and are partially effective.Their prolong exposurecan cause side effects.Therefore continuous efforts are found to be paid towards search of therapeutics for pain/ inflammation control with alternativemechanism of action having no side effects.The new effective drugs with better safety profilewill always in demand to relivesevere inflammatory conditions. Pyrazole derivatives are known to possess a wide spectrum of biological activities including anti-inflammatory. Celecoxibis well-known NSAIDhaving pyrazole nucleus and hasa fewside effects. Thiazole and 4-thiazolidinone heterocyclic nuclei are emergingas potential anti-inflammatory agents. Literature survey reveals that there is scanty information on the molecules having pyrazole, thiazole and thiazolidinone heterocyclic ringsin onemolecular frame. Considering the pharmacological importance of the above biodynamic rings and the side effects associated with the existing drugshere a series of N-phenyl-3-(2’methyl/phenyl- 4’-methylthiazole-5’-yl)-4(3’-aryl-thiazolidin-4’-on-2’-yl)pyrazoles (3a-j)has been synthesized starting from 3-(4-methyl-2- substitutedthiazol-5-yl)-1-phenyl-1H-pyrazole- 4-carbaldehydes (1a-b). With hope to obtained better anti-inflammatory agents. The details of theone pot synthetic route, developed for the entitled products and biological activity willbe provided in the presentation.
N N R R N S N S N N S O N H O R'
(3a-j) (1a-b)
References: [1] G. Dannhardt, W. Kiefer, Eur. J. Med. Chem. 36 (2001) 109 [2] F. F. Barsoum, H. M. Hosnib, A. S. Girgis, Bioorg. Med. Chem. 14 (2006) 3929. [3] D. Chiarino, G. Grancini, V. Frigeni, I. Biasini, A. Carenzi, J. Med. Chem. 34 (1991) 400.
P-342: Study Of complexation between Quinoline & various calixarenes Rupali Thoravea, Sanhita Patilb,Nitin Lavandec,D.D.Malkhede* Physical Chemietry Dept. S.P.Pune University,Ganeshkhind-411007,Pune Email: [email protected]
Abstract
We have studied the complexation of Quinoline dye with p-sulfonato calix (4) arene ligand, p- sulfonatocalix(6) arene ligand & p-sulfothia calix(4) arene sodium salt ligand by UV-Visible Spectrophotometry & Fluorescence spectroscopy. It is a supramolecular chemistry in which interaction between host and guest is studied at molecular level. The Quenching constant for all three complexes was determined by Stern-Volmer method. Also the stability constants were determined for all three complexes. All studies had been done in DMSO. The fluorescence lifetime studies and electrochemical studies by cyclic voltammetry are in pipeline.
‘
2mlq in DMSO y = 2.01*10^-4x+1.813 2mlQ+1ulThia Ks = 1.1086*10^-4 2mlQ+5ulThia y = 2.0109*10^-4x+2.8096 Q+scx6(313nm) 160 y = 3.23*10^-3x+3.6982 2mlQ in DMSO(313nm) 2mlQ+10ulThia 10 Q+scx4 12 Ks = 7.157*10^-5 2mlQ+1ulscx-6 140 R = 0.9447 2mlQ+20ulThia Ks = 8.733*10^-4 2mlQ+40ulThia R=0.9677 1000 1600 2mlQ+5ulscx-6 9 R=0.9910 120 2mlQ+60ulThia 10 2mlQ+10ulscx-6 2mlQ+80ulThia 2mlQ+20ulscx-6 100 1200 8 2mlQ+40ulscx-6 2mlQ+100ulThia 8 80 2mlQ+120ulThia 2mlQ+60ulscx-6 7 2mlQ+80ulscx-6 2mlQ+140ulThia 60
I0/I0-I 2mlQ+160ulThia I0/I0-I 1400 6 2mlQ+100ulscx-6 6
2mlQ+180ulThia (I0/I0-I) 2mlQ+120ulscx-6 40 2mlQ+200ulThia 2mlQ+140ulscx-6 2mlQ+220ulThia 5 4 20 800 2mlQ+160ulscx-6 1000 2mlQ+240ulThia
2mlQ+180ulscx-6 1 4 0 2mlQ+260ulThia 2 2mlQ+200ulscx-6 A 2mlQ+280ulThia
1200 a 10000 20000 30000 40000 50000 2mlQ+220ulscx-6 -20 2mlQ+300ulThia 3 0 50000 100000150000200000250000300000350000400000450000 7600 7800 8000 8200 8400 8600 8800 9000 9200 9400 (p-scx4)^-1 (p-scx6)-1 (p-stcx^-1)
1.4 0.67 800 1000 scx6 Thiacalix 1.3 600 2.0 scx-4 0.66 1.2 1.8 0.65
1.1 1.6 0.64
I0/I 1.4 800 1.0 0.63 600 y = 8305.675x+0.7362 1.2 I0/I 0.9 0.62 R=0.9971 1.0 0.8 Intensity 400 0.61 Intensity I0/I y = 1081.749x+0.5906 2mlQ in DMSO 0.8 Intensity 600 0.60 0.7 2mlQ in DMSO+1ulscx-4 0.00006 0.00007 0.00008 0.00009 0.00010 0.00011 0.00012 0.00013 0.00014 2mlQ+5ulscx-4 0.6 R=0.9912 2mlQ+10ulscx-4 0.59 400 concentration 2mlQ+20ulscx-4 0.4 y = 3297.1049x+1.1071 0.000020.000030.000040.000050.000060.000070.000080.000090.00010 2mlQ+40ulscx-4 0.2 R=0.9882 2mlQ+60ulscx-4 conc 2mlQ+80ulscx-4 0.0 400 0.000020.000030.000040.000050.000060.000070.000080.000090.00010 200 2mlQ+100ulscx-4 2mlQ+120ulscx-4 2mlQ+140ulscx-4 conc 200 2mlQ+160ulscx-4 2mlQ+180ulscx-4 2mlQ+200ulscx-4 200 2mlQ+220ulscx-4 2mlQ+240ulscx-4 0 0 350 400 450 500 550 600 0 350 400 450 500 550 600 650 350 400 450 500 550 600 650 wavelength/nm X Axis Title wavelength/nm Fig: (i)Fluorescence Emission spectra of Quinoline[1x10-6M] in the presence of increasing amounts of pscx4 [1x10-3M] (00to240ul). (ii) Fluorescence Emission spectra of Quinoline [1x10-6M] in the presence increasing amounts of pscx6 [1x10-3M] (00to220ul). (iii) Fluorescence Emission spectra of Quinoline [1x10-6M] in the presence increasing amounts of pstcx4 [1x10-3M] (00to300ul).
Reference: 1. L.R.Naik, H.M. Suresh Kumar, S.R. Inamdar, &N.N.Math .Spectroscopy Letters, 38:645-659,2005. 2.Giuseppe Arena, Annalinda Contino, Giuseppe Maccarrone, Domenico Sciotto and Carmelo Sgarlata.Tetrahedron Letters 48 (2007)8274- 8276. P-343: Inclusion complex formation of ternary system: Fluoroscein-p- sulfonatocalix[4]arene-M2+by cooperative binding Sharadchandra Gawhale1, Ankita Jadhav2, Gajanan Chaudhari3*,Dipalee Malkhede2*
1Department of Applied Chemistry, AISSMS-CoE, Pune,India 2Department of Chemistry, University of Pune, Pune, India 3Department of Chemistry, Shri.Shivaji Science College, Amravati,India ------
Abstract
The aqueous solution of para-sulfonatocalix[4]arene-fluorescein-metal ion complex has been studied based on fluorescence and 1H NMR spectroscopic results. It was found that the fluorescence intensity quenched regularly upon addition of p-SCX4 and metal ion. The quenching constants and stability constants were determined for p-SCX4-FL and p-SCX4–FL-M2+ systems. 1:1 stoichiometry is obtained for p-SCX4-M2+ system by Continuous variation method. The proposed inclusion complex for binary and ternary system were discussed on 1H NMR results. Results were consistent with experimental data obtained from NMR spectroscopy. The combined results demonstrate the cooperative binding to design the complex for ternary system. The life time for binary and ternary system has been studied.
Key words: para-sulfonatocalix[4]arene, Fluorescein, ternary system, cooperative binding
DDM-23052014-SCX-4A-RH-5-1H 6.51 1.0 2500
0.9 40 y = 1.994E-5 x + 0.7758 R2 = 0.9999 0.8 30
0.7 20
2000 Io-I / Io 0.6
0.5 6.66 10 Normalized Intensity 0.4 4.27 0 0 500000 1000000 1500000 2000000 0.3 [p-Scx4]-1 M 7.22 7.93 7.74 7.66 7.19 7.95 1500 7.68
0.2 7.36 35 2.50 2.46 7.77 7.63 0.1 30 y = 4.95E-5 x + 3.1389 6.86 R2 = 0.9846 25 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 20 Chemical Shift (ppm) 15
1000 / Io-I Io Intensity 10 5
0 2+ 0 20000 40000 60000 fig :p-Scx4-Fl-Cu [Cu]-1 M 500
0 450 500 550 600 650 700 Wavelength
-6 fig: Fluorescence emission spectra (λex 511nm) of FL [1x10 M) at pH = 3.5; at different concentration of p-SCX4 (1 x 10-4M).
Reference. 1.KeisukeOhto, Yuko Fujimoto, Katsutoshi Inoue, Analytica Chimica Acta, 1999,387,61-69. 2.PaulpandianMuthuMareeswaran, EththiluBabu, VeerasamySathish, Byoungkook Kim, SeongIhi Woo and Seenivasan Rajagopal, New J. Chem., 2014, 38, 1336-1345.
P-344: Electrochemical investigation of oxygen evolution reaction (OER) on the under potential deposited cobalt film. H.S. Sonwalkar1, S.K. Haram1*. 1Department of Chemistry, Savitribai Phule Pune University, Ganeshkhind Pune-411007. Email-id:[email protected], [email protected]
The development of a catalyst for the water oxidation has attracted much attention in recent years due to the constant quest of transforming water into useful fuel i.e. H2. One of the major limitations however is the oxygen evolution reaction (OER) which is billionth time slower than the hydrogen evolution reaction (HER) at neutral pH. Thus, it is atmost important to develop the electro-catalyst for OER reaction which is not only efficient but also derived from earth abundant elements. Among various metals and their oxides proposed, cobalt, cobalt-oxides and phosphates [1] are found to be most promising one and thus well studied. Recently, under-potential deposited (UPD) film of Co has been found be better option than the bulk Co. The advantage of UPD Co is they form ad-atoms on the substrate which are found to be catalytically more active than surfactant- caped Co nano-particles [2, 3]. This background motivated us to study the under potential deposition of Co by electrochemical quartz crystal micro-balance (EQCM) [4] and quantifying the kinetics of OER reaction by Rotating Disk Electrode (RDE). The underpotential deposition on Quartz crystal gold substrate was carried out by cycling the potential in the under-potential range in cobalt chloride in ammonium chloride solution. The amount of Co deposited was estimated directly by noting the change in frequency after the deposition and using Sauerbrey equation: Δf = -C×f ×Δm. The electrodics of OER was studied on Co UPD on rotating gold disk electrode.
Fig.1: Cyclic voltammogram obtained in the Au/xCoCl2+1M NH4Cl with corresponding mass variation in RQCM study.
References: [1] Kanan et al, Science, 321, 1072, 2008. [2] Penner and Borovik et al, Langmuir, 29, 14728, 2013. [3] Mendoza-Huizar et al.Journal of Electroanalytical Chemistry, 521, 95-106, 2002. [4] Irshad et al, J. Phys. Chem. C, 117, 8001, 2013.
P-345: Experimental Determination of the Electrostatic Nature of Carbonyl Hydrogen-Bonding Interactions Somnath M. Kashid, Pranab Deb, Tapas Haldar, Sayan Bagchi* Physical Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, Maharashtra, India. *E-mail: [email protected]
Hydrogen bond is ubiquitous in nature and plays a fundamental role in determining the structure, function, and dynamics in several chemical and biological systems. Though the chemical concept of hydrogen bond was introduced in the early twentieth century; to date the literature contains several debates and discussions on the nature of the physical interactions that contribute to the hydrogen bonds. We present a novel experimental approach involving IR−13C NMR correlations to determine the physical nature of carbonyl hydrogen-bonding interactions. Our results provide a direct experimental evidence of the electrostatic nature of hydrogen-bonding interaction in carbonyls, independent of any theoretical approximation. These results will pave the way to experimentally verify the mechanism of several chemical/ biological reactions involving hydrogen-bonded carbonyl intermediates using spectroscopic techniques.
Reference 1. Fried S. D. et al., J. Am. Chem. Soc., 135, 11181−11192, 2013. 2. Kashid S. M. et al., J. Phys. Chem. Lett., 5, 3211-3215, 2014.
P-346: Temperature Dependent Reversible p-n-p Type Conduction Switching with Colossal Change in Thermopower of Semiconducting AgCuS Satya Narayan Guin and Kanishka Biswas* New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P.O., Bangalore 560 064, India E-mail: [email protected]
Semiconductors have been fundamental to various devices that are typically operated with electric field, such as transistors, memories, sensors, and resistive switches. There is growing interest in the development of novel inorganic materials for use in transistors and semiconductor switches, which can be operated with a temperature gradient. Here, we show that a crystalline semiconducting noble metal sulphide, AgCuS, exhibits a sharp temperature dependent reversible p-n-p type conduction switching, along with a colossal change in the thermopower (ΔS ~1757 µVK-1) at the superionic phase transition (T ~364 K). In addition, its thermal conductivity is ultra-low in 300-550 K range giving AgCuS the ability to maintain temperature gradients. We have developed fundamental understanding of the phase transition and p-n-p type conduction switching in AgCuS through temperature dependent synchrotron powder X-ray diffraction, heat capacity, Raman spectroscopy and positron annihilation spectroscopy measurements. Using first-principles calculations we show that this rare combination of properties originates from an effective decoupling of electrical conduction and phonon transport associated with electronic states of the rigid sulphur sublattice and soft vibrations of the disordered cation sublattices, respectively. Temperature dependent p-n-p type conduction switching makes AgCuS an ideal material for diode or transistor devices that operate reversibly on temperature or voltage changes near room temperature.
1000 AgCuS
500 p- type p- type V/K) orthorhombic
cubic µ 0 ∆S = 1757 S ( S -500 hexagonal n- type -1000 300 375 450 525 T (K)
Reference 1. S. N. Guin et al., J. Am. Chem. Soc., 136, 12712, 2014.
P-347: Synthesis and Characterization of Highly Selective, Ditopic,‘Turn- on’and ReversibleFluorescentChemosensor for Al+3Ion andIts Theoretical Calculations Sayed M. Hossain, Akhilesh K. Singh* School of Basic Sciences, IIT Bhubaneswar, Orissa, Bhubaneswar-751007, India E-mail: [email protected], [email protected]
A ditopic phenol derivative 6,6'-methylenebis(4-methyl-2-(1-((pyridin-2-ylmethyl)imino)ethyl)phenol) (H2L) Schiff-base ligand was designed and synthesized which may be used as highly selective ‘turn-on’ reversible fluorescent chemosensor for Al+3 ion in 99% methanol. Al+3-L (2:1) complexation was confirmed by 1HNMR, Job’s plot, modified Hill’s equation, ESI-MS etc. The designed system is an amalgamation of three mechanisms of fluorescence activity such as Aggregation Induced Emission (AIE), restriction of C=N isomerization and inhibition of high speed Intramolecular Proton Transfer (IPT) between phenolic OH and imine nitrogen. Due to presence of four aromatic ring, H2L shows AIE, due to presence of methyl group in imine carbon (R-C=N) its C=N isomerization becomes restricted and after complexation with Al+3 ion, high speed intramolecular proton transfer completely ceases. These are responsible for high fluorescence of Al+3-L (2:1) complex. Theoretical calculations were done at the level of B3LYP/6-31G* for ground state and TD- B3LYP/6-31G* for excited state both in methanol medium. a). b).
6 1.5x10 300
240 1.0x106 180
120 5.0x105
60 Fluorescence IntensityFluorescence
Fluorescence intensityFluorescence (a.u) 0.0 0 400 450 500 550 600 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 3+ 2+ 2+ 3+ 2+ 2+ 2+ 2+ Wavelength (nm) 1.H2L, 2.Al , 3.Mn , 4.Hg 5.Fe , 6.Co , 7.Ni , 8.Cu , 9.Zn ,
10.Ag+, 11.Na+, 12.K+, 13.Pb+, 14.Mg2+, 15.Ca2+, 16.Ga3+, 17.In3+
Fig.1:a) Fluorescence spectra of free H2L (10 μM), Al(NO)3 (20 μM) and their 1:2 metal complex(λex= 360 nm), b). Bar graph shows the relative emission intensity of H2L(10 μM) at 472 nm upon treatment with various metal ions(20 μM) in methanol-water (99:1).
These results would be highlighted.
Reference
1.Wu, J.; Liu, W.; Ge, J.; Zhang, H.; Wang, P.Chem. Soc. Rev., 2011, 40, 3483–3495.
2. Kim, S.; Noh, J.Y.; Kim, K.W.; Kim, J.H.; Kang, H.K.; Nam, S.W.; Kim, S.H.; Park, S.; Kim, S.; Kim, J. Inorg.Chem., 2012, 51, 3597−3602.
3. Cao, W.; Zheng, X.J.; Sun, J.P.; Wong, W.T.; Fang, D.C.; Zhang, J.X.; Jin, L.P. Inorg. Chem., 2014, 53, 3012-3021.
P-348: Acridinedione based “Turn off” Fluorescent chemodosimetry for Selective Detection of F- ion in Organic and Aqueous Medium R. Suresh, T. Senthilkumar, P. Ramamurthy* National Centre for Ultrafast Processes University of Madras, Taramani Campus, Chennai -113. E-mail: [email protected]
Fluoride is one of the essential anion for humans and it is a common additive to drinking water and toothpaste because of its beneficial effects on human health.[1] In the biological systems, certain levels of fluoride are critical to maintain the normal physiological functions (e.g., regulating cellular pH and osmosis).[2] While the optimal intake of fluoride according to the data published by the U.S. Public Health Service is 1 mg per day for humans,[3] too much will lead to poisoning effects, such as fluorosis and urolithiasis.[4] Thus, a rapid, facile and quantitative approach for the measurement of fluoride is highly needed. Over the years various types of fluoride sensors were designed among these reaction based fluoride sensors have a great impact due to its extreme selectivity. Although the desilylation based fluoride sensors significantly subsided the effects of interfering anions, long reaction time, up to several tens of minutes or even hours, has remarkably hampered their applications for samples containing fluoride with low concentration. To understand the factors determining the response time of desilylation based fluorescent probe, ADD-1, ADD-2 and ADD-3 were designed and synthesized [5] by using trimethylsilyl ether, tert-butyldimethylsilyl and tertbutyldiphenylsilyl ether as the recognition moiety to react with fluoride. Fluoride triggered desilylation significantly quenches the fluorescence via photoinduced electron transfer (PET) processes from the phenolate moiety to the acridinedione ring. By using these chemosensors fluoride anion concentration has been quantitatively determined in acetonitrile as well as in water.
Strong Fluorescence Weak Fluorescence
References :
1. F. Du, Y. Bao, B. Liu, J. Tian, Q. Li and R. Bai, Chem. Commun., 2013, 49, 4631. 2. M. Cametti and K. Rissanen, Chem. Soc. Rev., 2013, 42, 2016. 3. K. L. Kirk, Biochemistry of the Elemental Halogens and Inorganic Halides, Plenum, New York, 1991. 4. G. Waldbott, Clin. Toxicol., 1981, 18, 53. 5. Q. Song, A. Bamesberger, L. Yang, H. Houtwed and H. Cao, Analyst, 2014, 139, 3588.
Keywords: Fluoride anion, chemosensor, acridinedione, photoinduced electron transfer.
P-349: Recent development in sensing mechanism for the design of fluorescent chemosensors Mrituanjay D. Pandey* and Rampal Pandey* Department of Chemistry, (School of Chemical Science & Technology), Dr. H. S. Gour Central University Sagar, MP 470003, India. *E-mail: [email protected] (MDP); [email protected] (RP)
Keywords: Fluorescence, Sensor, Mechanisms
During the past decade, development of fluorescence sensors with superb selectivity and sensitivity has become an important area of research of supramolecular chemistry. The design of new fluorescent chemosensors and exploration of new sensing mechanisms is of continuing interest. The conventional sensing mechanisms including intramolecular charge transfer (ICT), photo-induced electron transfer (PET), twisted intramolecular charge transfer (TICT), metal–ligand charge transfer (MLCT), electronic energy transfer (EET), excimer/exciplex and fluorescence resonance energy transfer (FRET) formation have been investigated. In the past few years new sensing mechanism has been worked out such as C N isomerization, aggregation-induced emission (AIE), Two-Photon-Absorption Technique and excited-state intramolecular proton transfer (ESIPT).
Fig.1: Various methodologies developed and mechanisms discussed for chemosensing
Reference 1. Wu, J.; Liu, W.; Ge, J.; Zhanga, H.; Wang, P. Chem. Soc. Rev., 2011, 40, 3483-3495. 2. Chandrasekhar, V.; Pandey, M. D.; Maurya, S. K.; Sen P.; Goswami, D. Chemistry: An Asian J., 2011, 6(9), 2246– 2250. 3. Chandrasekhar, V.; Bag P.; Pandey, M. D. Tetrahedron, 2009, 65(47), 9876–9883. 4. Pandey R.; Gupta R. K.; Shahid M.; Maiti B.; Misra A.; Pandey D. S. Inorganic Chemistry 2012, 51, 298-311. 5. Pandey R.; Kumar P.; Singh A. K.; Shahid M.; Li P.-Z.; Singh S. K.; Xu Q.; Misra A.; Pandey D. S Inorganic Chemistry 2012, 51, 298-311.
P-350: Inorganic semiconductor-graphene quantum dots hybrid: A potential multifunctional material Anupam Biswas,1 Raja Das1 and Pankaj Poddar*,1 1. Physical & Materials Chemistry Division, CSIR-National Chemical Laboratory, Pune - 411008, India *E-mail: [email protected] Controlled introduction of defects in semiconductors draws considerable importance as these materials have immensely contributed in the development of optoelectronic devices in past. Surface-disordered anatase-TiO2 caught wide attention for its exceptional photocatalytic performance.1 We recently demonstrated, for the first time, single-pot synthesis of rutile, surface-disordered TiO2-graphene quantum dots (TiO2-GQDs) hybrid material, with in situ insertion of GQDs during the growth of rutile TiO2 particles. This TiO2-GQDs hybrid showed ~ 98% degradation of methylene blue (MB) dye within just 6 min under natural sunlight illumination. This new generation hybrid material will be potentially useful in all field of science due to its tailored band structure. 2 The powder x-ray diffraction (PXRD) patterns matched with PCPDF#894920 for rutile-TiO2. The rutile-TiO2 was prepared in an aqueous medium containing GQDs, so the growth of the TiO2 was hindered during the reaction. Therefore, instead of regular TiO2 structure, we found some small grains assembled together containing rutile-TiO2 and GQDs. In HRTEM images at higher magnification, we do find this type of texturing in the hybrid material. To confirm the TiO2 and GQDs distribution, we performed bright and dark field HRTEM imaging of the same region of the sample. For that purpose, we selected (101) diffracted beam of TiO2 and it 3 was observed that GQDs were present all over the matrix containing rutile TiO2. The reduction in photoluminescence intensity denotes lower charge recombination which, in turn will, be useful for the photocatalytic application.
Fig. 1: A comparison of room temperature XRD patterns of rutile-TiO2, rutile-TiO2-GQDs hybrid, and PCPDF#894920 data of rutile TiO2. The # marked peaks represent graphitic carbon. Fig. 2: A, B) Comparison of bright-field and dark-field {(101) diffracted beam of TiO2} images same area of rutile-TiO2-GQDs hybrid. Inset of B) shows the corresponding SAED pattern. Fig. 3: solid PL spectra of rutile-TiO2 and rutile TiO2- GQDs hybrid. The PL spectra were taken with an excitation wavelength of 370 nm. Fig. 4: A, B) HRTEM images show the distribution of rutile-TiO2 and GQDs in TiO2-GQDs hybrid. The 0.33 nm and 0.21 nm lattice spacing are for GQDs (111) and (100) plane. The 0.32 nm and 0.24 nm lattice spacing are for rutile-TiO2 (110) and (101) plane.
References 1. X. Chen et al. Science, 331,, 746. 2011. 2. S. Sadhu et al. RSC Adv,.3,, 1933, 2013. 3. A. Biswas et al. Communicated. P-351: Enzyme-immobilizedMicrotubular ZnO@ZnS Heterostructure:An Amperometric Cholesterol Biosensor with Excellent Sensitivity and Limit of detection ArnabKanti Giri,1Vinod Kumar Shahi2 andAsitBaran Panda*1 1Discipline of Inorganic Materials and Catalysis,Academy of Scientific and Innovative Research, Central Salt and Marine Chemicals Research Institute (Council of Scientific and Industrial Research), G.B. Marg, Bhavnagar-364002, Gujarat, India. 2Electro-Membrane Processes, Academy of Scientific and Innovative Research, Central Salt and Marine Chemicals Research Institute (Council of Scientific and Industrial Research), G.B. Marg, Bhavnagar-364002, Gujarat, India. *E-mail:[email protected]
The controlled synthesis of porous nanostructure materials and their use as active material for cholesterol sensing properties are of key importance in present frontier research for their high surface area, optical and electrical, and enhanced electron transport properties. Here, we have synthesized microtubular shaped ZnO@ZnS heterostructure from the corresponding ZnO microtubes through a simple aqueous wet chemical sulphidation process. ZnS microtubes have also synthesized through leaching of ZnO from ZnO@ZnS heterostructure by acetic acid. Both the ZnO@ZnS and ZnS microtubes showed modified band structure, i.e., electronic structure. The synthesized ZnO@ZnS heterostructure modified electrode showed excellent amperometric cholesterol sensing performance with sensitivity of 52.67 mAM-1cm-2, limit of detection (LOD) of 0.02 mM (S/N = 3), and 15 signal to noise ratio. The sensing performance i.e., both the sensitivity and LOD, of the ZnO@ZnS heterostructure is superior than that of reported ZnO based sensor as well as Au or Pt modified sensor.
Fig.1:a) SEM image of the ZnO microtubes;b,c) ZnO-ZnS microtubes;d) ZnS microtubes and e) Schematic representation of cholesterol sensing mechanism of microtubular ZnO@ZnS heterostructure.
References
1. A. B. Panda et al.,J.Mater.Chem. A, 2, 16997, 2014. 2. A. B. Panda et al.,J.Mater.Chem. A, 1, 814, 2013. 3. B. D. Malhotra et al.,Electroanalysis,,21, 965, 2009.
P-352: Synthesis and photocatalytic performance of graphene hybridized ZnO for degradation of Rhodamine B dye Dipali Kale1, Pragati Thakur1* Department of Chemistry, Savitribai Phule Pune University , Pune 411007, India. *E-mail: [email protected]
Synthetic Dyes have total annual production of 7x105 tons and have extensive use in many industries. It has been estimated that more than 10-15 % of these were discharged into environmental components during synthesis and dying process .Presence of Dyes and their degradation by-products in water are potential threats to environment, due to their biodegradation resistance, poor aesthetic quality of water, less growth of bacteria’s responsible for degradation, carcinogenetic and toxic effects. Among several methods available for removal of pollutants from wastewater, heterogeneous photocatalysis has gained increasing importance owing to its efficiency of environmental purification and complete mineralization. Photo-degradation by ZnO, a semiconductor with direct band gap of 3.37eV, has been widely used for removal of organic pollutants from water. However major limitations of ZnO to achieving high photocatalytic efficiency, is the quick recombination of photo-generated electron hole pairs and photo corrosion in aqueous solution. It has been shown that, in semiconductor-graphene composite, graphene can act as an excellent electron acceptor or transport material, therefore it can suppress electron hole recombination and thus can enhance activity of a photocatalyst .On the other hand, presence of photocatalyst nanoparticles reduces restacking and agglomeration of individual graphene sheets which provides high specific surface area. To exploit photocatalytic properties of ZnO have motivated us to synthesize ZnO-Graphene nano-composites. ZnO-Reduced graphene oxide (RGO) nano-composites were synthesized via the hydrazine assisted hydrothermal process by changing the initial amount of Graphene Oxide (GO). The prepared ZnO nanostructures and ZnO-RGO composites were characterized by x-ray diffraction [as shown in Fig 1(a)], transmission electron microscopy, Raman spectroscopy and UV-vis diffuse reflectance spectroscopy. The ZnO nanostructures were tested for photocatalytic activity for degradation of Rhodamine B dye under UV irradiation. As shown in Fig.1.(b), ZnO-RGO composites have enhanced photocatalytic efficiency compared to that of pure ZnO.
(a) 1.4 % graphene/ZnO (101) (002) (100) (110) (112) (102) (201) (103) (200) 0.5 % graphene /ZnO
Intensity(a.u.) ZnO
graphene oxide
10 20 30 40 50 60 70 80 2Θ(degree)
Fig.1: (a) XRD pattern of graphene oxide, pure ZnO and graphene/ZnO composites;(b) ln(Co/C) against irradiation time curves of degradation of Rhodamine B dye using pure ZnO and graphene/ZnO composites.
Reference 1. Li Q et al., Journal of the American Chemical Society, 133, 10878,2011. 2. Zhang Y et al., Acs Nano, 4, 7303,2010.
P-353: Amperometric biosensor based on immobilized ZnO nanoparticles for detection of organophosphorous pesticides Manisha Pabbi andSusheelK Mittal* School of Chemistry and Biochemistry, Thapar University, Patiala, Punjab-147004 Email: [email protected]
Abstract:ZnObased amperometric biosensor was fabricated using alkaline phosphatase (AP) enzyme bound on the surface of Chlorella sp. for the detection of organophosphorous pesticides- acephate, chloropyrifos, triazophos, malathion. Chlorella sp.was immobilized on the surface of ITO glassusing tetraethyl orthosilicate (TEOS). The system was optimised for parameters such as pH, concentration of algal cells, substrate. In the presence of pesticide, enzyme activity was inhibited; however, the extent of inhibition was different for different pesticides. The inhibition effect was monitored for the production of p-nitrophenol (PNP) from substrate p-nitrophenyl phosphate (PNPP). The trend of inhibition follows acephate>chloropyrifos>triazophos>malathion. The detection limit for acephatewas found to be 10-11 M and that for chloropyrifos is 10-8 M. The interference studies showed that malathion and triazophos does not interfere in the detection of acephate but chloropyrifosdoes. The developed biosensor is a promising tool for the detection of acephate in the presence of malathion and triazophos.
Keywords: ZnO, Alkaline phosphatase, organophosphorus pesticides
P-354: Conversion of Non-Porous Coordination Polymers into Porous Supramolecular Assemblies Using Neutral Linkers Navnita Kumar, 1 Sadhika Khullar, 1,2 Sanjay K. Mandal *1 1 Department of Chemical Sciences, Indian Institute of Science Education and Research, Mohali, Sector 81, Manauli PO, S.A.S. Nagar, Mohali (Punjab) 140306, INDIA 2 Department of Chemistry, DAV University, Jalandhar (Punjab) 144001, INDIA *E-mail: [email protected]
In recent years there is a huge leap in examples of coordination polymers (CPs) and supramolecular assemblies (SAs) reported in the literature. The architecture of these CPs and SAs relies on the extent of coordination and hydrogen bonds within these moieties. [1-5] While these two bonding are orthogonal in nature, the formation of CPs over SAs and vice versa could be due to the hierarchical importance of these two forces in the overall structure. An interconversion between these two sets of species can lead to a deeper insight of the role played by various bondings in their synthesis and thus allows the synthesis of desired materials with tunable properties. [6-8] In this presentation, various non-porous CPs synthesized from Cu(II) and L-serine based ligands (e.g. N-(2-hydroxybenzyl)-serine, N-(2-hydroxy-5-methoxybenzyl)-serine, N-(2-hydroxy-5- nitrobenzyl)-serine, N-(2-hydroxy-5-chlorobenzyl)-serine, N-(2-hydroxy-3-chlorobenzyl)-serine, N-(2-hydroxy- 3-methoxybenzyl)-serine) are reported. Furthermore, by using neutral linkers like 4,4′-bipyridine, conversion of the non-porous CPs to porous SAs with tunable properties is also addressed. In doing so, evidence for the important role played by hydrogen bonding in the stabilization of the SAs is also established.
OH OH
O HN
OH Y X
Fig.1: Various ligands used in the study where X and Y = H and NO2; H and Cl; H and OMe.
N N
Methanol Reflux for 6 hours Coordination polymer formed using Conversion to Supramolecular Assembly Cu(II) and N-(2-hydroxybenzyl)-serine by insertion of the Linker between metal centers
Fig.2: Conversion of a CP into SA by insertion of a neutral Linker between two metal centers.
Reference 1. A. D. Burrows et al., Chem. Soc. Rev., 24, 329, 1995. 2. A. M. Beatty, CrystEngComm, 3, 243, 2001. 3. C. B. Aakeroy et al., Aust. J. Chem., 54, 409, 2001. 4. G. R. Desiraju, J. Chem. Soc., Dalton Trans., 3745, 2000. 5. S. Subramanian et al., Coord. Chem. Rev., 137, 357, 1994. 6. J. D. Ranford et al. Angew. Chem., Int. Ed., 37, 1114, 1998. 7. J. D. Ranford et al. Angew. Chem., Int. Ed., 38, 3498, 1999. 8. N. Kumar et al. CrystEngComm, 16, 6730, 2014.
P-355:Chemistry and applications of Selenadiazoles in nanotechnology
Aditi Jadhav, P. K. Khanna*. Nanochemistry Lab, Department of Applied Chemistry, Defence Institutes of Advanced Technology (DIAT), Girinagar, Pune *Email: [email protected]
Abstract Organoselenium compounds are highly recognized class of chalcogens because of their remarkable reactivity and chemical properties. We are focusing mainly on organoselenium compounds containing Se- & N-elements particularly, selenadiazoles. There are various types of selenadiazoles. These have attracted much attention due to their anticancer, anti microbial and other pharmaceutical applications Mousa Al-Smadi etal [2]. Additionally, 1,2,3-selanadiazoles have been proven to be excellent precursors for ligand chemistry as well as material chemistry. Applications of 1,2,3-selenadiazoles in material chemistry are mainly due to their ability to release free active Se during thermolysis or photolysis. The by-product of 1,2,3-selenadiazole under these conditions is an alkyne molecule which is considered to be useful during formation of semiconductor nano particles particularly, of metal selenide quantum dots. Quantum dots are useful in solar cells and biology. This Presentation describes chemistry of various 1,2,3-selenadiazoles were synthesised and characterized by various spectroscopic tools. The new selenadiazoles were found to be excellent precursors for preparation of quantum dots and MSNCS of CdSe and other metal selenides which can alter the face of nanotechnology
O R N N H2SeO3 R N NH NH2 RT Se R H Scheme 1. Synthesis of 1,2,3-selenadiazole from semicarbazone and selenious acid.
R N N CdSe Se R' Scheme 2. Synthesis of CdSe quantum dots from selenadiazole.
2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 Density distribution q3* distribution Density 0.8 0.6 0.4 0.2 0.0 0.6 0.8 1.0 2 4 6 8 10 20 40 60 80 100 particle size / nm
. Figures. XRD,UV-Visible, PL, XRD and Particle size spectra of CdSe Nanoclusters.
.
References: [1] Chacogenadiazoles-chemistryand Applications. Taylor & Francis Group, LLC, 215, 2012. [2] Mousa Al-Smadi and Fouad Al-Momani, Molecules 13, 2740 (2008 [3] P.K.Khanna, Journal of Nanoscience and Nanotechnology, 11, 1, 2011. [4] P.K.Khanna, R.M. Gorte, R.Gokhale, Material Letters 58, 966, 2004. [5] P.K.Khanna, Priyesh More, Rahul Shewate, R. K. Beri, A. Kasi Viswanath, Vidyanand Singh, Bodh R. Mehta, Chemistry Letters, 38, 7, 2009.
P-356: Design of solid catalyst for the transformation of glycerol to glycidol via glycerol carbonate
Sunil Galani, Tapan Sahoo, Asit Baran Panda and Subhash Chandra Ghosh* Discipline of Inorganic Materials and Catalysis, Academy of Scientific and Innovative Research, CSIR- Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, Gujarat, India E-mail: [email protected]; [email protected],
Glycerol is the main co-product of the biodiesel production as well as other vegetable oils industry. As the production of glycerol is increasing very fast so to find out new applications of glycerol to some value added product is challenging task for chemists. Glycidol is one of the most attractive and valuable derivatives of glycerol. Glycidol synthesized from glycerol via formation of glycerol carbonate using urea or DMC (dimethyl carbonate) over metal (K, Fe, Cu, Al, etc.) loaded mesoporous zirconium phosphate (m-ZrP) under conventional heating. The present methodology is environmentally benign as no hazardous chemical is use and the metal loaded m-Zrp is reusable.
Fig.1 Fig.2 Fig.1: Synthesis of glycidol from glycerol Fig.2: SEM (a) and TEM (b) image of m-ZrP References 1. C.-H. Zhou et al Chem. Soc. Rev.,37, 527, 2008. 2. R. Palkovitset alChem. Commun. 47, 576, 2011. 3. S. H. Cho et al. Angew. Chem. Int. Ed. 48, 9127, 2009.
P-357: Electrodeposited Cu2S as efficient counter electrode for CdSe/CdS sensitized solar cell Chaitanya Krishna Kamaja, 1 and Manjusha V. Shelke* 1 1Physical and material Chemistry Division, National Chemical Laboratory, Pune 411008, India
E-mail: [email protected]
Abstract
In quantum dot sensitized solar cells counter electrode plays vital role in the reduction of polysulfide electrolyte. Hodes et al. studied the electrocatalytic behaviour of several metal sulphides and found that Cu2S is a good candidate for the reduction for polysulfide electrolyte. For the preparation of thin films, electrodeposition has been widely used from long back century because of its low cost, low temperature processability, thickness tunability, morphological control and easily fabricated to the large area. The present works presents the simple one step electrodeposition of Cu2S on transparent conductive FTO/ glass substrate. When these electrodes are used in CdS/Cdse sensitized solar cell, The power conversion efficiencies (η) of electrodeposited Cu2S is 4.68%, which is higher when compared to chemically synthesized CuS (η=2.22%) and Pt (0.8 %) counter electrodes.
.
Figure.1: J-V Characteristics of QDSSCs with CuS, Pt and electrodeposited Cu2S counter electrodes.
References:
1) Mora-Seró, I et al., The Journal of Physical Chemistry Letters, 1, 3046, 2010.
2) Hodes, G et al., Journal of The Electrochemical Society, 127, 544, 1980.
P-358: Rh(III)-catalyzed regioselective relay-like catalysis: A rapid, sequential construction of polysubstituted isoquinolones triggered by double directing group
Vinod Gokulkrishna Landge† and Ekambaram Balaraman†* †Catalysis & Inorganic Chemistry Division, CSIR-National Chemical Laboratory (CSIR- NCL), Dr. Homi Bhabha Road, Pune 411008, INDIA e-mail: [email protected]
Design of new chemical approaches that enable increasingly rapid access to structural complexity by sequential transformations from simple starting materials remains a challenging and very important paradigm for the chemical sciences. In this perception, transition-metal catalyzed directed C-H functionalization received much attention and is an emerging area of research. Thus, a strategy allowing for rapid construction of molecular complexity using the C–H activation concept would require a multipurpose functional group. Isoquinolin-1(2H)-one derivatives are found in various natural products such as thalifoline, dorianine, ruprechstyril, narciclasine, pancratistatin and lycoricidine and serve as a versatile building blocks for the total synthesis of several alkaloids. Substituted isoquinolin-1(2H)- ones exhibit biological and medicinal activities such as antihypertensive activity. With this background, herein we report an efficient and highly regioselective Rh(III)-catalyzed stepwise C-H functionalization of benhydrazide with carbene, alkene, and alkyne respectively leads to polysubstituted isoquinolin-1(2H)-one (Scheme 1).
P-359: Palladium catalyzed C-C & C-N bond formation of sesquiterpene lactone, zaluzanin D isolated from the plant, Vernonia arborea
Innaiah K. Polanki,Tushar R. Valkute, Asish K. Bhattacharya*
Division of Organic Chemistry, CSIR-National Chemical Laboratory, Pune 411008, India
*E-mail: [email protected]
Zaluzanin D1 (1), α-methylene-γ-lactone sesquiterpene lactone isolated from Vernonia arborea when subjected 2 to arylation using Pd(OAc)2 as a catalyst using Heck reaction with various substituted aryl iodides resulted in the formation of a single isomer, E-olefin as a major product which was obtained in moderate to good yields.On the other hand, palladium catalyzed allylic amination of zaluzanin D (1) with diverse amines as nucleophiles under Tsuji-Trost3 reaction conditions led to the formation of a new C-N bond furnishing the amino derivatives in good yields. The chemistry of C-C and C-N bond formation reactions of zaluzanin D (1) will be discussed in detail.
References:
1. Romo, J.et al Terahedron. 1967, 23, 3903. 2. Arcadi, A.et al Org. Lett. 2000, 2, 69. 3. Trost, B. M.et al J.Org. Chem. 2004, 69, 581
P-360: Tuning the Formation of Encapsulated Water Cluster in Coordination Architectures via Chemical Modification in the Ancillary Ligands Sandeep Kumar,SadhikaKhullar and Sanjay Mandal* Department of Chemical Sciences, Indian Institute of Science Education and Research, Mohali, Sector 81, Manauli PO, S.A.S. Nagar, Mohali (Punjab) 140306, INDIA Email: [email protected] In the past 15 years, a large number of coordination architectures have been designed and developed for their diverse structural aesthetics and for a variety of potential applications [1-2]. These are prepared from a variety of metal centers or metal atom clusters and multiatom organic linkers. These architectures are held together through various supramolecularinteractions, such as metal-donor atom coordinate bonds, strong/or weak hydrogen bonds, π−πstacking of aromatic moieties, C-H…O interactions [3]. For our efforts [4] in this area, we have found that asimple chemical modification in thetridentate polypyridyl ancillary ligandsprovides an opportunity to tune the formation of encapsulated water clusters (dimers, pentamers, hexamers, etc.)in the M(II)-aliphatic dicarboxylate systems (where M = Mn(II), Ni(II), etc.). Furthermore, demonstration of anion exchange in the architectures has provided a better understanding of the hydrogen bonding interactions among the M(II)-carboxylate subunits and water clusters. In this presentation, few examples of Ni(II) will be used to elaborate the effect of the simple chemical modification (incorporation of methyl group(s) in the pyridine ring(s)) on the formation of encapsulated water clusters.
Figure: Diverse encapsulated water clusters in coordination architectures formed through supramolecular interactions.
REFERENCES
2. [1] (a) Cook, T. R.; Zheng, Y-R.; Stang, P. J. Chem. Rev., 2013, 133, 734. (b) Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012,112,673. (b) O’Keeffe, M.;Yaghi, O. M. Chem. Rev. 2012,112,675. (c) Stock, N.; Biswas, S. Chem. Rev. 2012,112,933. (d) Li, J.-R.; Sculley, J.; Zhou, H.-C. Chem. Rev. 2012,112, 869. 3. [2] (a) Dmitriev, A.; Lin, N.; Barth, J. V.; Kern, K. Angew. Chem. Int. Ed. 2003, 42, 2670. (b) Yaghi, O. M.; O’ Keeffe, M.; Ockwing, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature, 2003, 423, 705. (c) Stepanow, S.; Lingenfelder, M.; Dmitriev, A.; Spillmann,H.; Delvigne, E.; Lin, N.; Cai, C.; Barth, J. V.; Kern, K. Nat. Mater. 2004, 3, 229. (d) Kitagawa, S.; Kitaura, R.; Noro S. Angew. Chem. Int. Ed. 2004, 43, 2334. [3](a) Braga, D.; Grepioni, F. Acc. Chem. Res. 2000, 33, 601. (b) Desiraju, G. R.; Vittal, J. J.; Ramanan, A. Crystal Engineering. World Scientific Publishing Company: Singapore, 2011. [4] (a) Khullar, S.; Mandal, S. K. Cryst. Growth Des. 2012, 12, 5329. (b) Khullar, S.; Mandal, S. K. CrystEnggComm2013, 15, 6652.(c) ) Khullar, S.; Gupta, V.; Mandal, S. K. CrystEnggComm2014, 16, 5705.
P-361: Stable M(III/IV) Complexes in Dipyrromethane Platform (M=Cr, Mn, Fe, Co) Soumen Dey* Center for Applied Chemistry, School of Natural Sciences, Central University of Jharkhand, Ranchi-835205, India. *E-mail: [email protected], [email protected]
Chemistry of higher valent transition metals in various ligand platforms is of immense importance. Synthesis and transition metal chemistry of diphenyldipyrollide (DPDP) is shown here. This ligand is particularly promising due to its close structural resemblance to the ansa-metallocene ligand system. Diphenyldipyrrolide ligand was synthesized by condensing benzophenone and pyrrole in 1:3 ratios in water / ethanol medium in moderate high yield using our eco-friendly strategy. Metalation was carried out using different metal ions namely MnIII, FeIII, CoIII and VIV. The complexes were isolated as tetraethylammonium or tetraphenylphosphonium salt. All the complexes were characterized by elemental analysis and conventional spectroscopic techniques. Crystals for FeIII was not suitable for diffraction. Electrochemical study of FeIII complex in DMSO undergoes one electron reversible reduction at –0.54 V which may be due to FeIII / FeII couple. An additional peak appeared at –1.7 V. An oxidative response was found at +0.5 V which may be due to ligand oxidation. When the electrochemistry was performed in dichloromethane, the reduction peak shifts towards more potential and comes at –0.8 V. Solid state magnetic moments were measured in VSM and corresponding oxidation states were ascertained in the complex. Axial coordination chemistry in under progress.
Figure 1. Left: Synthesis of the complexes; Right: Cyclic voltammogram of FeIII-DPDP complex (a: in DMSO; b: in DCM).
References: 1. Setsune, J.; Muraoka, S.; and Yokoyama, T; Inorg. Chem. 1997, 36, 5135. 2. Scott, J.; Gambarotta, S.; Yap, G. P. A.; and Rancourt, D. G. Organometallics 2003, 22, 2325. 3. Gao, G.; Korobkov, I.; and Sandro Gambarotta Inorg. Chem. 2004, 43, 1108. 4. Tayebani, M.; Conoci, S.; Feghali, K.; Gambarotta, S.; and Yap, G. P. A. Organometallics 2000, 19, 4568.
P-362: New trans-[Pd(Imidate)2(PTA)2] complexes: Water Soluble Recyclable Catalysts for the synthesis of C5-arylated pyrimidine nucleosides via Suzuki-Miyaura cross-coupling. Anant Kapdi[a],* Vijay Gayakhe[a], Yogesh S. Sanghvi[b] Joaquín García[c] , Pedro Lozano[d], Ivan da Silva[e], José Pérez[f] and J. Luis Serrano[f]* a Dept.of Chemistry,Institute of Chemical Technology, Mumbai, Nathalal road, Matunga, Mumbai-400019, India. b Rasayan Inc. 2802, Crystal Ridge Road, Encinitas, California, 92024-6615, United States of America cDepartamento de Química Inorgánica, Regional Campus of International Excellence “Campus Mare Nostrum” Universidad de Murcia, 30071 Murcia, Spain. d Departamento de Bioquímica y Biología Molecular B e Inmunología. Facultad de Química, Regional Campus of International Excellence “Campus Mare Nostrum”,Universidad de Murcia, 30071 Murcia, Spain e ISIS Facility, Rutherford Appleton Laboratory, Chilton, Oxfordshire, OX11 0QX UK f Departamento de Ingeniería Minera, Geológica y Cartográfica. Universidad Politécnica de Cartagena. Área de Química Inorgánica, Regional Campus of International Excellence "Campus Mare Nostrum", Universidad Politécnica de Cartagena, 30203, Cartagena, Spain *E-mail: [email protected]
Nucleosides and their modification via metal-mediated cross-coupling processes have attracted considerable attention during the last decades due to their biological properties.1Palladium complexes have shown excellent reactivity towards the modification of nucleosides containing purines or pyrimidine series.2Arylation of 5-halo-2´-deoxyuridine has been demonstrated consistently using palladium-catalysed Suzuki-Miyaura or Stille cross-coupling reactions by several research groups. However, most of these reactions have been performed in organic solvents making the synthetic procedures environmentally less attractive3. So we developed a new water soluble complex which can be easily synthesized by the direct reactions between the precursors trans-[Pd(Imidate)2(SMe2)2] and 1,3,5-triaza-7-phosphaadamantane (PTA) yield new water-soluble palladium(II) complexes of general formula trans-[Pd(Imidate)2(PTA)2](Imidate = succinimidate (suc) 1, maleimidate (mal) 2, phthalimidate (phthal) 3 or saccharinate (sacc) 4. Spectroscopic techniques and structural characterisation by X-ray diffraction of complex 4 confirmed the proposed formulae. The new complexes have revealed as excellent catalysts for environmentally friendly, highly efficient Suzuki-Miyaura cross-coupling of (hetero)aryl halides as well as more challenging substrates like the antiviral nucleoside analogue 5-iodo-2´- deoxyuridine in water as solvent.
Fig. 1: General reaction of Suzuki-Miyaura cross coupling of 5-IdU/5-IdC Reference 1. I J S Fairlamb et al.,in "C-H and C-X bond activation",Catalytic C-H/C-X bond functionalisation of nucleosides, nucleotides, nucleic acids, amino acids, peptides and proteins 2013, Ed.: X.Ribas, Chapter 14, RSC book publishing. 2. a)H.W.-Rajchel et al.,J. Fluorine Chem.,135, 225–230,2012.b) G. S.Rani et al., J. Nat. Sci. Res.,3, 123, 2013,c)P. M. Gannett et al., Molecules 2009, 14, 3339-3352. 3. L. A. Agrofoglio et al.,Chem. Rev.,103, 1875-1916,2003.
P-363: Chemical and microbiological deterioration of ghol fish (Protonibea diacanthus) before transport to the landing center Ratish R. Nair,1 Nidhi Joshi,2 Vinod P. Boricha,2 Soumya Haldar,2* Pabitra B. Chatterjee1*
1Analytical Discipline and Centralized Instrument Facility, CSIR-CSMCRI, G. B. Marg, Bhavnagar- 364002, Gujarat, India. 2Marine Biotechnology and Ecology Discipline, CSIR-CSMCRI, G. B. Marg, Bhavnagar-364002, Gujarat, India. [email protected]
Abstract: One of the key factors for the production of quality seafood depends on the evaluation of raw materials quality before acceptance in the processing plants. Most of the available/practiced identification methods are conventional bio- chemical-based, non-specific, and lengthy. To evaluate the quality of fishery products rapidly and accurately which would provide revised guidelines for quality control, a combination of analytical and microbiological investigations on fish spoilage is needed. In this regard, we have initiated a project to identify few key biochemical transformations occurring during spoilage of edible marine fishes by studying concentration changes of crucial metabolites linked to such spoilage using time-scale 1H NMR spectroscopy. Studies on 1H NMR spectroscopy-based metabolic analysis and bacteriological degradation based on changes in heterotrophic plate counts (HPC) as well as functional diversity of ghol fish (Protonibea diacanthus ) tissue extracts were carried out to obtain information on quality changes during its storage in ice. This study revealed a wide distribution of metabolic signatures with the post mortem age of iced fish. Up to 4 days of ice storage there were little changes in concentration for few metabolites such as pyruvate, TMAO, and creatine/phosphocreatine which altered significantly afterwards. There was a drastic increase in total bacterial count after 9 days of ice storing and average well colour development (AWCD) value also increased with time. Interestingly, principal component analysis (PCA) on the basis of 31 carbon sources utilization by associated bacteria revealed closed clusters for initial day’s samples along with control.
P-364: Synthesis and characterization of Lanthanide(III) complexes of a mesogenic Schiff base derived from 2-(dodecylthio)-1H-benzimidazole Rajasekhar Yerrasani, M Karunakar and T.R.Rao*
Department of Chemistry, Banaras Hindu University, Varanasi-221005.
Abstract
Benzimidazole containing mesogenic ligand, 4"-(((2-(dodecylthio)-1H-benzimidazol-5- yl)imino)methyl)-3"-hydroxyphenyl-4'-(octyloxy)benzoate, (HL), has been synthesized and its complexation with hydrated lanthanide(ɪɪɪ) nitrates, was found to yield Lnɪɪɪ complexes of
the general composition [Ln(LH)3(NO3)3], where Ln = La, Pr, Nd, Sm, Eu, Tb and Dy. The ligand and the Ln(III) complexes were characterized by FTIR, NMR, UV-Vis, Fluorescence and mass spectrometry. Their phase transition behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. The IR and NMR spectral data imply a mono-dentate bonding (through phenolate oxygen) of the Schiff-base in its zwitterionic form (as LH) to the Ln(III) ions, rendering an overall nine-coordinated geometry to the complexes.
References
1. Lina Zhang, Xinbing Chen, Fengqi Zhao, Xuezhong Fan, Pei Chen & Zhongwei An. Liquid Crystals, 2013 Vol. 40, No. 3, 396–410
P-365: Transition-Metal-Free Multicomponent Reactions Involving Arynes Initiated by N-Heterocycles/Phosphines
Anup Bhunia, Tony Roy and Akkattu T. Biju *
Organic Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune - 411008, India, [email protected]
Arynes are highly electrophilic reactive intermediates, which have been extensively utilized in various carbon-carbon and carbon-heteroatom bond-forming reactions.1 One of the important modes of aryne reactivity is the participation in transition-metal-free multicomponent reactions (MCRs). In aryne MCRs, a nucleophile adds to aryne generating the aryl anion intermediate, which is subsequently quenched by electrophile leading to the synthesis of 1,2-disubstituted arenes of structural complexity. In the area of aryne MCRs, we have recently developed a transition-metal-free reaction involving arynes, N-heterocycles and various carbonyl compounds.2 With (iso)quinoline as the nucleophile, and carbonyl compounds such as aldehydes, ketones, and N-substituted isatins as electrophiles, the reaction afforded oxazino (iso)quinoline derivatives and the reaction proceeded via 1,4-dipolar intermediates. Interestingly, when the nucleophilic trigger used is pyridine, the reaction furnished indolin-2-one derivatives, and it is probable that the reaction proceeds via a pyridylidene intermediate. Moreover, with phosphines as nucleophiles, the aryne MCRs furnished functionalized benzooxaphospholes with wide variety of carbonyl compounds as the electrophilic third-component.3 The details of this work will be presented.
References 1(a) Bhojgude. S. S; Biju, A. T. Angew. Chem. Int. Ed. 2012, 51, 1520. (b) Bhunia, A.; Yetra, S. R.; Biju, A. T. Chem. Soc. Rev. 2012, 41, 3140. 2(a) Bhunia, A.; Roy, T.; Pachfule, P.; Rajamohanan, P. R.; Biju, A. T. Angew. Chem., Int. Ed. 2013, 52, 10040. (b) Bhunia A.; Porwal D.; Gonnade R. G.; Biju A. T. Org. Lett. 2013, 15, 4620, 3(a) Bhunia, A.; Kaicharla, T.; Porwal, D.; Gonnade, R. G.; Biju, A. T. Chem. Commun. 2014, 50, 11389.; (b) Bhunia, A.; Roy, T.; Gonnade, R. G.; Biju, A. T. Org. Lett. 2014, 16, 5132.
P-366: Functionalization of alkyne using TsNBr2: Synthesis of dibromodimethyl Ketals. Key word: TsNBr2, alkyne, dibromodimethyl ketals.
Kamal Krishna Rajbongshi, Prodeep Phukan*1 1Department of Chemistry, Gauhati University, Guwahati, 781014, Assam, India E-mail: [email protected]
Activation and functionalization of C-C triple bond is an attractive goal for some important organic transformation reaction in synthetic chemistry [1]. N,N-dibromo-p-toluenesulfonamide (TsNBr2) is a very efficient and powerful reagent for various organic transformations [2]. TsNBr2 reacts with alkyne in the presence methanol to form α,α-dibromodimethyl ketals instantaneously [3]. The reaction proceeds smoothly and instantaneously without using any other catalyst. The one step reaction can be carried out with most of the alkynes in high yield with high regio and stereoselectivities.
1 2 TsNBr2 H3CO OCH3 1 2 R R R MeOH,rt, N2 R Br Br
R1 and R2 may be alkyl, aryl, and H
Scheme1. Synthesis α, α-dibromodimethyl ketals using TsNBr2
Reference
1. Liu, B.; Brabander, J. K. Org. Lett. 2006, 8, 4907- 4910 2. (a) Prodeep Phukan, P.; Chakraborty, P.; Kataki, D. J. Org. Chem. 2006, 71, 7533-7537; (b) Saikia, I.; Phukan, P.; Tetrahedron Lett. 2009, 50, 5083–5087; (b) Saikia, I.;Kashyap, B.; Phukan, P. Chem. Commun. 2011, 47, 2967– 2969. (c) Saikia, I.; Rajbongshi, K. K.; Phukan, P. Tetrahedron Lett. 2011, 53, 758-761.(d) Borah, A. J.; Phukan, P. Chem. Commun. 2012, 48, 5491-5493. (e) Rajbongshi, K. K.; Sarma, M. J.; Phukan, P. Tetrahedron Lett. 2014, 55, 5358-5360.
3. Rajbongshi, K. K.; Phukan, P. Tetrahedron Lett. 2014, 55, 1877.
P-367: N-Heterocyclic Carbene (NHC)-Catalyzed Enantioselective Synthesis of Functionalized Cyclopentenes via α,β-Unsaturated Acyl Azoliums
Santigopal Mondal, Santhivardhana Reddy Yetra, Atanu Patra, Sunita S. Kunte, Rajesh G. Gonnade, and Akkattu T. Biju*
E-mail: [email protected]
The N-heterocyclic carbene (NHC)-catalyzed generation of α,β-unsaturated acyl azoliums followed by its interception with various nucleophiles is well documented.1 Intriguingly, however, the NHC-catalyzed generation of chiral α,β-unsaturated acyl azoliums is relatively rare. Recently we reported a highly enantioselective NHC-organocatalyzed synthesis of functionalized cyclopentenes.2 This organocascade reaction of modified enals with malonic ester derivatives having a γ-benzoyl group under NHC-catalysis proceeds via the chiral α,β-unsaturated acyl azolium intermediates. The efficient cascade reaction involves the Michael- intramolecular aldol-β-lactonization-decarboxylation sequence to deliver cyclopentenes in moderate to good yields and excellent ee values. Moreover, the reaction of 2-bromoenals with malonate derivatives possessing an aliphatic keto group under the chiral NHC-catalyzed conditions, furnished the highly diastereoselective and enantioselective synthesis of cyclopentane-fused β-lactone derivatives. The details of this work will be presented.
References
1. For selected recent reviews on NHC organocatalysis, see: (a) De Sarkar, S.; Biswas, A.; Samanta, R. C.; Studer, A. Chem. Eur. J. 2013, 19, 4664. (b) Ryan, S. J.; Candish, L.; Lupton, D. W. Chem. Soc. Rev. 2013, 42, 4906. (c) Bugaut, X.; Glorius, F. Chem. Soc. Rev. 2012, 41, 351. (d) Nair, V.; Menon, R. S.; Biju, A. T.; Sinu, C. R.; Paul, R. R.; Jose, A.; Vellalath, S. Chem. Soc. Rev. 2011, 40, 5336. 2. Mondal, S.; Yetra, S. R.; Patra, A.; Kunte, S. S.; Gonade, R. G, Biju, A. T. Chem.Commun. 2014, 50, 14539.
P-368: Hexamethyl benzene-1,3,5-triyltris(methylene)triphosphonate (HMBTP): A common internal standard for quantification of analytes by HPLC-UV, 1H-NMR and 31P{1H }-NMR spectroscopy
Avik Mazumder,* Ajeet Kumar and Devendra K. Dubey Vertox Laboratory, Defence R & D Establishment, Jhansi Road, Gwalior-474002.
Abstract: The simultaneous analyses of organophosphorus compounds by different analytical techniques (viz. HPLC-UV, 1H-NMR and 31P{1H}-NMR spectroscopy) entails multiple sample preparation and use of technique specific internal standards [1-15]. We introduce hexamethyl benzene-1,3,5-triyltris(methylene)triphosphonate (HMBTP), a new universal internal standard for quantification of organophosphorus compounds by the above techniques. The proposed standard HMBTP eliminates multiple sample preparations for quantitative experiments using the above mentioned analytical techniques. This compound can be synthesized easily from commercially available materials and it can be obtained in highly pure state. Thermal stability of HMBTP has also been demonstrated herein and variable temperature NMR spectroscopy also reveals that there is minimal variation in chemical shifts with change in solvent, pH and temperature. Since HMBTP is soluble in and compatible with a variety of solvents (from benzene to water) different organophosphorus analytes can be quantified using this compound. Suitability of HMBTP as an internal standard was also demonstrated by comparison with results obtained for reference materials reported earlier and also against extensively characterized organophosphorus compounds. Precision data (~1%) on a statistically significant set of analytes has been demonstrated. Use of HMBTP as an internal standard would result in minimal sample requirement and speed-up of the whole analytical process, without compromising the quality of analytical results.
Keywords: Internal standard, quantitative NMR spectroscopy, LC-UV, organophosphorus compounds.
References: [1] A. Mazumder, D.K. Dubey, Nuclear Magnetic Resonance (NMR) Spectroscopy. In: Reedijk, J. (Ed.) Elsevier Reference Module in Chemistry, Molecular Sciences and Chemical Engineering, Elsevier: Waltham, MA, USA., 2013. [2] A. Mazumder, P. Garg, D. Pardasani, A. Kumar, A.K. Purohit, D.K. Dubey, Analytical Methods 3 (2011) 1574. [3] A. Mazumder, H.K. Gupta, P. Garg, R. Jain, D.K. Dubey, J. Chromatogr. A 1216 (2009) 5228. [4] A. Mazumder, H.K. Gupta, R.K. Srivastava, D. Dubey, Defence Sci. J. 60 (2010) 502. [5] A. Mazumder, A. Kumar, D.K. Dubey, J. Chromatogr. A 1284 (2013) 88. [6] A. Mazumder, A. Kumar, D.K. Dubey, Indian J. Chem., Sect B (2014) 95. [7] A. Mazumder, A. Kumar, A.K. Purohit, D.K. Dubey, J. Chromatogr. A 1217 (2010) 2887. [8] A. Mazumder, A. Kumar, A.K. Purohit, D.K. Dubey, Anal. Bioanal. Chem. 402 (2012) 1643. [9] M.F. Alum, P.A. Shaw, B.C. Sweatman, B.K. Ubhi, J.N. Haselden, S.C. Connor, Metabolomics 4 (2008) 122. [10] A. Shimizu, M. Ikeguchi, S. Sugai, J. Biomol. NMR 4 (1994) 859. [11] G. Shao, R. Kautz, S. Peng, G. Cui, R.W. Giese, J. Chromatogr. A 1138 (2007) 305. [12] J.S. Nowick, O. Khakshoor, M. Hashemzadeh, J.O. Brower, Org. Lett. 5 (2003) 3511. [13] G. Maniara, K. Rajamoorthi, S. Rajan, G.W. Stockton, Anal. Chem. 70 (1998) 4921. [14] G.F. Pauli, Phytochem. Anal. 12 (2001) 28. [15] D.S. Argyropoulos, J Wood Chem. Technol. 14 (1994) 65.
P-369: Diels−Alder Reaction of Tropones with Arynes: Synthesis of Functionalized Benzobicyclo[3.2.2]nonatrienones Manikandan Thangaraj,a Sachin Suresh Bhojgude,a Rajesh H. Bisht,b Rajesh G. Gonnade,c and Akkattu T. Biju*,a
a Organic Chemistry Division, b Physical and Materials Chemistry Division, c Centre for Materials Characterization, CSIR-National Chemical Laboratory (CSIR-NCL), Dr. Homi Bhabha Road, Pune - 411008, India, Email address: [email protected]
Arynes are highly electrophilic reactive intermediates, which have been extensively utilized in various carbon-carbon and carbon-heteroatom bond-forming reactions.1 Recent developments in aryne chemistry have been devoted to transition-metal-free reactions, which include the Diels-Alder reaction of aryne with different dienes. We have recently developed highly selective, scalable, and broad scope Diels-Alder reaction of tropones with arynes generated from 2-(trimethylsilyl)aryl triflates leading to the practical synthesis of benzobicyclo[3.2.2]nonatrienone derivatives.2 In addition application of the tropone-aryne [4 + 2] cycloaddition reaction has been examined by the photochemical rearrangement of the cycloadduct to form the functionalized naphthalene derivative. Moreover, preliminary studies on photophysical properties of some of the cycloadducts have been carried out. The details of this work will be presented.
References 1. (a) Bhojgude. S. S; Biju, A. T. Angew. Chem. Int. Ed. 2012, 51, 1520. (b) Tadross, P. M.; Stoltz, B. M. Chem. Rev. 2012, 112, 3550. (c) Bhunia, A.; Yetra, S. R.; Biju, A. T. Chem. Soc. Rev. 2012, 41, 3140. 2. Thangaraj, M.; Bhojgude S. S.; Bisht R. H.; Gonnade R. G.; Biju A. T. J. Org. Chem. 2014, 79, 4757.
P-370: Synthetic Approaches towards Biologically Active Natural Products Employing Selenium mediated Oxidative De-aromatization and Ruthenium catalysis Manoj Kumar Ghosh , Nilendri Rout, Neha Chowdhury, Dr. Debayan Sarkar *, Department of Chemistry, National Institute Of Technology, Rourkela, Odisha, India Email: [email protected]
Synthetic efficiency has to be addressed not only by selectivity but also economically.1,2 Cationic Ruthenium (+2) complexes catalyse the coupling of alkynes and alkenes (an Alder–ene type reaction). A mechanism involving generation of a π-allyl ruthenium complex from activation of the alkene’s C-H was originally proposed; however, it is now generally believed that the reaction proceeds via a ruthenacyclopentene.3 The reaction has been investigated further with suitable coupling partners to generate piperidones in an atom - economic fashion. The substituted piperidones exhibit an appealing entry to a huge class of natural products. Coupling with Non-Michael acceptors have been initiated.
O H H O
H H HO R Penostatin A OH O ( Significant Cytotoxicity) [Se Catalyst] Se H H O O H R1 [Base] R1 H OH O Pseudoguaianolide ( Potent NO- inhibitor)
In another approach, a new Selenium mediated approach towards oxidative dearomatization of phenols lead to a novel seleno ─ enol intermediate which pave way towards newer synthetic intrigues towards bio- active natural products like Penostatins and pseudoguaianolides.
Concurrently, a novel and unprecedented C-methylation of chromane carboxylates has been accomplished with Corey-Chaykovsky Reagent. 4
TMSOI/NaH R O R1 O 1 DMSO (Dry) R2 R2 00C-rt O O R O R3 O 3 R O R4 O 4
Referrences : 1. B.M.Trost, Science 1991, 254, 1471. 2. B.M.Trost, Angrew. Chem. 1995, 107, 285; Angrew. Chem. Int. Ed. Engl. 1995, 34, 259. 3. a) Trost, B.M.; Indolese, A. J.Am.Chem. Soc. 1993, 115, 4361. (b) Trost, B.M.; Indolese, A.F., Muller , T.J.J.; Treptow, B. J.Am. Chem. Soc. 1995, 117, 615. 4. S.Ghosh, N.B.Chandar, D.Sarkar, M.K.Ghosh, B.Ganguly, I.Chakraborty, Synlett 2014, 25,000A-000E.
P-371: Novel Analogues of Lupeol and Their Anti diabetic Activity Kapil Dev,1 Akhilesh K. Tamrakar,2 Rakesh Maurya*1 1Medicinal & Process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow- 226031, India. 2Biochemistry Division, CSIR-Central Drug Research Institute, Lucknow-226031, India. E-mail: [email protected], [email protected] Keywords: Type 2 diabetes mellitus, Lupeol, Isopropylene moiety, Glucose uptake stimulation
Structure modifications of lupeol at the isopropylene moiety have been described via allylic oxidation using selenium dioxide [Jean et al (1)]. The antidiabetic efficacy of lupeol analogues were evaluated in vitro as glucose uptake stimulatory effect in L6 skeletal muscle cells. From all seventeen tested compounds, 2, 3, 4b and 6b showed significant stimulation of glucose uptake with respective percent stimulation of 173.1 (p<0.001), 114.1 (p<0.001), 98.3 (p<0.001) and 107.3 (p<0.001) at 10 µM concentration. Stimulation of glucose uptake by these compounds is associated with enhanced translocation of glucose transporter 4 (GLUT4) and activation of IRS-1/PI3-K/AKT-dependent signaling pathway in L6 cells [Khan et al (2)]. Structure-activity relationship analysis of these analogues demonstrated that the integrity of α, β-unsaturated carbonyl and acetyl moieties were important in the retention of glucose uptake stimulatory effect. It is therefore, proposed that naturally occurring lupeol and their analogues might reduce blood glucose, at least in part, through stimulating glucose utilization by skeletal muscles.
Fig. 1: Basic skeleton of Lupeol, showing the possible chemically active centers.
Reference: 1. F. D. Jean; B. Scott; L. L. Mara; G. Elias; G. Rukunga; N. E. Augustin, J. Nat. Prod. 69, 62, 2006. 2. M. F. Khan; C. K. Maurya; K. Dev; D. Arha; A. K. Rai; A. K. Tamrakar; R. Maurya, Bioorg. Med. Chem. Lett. 24, 2674, 2014.
P-372: Stories of Design and Surprise: Diels-Alder Reaction of Arynes with Unconventional Dienes S. S. Bhojgude,a T. Kaicharla,b M. Thangaraj,c A. Bhunia,d A. T. Biju*
Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Pune- 411008
Arynes are highly reactive intermediates that garnered tremendous attention from the chemical community for the construction of multisubstituted arenes of structural diversity and complexity. Due to their high electrophilicity, arynes have been shown to react with a wide variety of dienes and dipoles.1 The Diels–Alder reaction is one of the important reactions of arynes, which is a powerful tool for constructing various carbocycles and heterocycles of synthetic importance. We have developed a practical, scalable and efficient Diels-Alder Reaction of pentafulvenes with arynes leading to benzonorbornadiene derivatives.2 In addition the Diels-Alder reaction of arynes can be coupled with other organic transformations there by leading to efficient cascade processes. We have recently reported the reaction of arynes with styrenes leading to the synthesis of 9- aryldihydrophenanthrene derivatives. The reaction proceeds via a cascade process initiated by a Diels-Alder reaction of styrenes with arynes followed by a selective ene reaction.3 This is very interesting as the utility of styrenes as the 4π-component in Diels−Alder reactions utilizing a carbon-carbon double bond, which is involved in aromaticity. In this context, we have developed a facile and general reaction of arynes with indene/benzofurans. The reaction took place via a tandem [4+2]/[2+2] cycloaddition sequence resulting in the formation of dihydrobenzocyclobutaphenanthrene derivatives in moderate to good yields and in excellent diastereoselectivity.4 The details of the work on Diels-Alder reaction of arynes with challenging dienes and the application of arynes in various carbon-carbon bond-forming reactions will be presented.
Reference
[1] A. Bhunia, S. R. Yetra, A. T. Biju, Chem. Soc. Rev. 2012, 41, 3140. [2] S. S. Bhojgude, T. Kaicharla, A. Bhunia, A. T. Biju, Org. Lett. 2012, 14, 4098. [3] S. S. Bhojgude, A. Bhunia, R. G. Gonnade, A. T. Biju, Org. Lett. 2014, 16, 676. [4] S. S. Bhojgude, M. Thangaraj, E. Suresh, A. T. Biju, Org. Lett. 2014, 16, 3576.
P-373: Facile Synthesis of γ‑Ketophosphonates by an Intermolecular Stetter Reaction onto Vinylphosphonates
Atanu Patra, Anup Bhunia and Akkattu T. Biju* Organic Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune - 411008, India, [email protected]
Organophosphorus compounds are an important class of molecules having potential application in various areas of chemistry including materials chemistry, pharmaceuticals, agrochemicals, and in catalysis.1 Among the various organophosphorus compounds, phosphonates in general and γ-ketophosphonates in particular are associated with diverse biological properties.2 One of the versatile and powerful methods for the synthesis of γ- ketophosphonates is via the phospha-Michael reaction by the addition of phosphorus nucleophiles to α,β-unsaturated ketones.3 In this context, we reported a new approach to the synthesis of γ-ketophosphonates by generating the acyl anion equivalents by the umpolung of aldehydes under N-heterocyclic carbene (NHC) catalysis, followed by its subsequent interception with α,β- unsaturated phosphonates. A wide variety of electronically and sterically different aldehydes, and several α,α-disubstituted α,β- unsaturated phosphonates are well tolarated under the optimized reaction conditions. The present reaction can be considered as a hydroacylation to moderately electron-poor C−C double bond of vinylphosphonates.4 The details of this work will be presented.
References 1 (a) Stolar, M.; Baumgartner, T. Chem.- Asian J. 2014, 9, 1212. (b) Mathey, F. Angew. Chem., Int. Ed. 2003, 42, 1578. (c) Bialy, L.; Waldmann, H. Angew. Chem., Int. Ed. 2005, 44, 3814. 2(a) Romanenko, V. D.; Kukhar, V. P. Chem. Rev. 2006, 106, 3868. (b) Moonen, K.; Laureyn, I.; Stevens, C. V. Chem. Rev. 2004, 104, 6177. 3For a review, see: Enders, D.; Saint-Dizier, A.; Lannou, M.; Lenzen, A. Eur. J. Org. Chem. 2006, 29. 4 Patra, A.; Bhunia, A.; Biju, A. T. Org. Lett. 2014, 16, 4798.
P-374: Functional polymers and polymer derived nanostructures: fabrication, physical properties and detailed spectroscopic investigations Pragyan Pallavi, Sujoy Bandyopadhyay, Ravindra G and Abhijit Patra* Department of Chemistry, Indian Institute of Science Education and Research, Bhopal 462066, India. E-mail: [email protected]
The past few years have witnessed an avalanche of research activities in nanomaterials based on fluorescent polymers. Due to their unique light harvesting ability, fluorescent conjugated polymer (FCP) nanoparticles have emerged as important candidates in fluorescence-based sensing and imaging devices.[1] FCP nanoparticles of polyfluorene (PF) and poly(triphenylamine) (PTPA3) were fabricated by mini-emulsion technique (Fig. 1a, b). Triplet emitters (Ru complexes) were attached to the surface of these surfactant stabilized nanoparticles through electrostatic interactions. Energy transfer photophysics of these nanostructured, multichromophoric systems are being probed by steady state and time resolved fluorescence measurements. Besides FCP, microporous organic polymers (MOPs) with extended π-electron conjugated segments have been explored recently for various optical applications in addition to gas storage and gas separation.[2, 3] In view of the development of functional, conjugated, porous polymers, we have designed monomer 4,4',4'',4'''- (5,5-dioctylcyclopenta-1,3-diene-1,2,3,4-tetrayl)tetrakis(bromobenzene) (DCTB). Network polymers were synthesized by palladium-catalyzed Sonogashira cross-coupling reactions. Fine tuning of fabrication conditions led to the formation of polymers in the form of amorphous solid, strongly fluorescent solution as well as in the form of nanoparticles. Detailed spectroscopic and microscopic characterizations, gas adsorption studies, molecular dynamic simulations (Fig. 1c) and photophysical investigations have been carried out. The present study establishes DCTB based MOPs as a new material that exhibits efficient light emission in different physical states in addition to surface properties, paving the way to potential future applications.
a) b) c)
Fig.1: FESEM images of (a) PF nanoparticles (b) PTPA3 nanoparticles. (c) Illustration of amorphous cell of DCTB based MOP at 77K (dots: adsorbed N2 molecules, shades: solvent accessible surface area).
Reference 1. J Pecher, S Mecking, Chem. Rev., 110, 6260, 2010. 2. Patra, A.; Scherf, U. Chem. Eur. J., 18, 10074, 2012. 3. Cheng, G.; Bonillo, B.; Sprick, R. S.; Adams, D. J.; Hasell, T.; Cooper, A. I. Adv. Funct. Mater., 24, 5219, 2014.
P-375: Enhanced removal of Mn(II) from aqueous solution using surfactant- modified alumina: kinetics, equilibrium and thermodynamic study
M.U. Khobragade1, A. Pal2
1Research scholar, Civil Engineering Department, Indian Institute of Technology, Kharagpur- 721302, India. Email:[email protected] 2Associate Professor, Civil Engineering Department, Indian Institute of Technology, Kharagpur-721302, India
Abstract This paper describes the adsorption of Mn(II) from aqueous solutions by modified alumina. The alumina has been modified with sodium dodecyl sulfate (SDS), an anionic surfactant to have admicellar structure on its surface. This admicelle has the capability to adsorb organic molecules as well as metal ions through a process called ‘adsolubilization’. The adsorption of Mn(II) follows pseudo-second order kinetic model. The adsorption obeys Freundlich isotherm. The ∆G, ∆H and ∆S values of the adsorption process indicate that the adsorption process is spontaneous and endothermic. The adsorption results obtained by batch technique demonstrate that, SMA can be used as a potential adsorbent for the removal of Mn(II) from aqueous solution.
Keywords: Surfactant-modified alumina; Mn(II) removal; Kinetics; Isotherm models; Thermodynamics
P-376: Recent development in sensing mechanism for the design of fluorescent chemosensors Mrituanjay D. Pandey* and Rampal Pandey* Department of Chemistry, (School of Chemical Science & Technology), Dr. H. S. Gour Central University Sagar, MP 470003, India. *E-mail: [email protected] (MDP); [email protected] (RP)
Keywords: Fluorescence, Sensor, Mechanisms
During the past decade, development of fluorescence sensors with superb selectivity and sensitivity has become an important area of research of supramolecular chemistry. The design of new fluorescent chemosensors and exploration of new sensing mechanisms is of continuing interest. The conventional sensing mechanisms including intramolecular charge transfer (ICT), photo-induced electron transfer (PET), twisted intramolecular charge transfer (TICT), metal–ligand charge transfer (MLCT), electronic energy transfer (EET), excimer/exciplex and fluorescence resonance energy transfer (FRET) formation have been investigated. In the past few years new sensing mechanism has been worked out such as C N isomerization, aggregation-induced emission (AIE), Two-Photon-Absorption Technique and excited-state intramolecular proton transfer (ESIPT).
Fig.1: Various methodologies developed and mechanisms discussed for chemosensing
Reference 1. Wu, J.; Liu, W.; Ge, J.; Zhanga, H.; Wang, P. Chem. Soc. Rev., 2011, 40, 3483-3495. 2. Chandrasekhar, V.; Pandey, M. D.; Maurya, S. K.; Sen P.; Goswami, D. Chemistry: An Asian J., 2011, 6(9), 2246– 2250. 3. Chandrasekhar, V.; Bag P.; Pandey, M. D. Tetrahedron, 2009, 65(47), 9876–9883. 4. Pandey R.; Gupta R. K.; Shahid M.; Maiti B.; Misra A.; Pandey D. S. Inorganic Chemistry 2012, 51, 298-311. 5. Pandey R.; Kumar P.; Singh A. K.; Shahid M.; Li P.-Z.; Singh S. K.; Xu Q.; Misra A.; Pandey D. S Inorganic Chemistry 2012, 51, 298-311.
P-377: DFT Investigation of the Aromatic Character of Phosphacyclopentadienide Anions Raakhi Gupta*, Pooja Maheshwari, Swati Mahawar Department of Chemistry, The IIS University, Mansarovar, Jaipur 302 020, India *E-mail: [email protected]
Keywords: Phosphacyclopentadienide anions, Aromaticity, DFT study, 1H NMR values, NICS
Abstract: The concept of aromaticity has fascinated chemists since its introduction by Kekule in the year 1865. Over the years, new and new criteria have been proposed to ascertain whether a particular system is aromatic or not. Greater stability, equalization of bonds, induction of a diatropic ring current by an external magnetic field resulting in deshielding of ring protons are some of these criteria. Nucleus independent chemical shift (NICS) is the latest addition to this list [1,2]. Cyclopentadienyl anion (cyclopentadienide) is a well known aromatic system, fulfilling most of these criteria. In accordance with the diagonal relationship in the periodic table, phosphorous resembles carbon more than the nitrogen [3]. Due to this reason, phosphorous has been called “Carbon Copy of the Carbon”. It motivated us to investigate the effect of CH/P exchange in cyclopentadienide on its aromatic character theoretically. We have studied the following systems at the DFT level (B3LYP/6-31+G**):
P
P C P P P H
P P PP PP
P P P P P P P P P
Isodesmic reactions reveal that CH/P exchange in cyclopentadienyl anion is accompanied by high stabilization energies (-9 to -27 kcal mol-1) indicating comparable or even higher aromatic character of the resulting phosphacyclopentadienide anions. The Natural Bond Orbital (NBO) studies show that anionic charge in phosphacyclopentadienide anions, as in cyclopentadienyl anion, interacts strongly with the π orbitals leading to complete delocalization of six electrons. The calculated 1H NMR chemical shift values of both, cyclopentadienyl anion and phosphacyclopentadienide anions fall in the aromatic region, ca. δ 6 and 7 ppm respectively. Furthermore, the NICS values, NICS (0) and NICS (1), ca. -14.06 and -9.71 also support the aromatic character of the phosphacyclopentadienide anions.
References [1] P.v.R Schleyer; M. Manoharan; H. Jiao; F. Stahl, Organic Lett., 3, 3643, 2001. [2] P.v.R. Schleyer; H. Jiao; N.J.R.v.E. Hommes; V.G. Malkin; O.L. Malkina, J. Am. Chem. Soc., 119, 12669, 1997. [3] A. Schmidpeter, Heteroat. Chem., 10, 529, 1999.
P-378: A comparative study to the molecular association of 2-hydroxy-1,4- naphthoquinone and its C(3) derivatives by X-ray crystallography and electrochemical studies Umar Dar, Yogesh Shinde, Sujit Bhand, Sunita Salunke-Gawali* 1Department of Chemistry, Savitribai Phule Pune University, Pune- 411007, India *Corresponding author-e-mail: [email protected]
2-hydroxy-1,4-naphthoquinone commonly known as lawsone, it is the main component of Heena plant namely Lawsonia Alba and Lawsonia inermis. This compound commonly used in dye industry, pharmacological industry. Few new applications were also emerged to lawsone viz, as finger print marker, and dye sensitized solar cells in recent years. Pharmacological and other applications of quinones are because of their redox activity; they could either accept or donate electrons with respect to the need of biological function and moreover these redox processes may involve the molecular association of quinone molecules in solution. Molecular structures of lawsone and its C(3) derivatives showed polymorphic forms in solid states and polymeric molecular assemblies were formed by intermolecular hydrogen bonding and π-π stacking interactions [1]. Intermolecular hydrogen bonding includes C-H∙∙∙O and strong O-H∙∙∙O. interactions. Molecular association of hydroxy naphthoquinones was also observed in solution, which can be determined by electrochemical studies. In present investigation comparative studies of molecular association of lawsone and its C(3) derivatives have been made in solid state by single crystal X-ray crystallography and in solution state by electrochemical studies. Molecular structures of methyl (Fig.1 left) and bromo (Fig.1 right) derivatives were reported.
Fig.1: Molecular association of 3-methyl 2-hydroxy-1,4-naphhoquinone (left) and 2-bromo-3-hydroxy-1,4- naphthoquinone(right)
References
1. S. Salunke-Gawali, L. Kathawate, Y. Shinde, V.G.Puranik, J. Mol. Struct,. 1010(2012)38-45.
P-379: Quantum dots based on-chip label free electrochemical DNA aptamer sensor for pancreatic cancer Preeti Nigam Joshi, Michelle Louis, Dhiman Sarkar Combichem Bioresource Center, National Chemical Laboratory, Pune –India-411008 Email: [email protected]
Pancreatic cancer is the most fatal cancer and the most difficult maligency to handle due to its late diagnosis and poor prognosis. The conventional detection methods are tedious procedures and early detection is not possible in most of the cases. That makes it imperative to discover newer detection methods for early diagnosis of this deadly disease. Here for the first time we are reporting a new miniaturized on-chip DNA aptamer based biosensor for mucin -1 (MUC-1) protein over-expressed in pancreatic cancer and can be explored for early diagnosis of pancreatic cancer. A miniaturized on-chip three electrode electrochemical assembly was fabricated. Graphene quantum dots were utilized for modification of glassy carbon working electrode and MUC-1 specific aptamer [1] was immobilized on quantum dots modified working electrode surface. Impedance spectroscopy was the preferred technique to detect the specificity of aptamer against MUC-1 in pancreatic cancer cell suspension and real blood samples. Fig 1 exhibits the impedance spectra of MUC-1- aptamer interaction and change in resistant on electrode surface was measured. Based on the experimental findings, it can be concluded that the above described methodology has the potential to be explored as an efficient detection tool for early detection of pancreatic cancer.
Figure 1: Impedance spectra of Aptamer- MUCI1 interaction on graphene quantum dots modified glassy carbon electrode
Reference:
[1] Ferreira et. al. DNA aptamers that bind to MUC1 tumour marker: Design and characterization of MUC1-binding single- stranded DNA aptamersTumor. Biol. 27, 289, 2006.
P-380: Synthesis of visible light driven ZnO: Characterization and photocatalytic performance Waseem. Raza, M.M. Haque, M. Muneer*
Department of Chemistry, Aligarh Muslim University, Aligarh – 202002, India
Nanocrystalline materials of pure and doped ZnO with La/Ce metals have been successfully synthesized using sol gel method. The prepared materials were characterized by standard analytical techniques, i.e., XRD, SEM, EDX, UV–vis Spectroscopy and FTIR. The (XRD) analysis showed that the obtained particles are present in partial crystalline nature with Hexagonal wurtzite phase and exhibit no other impurity phase. The EDX and (SEM) images depicted that La and Ce metals have been successfully loaded on the surface of ZnO. FTIR of La doped ZnO showed an additional absorption band at−1, 910 cm characteristic of La–O absorption band indicating the incorporation of dopant into the ZnO lattice in addition to a broad and strong absorption band in the region of 410–580 cm−1 due to Zn–O stretching. The UV–vis absorption spectra of synthesized particles indicate that the doping of La and Ce metals into the ZnO lattice shift the absorption band towards the visible region. Thermal analysis, measurement of the synthesized sample showed that the thermal stability of pure ZnO is decreased due to increase in dopant concentration. The photocatalytic activity of the synthesized particles was studied by measuring the change in concentration of three different chromophoric dyes as a function of irradiation time. The photocatalytic activity of doped ZnO was found to increase with increase in dopant concentration of Ce from 0 to 2.0% and La from 0 to 0.9%. A further increase in dopant concentration led to decrease in the degradation rate of dyes. Keywords: Doped ZnO; Degradation; Sol-gel; Dyes; Photocatalysis; Visible light. *Corresponding author. Tel.: +91-571-2700920 ext. 3365. E-mail address: [email protected]; [email protected] (M. Muneer)
P-381: In-gel Colorimetric Detection of Proteins in Activity based Protein Profiling S.Kumari, 1 C.Panda, 1 S. S.Gupta, 1 1Chemical Engineering Division, National Chemical Laboratory, Pune 411008, India *E-mail: [email protected]
The sensitivity of any analytical protocol is determined by the correlation between the analyte concentration and the strength of the output signal. The importance of this correlation is illustrated by the development of biological assays such as the introduction of enzyme-linked immunosorbent assays (ELISA’s). The conceptual novelty lies in the application of signal amplification: a single analyte molecule recruits an enzyme able to generate a multitude of reporter molecules, which is ultimately determined by the turn-over number of the enzyme. One enzyme which is very routinely used for signal amplification is horseradish peroxidise (HRP), which in the presence of H2O2 converts a non-chemiluminiscent molecule into a chemiluminiscent molecule with several thousand turnovers, thus decreasing the detection limits by several folds. FeIII biuret complexes1 are excellent functional mimics of the enzyme HRP and they have been shown to convert colorless substrates like TMB into their blue colored one-electron oxidized product in the presence of III H2O2. We propose to develop protocols and methods in which Fe biuret can replace HRP as a probe for analyte detection. Special emphasis would be given to the usage of FeIIIbiuret in activity based protein profiling (ABPP). ABPP relies on the design of active-site directed covalent probes to investigate specific families of enzymes in complex proteomes2. The fundamental building blocks of ABPP are small-molecule probes that covalently label the active site of a given enzyme or enzymes. These inhibitor probes which get covalently bound to the enzyme of interest are attached to a reporter tag to facilitate target characterization. Examples of reporter tags include fluorophores, biotin, and latent analytical handles such as alkynes or azides, which can be modified by click chemistry methods to visualize protein targets post-labeling by gel electrophoresis as has been shown by Cravatt et. Al3. Typically fluorescent probes like rhodamine is used as the reporter tag and this limits the detection limit for the enzyme of interest. We propose the replacement of fluorescent probe with FeIIIbiuret, which is a peroxidise mimic and would amplify the signal to lower the detection limit. We have designed a flurophosphonate probe that targets the serine hydrolase family of enzymes, was covalently attached to FeIII biuret complexes using azide-alkyne cycloaddition chemistry. Then it was analyzed by SDS-PAGE and in-gel colorimetric detection of proteins, using a mixture of H2O2 and a peroxidase substrate (TMB) which generates a blue coloured band. This allows visual detection of proteins upto 50 ng/ml and also shows that the CuAAC was very efficient (protein conc. of <1.5µM). It also shows selectivity towards the serine hydrolases, when the reaction was carried out in a mixture of proteins.
Fig.1: Schematic for signal amplification by FeIII biuret in ABPP
Reference 1. S.S. Gupta et al., Chem. Commun., 49, 2216, 2013 2. B. F. Cravatt et al., PNAS., 96, 14694, 1999. 3. B.F. Cravatt et al., J. Am. Chem. Soc., 125, 4686, 2003
P-382: Biomilling of Geothite nanorods by yeast S. cerevisiae
Chandrashekhar Sharan, Pankaj Poddar* Physical and Materials Chemistry Division, National Chemical Laboratory, Pune 411008, India E-mail: [email protected]
Iron has been the most widely used metal since Iron Age. Its applicability is greatly limited due to oxidation to form rust/corrosion (oxides and oxyhydroxide), because of a large difference in standard redox potential between iron and oxygen. It has been highly desirable to use rust materials, by value addition to it. Since last decade, our group has pioneered in successfully utilizing the bioleaching process for the synthesis of nanoparticles. This method has been validated for the breakdown of micron-sized particles down to few nanometers, termed as biomilling. In the present work, biomilling is explored to convert anisotropic oxyhydroxide particles into isotropic particles, with the help of yeast Saccharomyces cerevisiae (NCIM 3064). In order to mimic the natural rust of iron, we have synthesized its main component i.e. α-FeO(OH) (geothite) nanorods, by low temperature, surfactant free route. The as-synthesized nanoparticles have well- defined rod-shaped morphology of length (200 - 400 nm) and diameter (~ 30 nm). After biomilling for 120 h, these nanorods were broken down to form quasi-spherical nanoparticles below 10 nm. The transmission electron micrographs (TEM) as well as atomic force microscopy (AFM) images revealed the way of disintegration of particles. The particles obtained after biomilling, were quasi-spherical in shape and are notably different from parent nanorods. The proteins secreted from yeast cells, formed a robust capping around biomilled nanoparticles, which improves their aqueous dispersion and biocompatibility.
Fig.1. Schematic of the experiment. 2. UV-vis spectra of samples collected at different times, 3. TEM images shows the disintegration of particles from rod-shaped into quasi-spherical form (A) 0 h, (B) 24 h, (C) 48 h, (D) 96 h, and (E) 120 h. Inset zoom to show the isolated nanoparticles. (F) Dark-field image of same area of (E). 4. The X-ray diffractograms of particle before and after biomilling could be indexed to orthorhombic phase of α- FeOOH, as per JCPDS 86-493. 5. FTIR spectra of samples collected at different times, showing amide bands of protein corona around biomilled nanoparticles. 6. AFM phase image, and 7. TEM image of 96 h sample reveals the fine details of the biomilling process.
Reference 1. B. Mazumder et al., J. Mater. Chem., 17, 3910-3914, 2007. 2. P.V. Adhyapak et al., J. Am. Ceram. Soc., 96, 731-735, 2013. 3. I. Uddin et al., Int. J. Innov. Biol. Res., 2, 1-5, 2013.
P-383: One Pot Hydrothermal Synthesis of Morphology Based Monoclinic BiVO4 and Enhanced Photo-Catalytic Activity Aniruddha Mondal, Dr. Subhash C. Ghosh and Dr Asit B. Panda* Discipline of Inorganic Materials and Catalysis, Academy of Scientific and Innovative Research, CSIR-Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, Gujarat, India. E-mail:[email protected],[email protected]
Recent day’ssynthesis of nanostructuredBiVO4 with varying size, shape and morphology gained remarkable attentiondue to its characteristic visible light absorption and improved visible active photocatalytic activity.
Triethanoloamine (TEA) assisted,rice shaped morphology based BiVO4has been synthesized by one pot hydrothermal process(Figure-1).The synthesized BiVO4was characterised by P-XRD,UV-DRS, SEM, TEM,
BET-surface area and H2-TPR analysis.XRD analysis of calcinedmaterial confirmed the formation of pure monoclinic phase. TEM analysis of the BiVO4depicts crystalline in nature. Here it is essential to mentioned that theTEAhas a key role for the shape selective synthesis and BiVO4with varying morphology was synthesized by varying the amount of TEA. The synthesized rice shaped BiVO4showed improved photocatalytic activity for selective oxidation of cyclohexene to cyclohexenone, with 98% conversion and 72% selectivity, in presence of molecular oxygen at room temperature (Scheme 1).
Fig: 1. (a) SEM images and(b) P-XRD pattern of Calcined BiVO4.
Scheme 1. Photo Oxidation of Cyclohexene in presence of Visible Light
Reference: 1. W. Wang et alCrystEngComm12, 1754, 2010. 2. K. S. Suslicket al J. Phys. Chem. Letter, 113, 11980, 2009.
P-384: Synthesis, Characterization and Studies of Structural Properties of Mixed Ligand Photoluminescent Zn(II)/Cd(II) Coordination Polymers B. Parmar,1,2 K.K. Bisht1,2 and E. Suresh1,2* 1 Analytical Discipline and Centralized Instrument Facility, 2 Academy of Scientific and Innovative Research (AcSIR), CSIR–Central Salt and Marine Chemicals Research Institute, (CSIR-CSMCRI), G. B. Marg, Bhavnagar 364 002, Gujarat, India. *E-mail: [email protected]
Coordination Polymers (CPs)/Metal–organic frameworks (MOFs) have been the focus of great interest due not only to their structural and chemical diversities but also potential structure-related applications, such as gas storage, separations, catalysis, iodine adsorption[1], luminescence[2], sensing[3] and drug delivery[4]. Studies suggest that design and synthesis of CPs generally depend on several factors coordination ability of metal node, counter-anions, ligand flexibility, solvent etc. Mixed ligand CPs are distinguished class of solid materials due to the modulation and tunability of the metal centres and ligand moiety to achieve aesthetic structural assemblies for specific application. Two isostructural mixed ligand coordination polymers CPs have been fabricated by the judicious choice and combination of flexible dicarboxylate and N-donor Schiff base linkers. Thus, two mixed ligand 2D CPs, {[M(1,3CDC)(L)]}n comprising of (Cyclohexane-1,3-dicarboxylate) and hydrazone Schiff base ligand L (3-pyridylcarboxaldehyde isonicotinoylhydrazone) with different metal centres (M=Zn(II) 1 and Cd(II) 2)have been synthesized and by diffusion method and characterized by physicochemical techniques including single crystal X-ray diffraction. Crystallographic studies revealed that both CPs are isostructural and possesses an intriguing 2D framework. Selection of d10 metal nodes Cd(II) and Zn(II) in CPs afforded significant fluorescence in solid state. Syntheses, characterization, structural properties of the fluorescent Zn/Cd CPs 1 and 2 will be discussed in detail. We are currently exploring the application of these material towards molecular sensing, guest encapsulation and photocatalysis.
Fig.1: Packing diagram of (a) CP1 view down b axis and (b) CP2 view down a axis
Reference
1. (a) Chem. Rev., 112 (2), 2012; (b) Chem. Soc. Rev., 43, 2014. 2. J. Li et al., Chem. Soc. Rev., 43, 5815, 2014. 3. J.T. Hupp et al, Chem. Rev., 112, 1105, 2012. 4. C. Serre et al, Chem. Rev., 112, 1232, 2012.
P-385: One pot synthesis of stable 5,11,17,23-tetraamino-calix[4]arene and SnO2 nanoparticles as potential sensor of Fe(III) in aqueous media
Gaurav Vyas1, Anshu kumar1,2, Parimal Paul*1,2 1Analytical Discipline and Centralized Instrument Facility, Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, India 2Academy of Scientific and Innovative Research, Central Salt and Marine Chemicals Research Institute, Bhavnagar-364002, India *E-mail: [email protected]
Sensing of targeted metal ions in different medium is an important area of research and different methods and tools have been developed for this purpose. Calixarene is one among the most readily available synthetic molecular baskets for sensing application. It is widely used as molecular receptor with different types of substituents on its hydrophobic upper rim, hydrophilic lower rim and also at methyl bridge1-3. Several lower rim substituted calix[4]arene derivatives were developed for sensing of various analytes. We have synthesized upper rim tetraamine substituted calix[4]arene conjugate. The stable form of 5,11,17,23-tetraamino- calix[4]arene is synthesized by reduction of tetranitro-calix[4]arene using SnCl2.2H2O with some modification 1 of the literature procedure and characterized by H NMR, MS and FT-IR (Fig.1). During this synthesis, SnO2 nanoparticles were also generated, which exhibited selective sensing of Fe(III) in aqueous media. Iron is most abundant element on the earth and also essential transition metal which plays important 4 role in biological system . The above mentioned in situ generated SnO2 nanoparticles is used for sensing of Fe(III) in presence of other metal ions studied in water system. The detailed synthetic methodology and sensing studies will be presented in our poster.
Fig.1: Synthetic route of 5,11,17,23 tetraamine calix[4]arene & SnO2 nanoparticles
Reference 1. Y. Zhao et al., J. Org. Chem., 71, 9491, 2006. 2. P.Paul et al., New J. Chem., 36, 988, 2012. 3. S.E. Biali et al., J. Org. Chem., 79, 538, 2014. 4. D. Kumar et al., Microchemical J. 113, 77, 2014
P-386: Heterogeneously Porous γ-MnO2-Catalyzed Direct Oxidative Amination of Benzoxazole through C-H Activation in the Presence of green oxidant O2 Harshvardhan Singh, Asit B. Panda*, Subhash C. Ghosh*, Discipline of Inorganic Materials and Catalysis, Academy of Scientific and Innovative Research, CSIR- Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, Gujarat, India. E-mail: [email protected], [email protected]
The C-N bond formation reaction of aromatic and heteroaromatic compounds is one of the most important and vastly used transformations in synthetic organic chemistry. It is ever demanding simply because of the great interest in nitrogen-containing heteroaromatic molecules in pharmaceutical, biological, and materials sciences. However, most of the reported methods are performed under homogeneous reaction conditions using excess reagents and additives. Herein, we report the heterogeneous, porous ɣ-MnO2-catalyzed direct amination of benzoxazole with wide range of primary and secondary amines. The amination was carried under mild reaction conditions and using molecular oxygen as a green oxidant, without any additives. It is important to note that, the reaction is well tolerated with functional group like alcohol indicating the broad applicability of this reaction. The catalyst can easily be separated by filtration and reused several times without a significant loss of its catalytic performance.
Scheme 1. Amination of benzoxazole with amine.
Figure 1 a) XRD; b) SEM, c) TEM and d) BET Table 1. Amination of benzoxazole with amines surface area of our synthesized γ –MnO2 catalyst
Reference: 1. J. Y. Kim et. al., Angew. Chem. Int. Ed. 49, 9899, 2010. 2. P. Pal et. al., J. Mater. Chem. A, 1, 10251, 2013. 3. P. Pal et. al., Chem. Asian J. 9, 2392, 2014
P-387: Potential-Controlled Synthesis of Bismuth Particle from nitric acid bath: A Study of Various Morphologies, Optical properties. Ashis Das, 1 M.V.Sangaranarayanan *1 1Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India *E-mail: [email protected]
Various morphologies such as triangle, flower, dendritic bismuth nanostructures have been electrodeposited on conductive ITO surface via a facile constant potential Electrodeposition method at room temperature. Different geometries of bismuth were controlled majorly through potential, time of deposition and concentration of nitric acid. The phase and morphology of the deposits were characterized by means of powder X-ray diffraction (XRD), energy dispersive spectrometer (EDS), (high resolution) transmission electron microscopy (HR/TEM), selected area electron pattern (SAED) and scanning electron microscopy (SEM) respectively. The ultraviolet-visible (UV-VIS) absorbance spectrum of the bismuth particle showed at 338 and 445 nm, which could be ascribed to the effect of the surface plasmon resonance and light scattering.
Fig.1: SEM image of various bismuth particles; (a) and (b) Triangles, (c) dendrites and (d) flowers.
References 1. Ruiling Fu et al., Cryst. Growth Des., 2005, 5, 1379–1385. 2. A. R. Rajamani et al., CrystEngComm, 2014, 16, 2032-2038.
P-388: Potential-Controlled Synthesis of Bismuth Particle from nitric acid bath: A Study of Various Morphologies, Optical properties. Ashis Das, 1 M.V.Sangaranarayanan *1 1Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India *E-mail: [email protected]
Various morphologies such as triangle, flower, dendritic bismuth nanostructures have been electrodeposited on conductive ITO surface via a facile constant potential Electrodeposition method at room temperature. Different geometries of bismuth were controlled majorly through potential, time of deposition and concentration of nitric acid. The phase and morphology of the deposits were characterized by means of powder X-ray diffraction (XRD), energy dispersive spectrometer (EDS), (high resolution) transmission electron microscopy (HR/TEM), selected area electron pattern (SAED) and scanning electron microscopy (SEM) respectively. The ultraviolet-visible (UV-VIS) absorbance spectrum of the bismuth particle showed at 338 and 445 nm, which could be ascribed to the effect of the surface plasmon resonance and light scattering.
Fig.1: SEM image of various bismuth particles; (a) and (b) Triangles, (c) dendrites and (d) flowers.
References 1. Ruiling Fu et al., Cryst. Growth Des., 2005, 5, 1379–1385. 2. A. R. Rajamani et al., CrystEngComm, 2014, 16, 2032-2038.
P-389: Eco friendly synthesis of magnetite nano particles and their characterization.
Manisha Bora, 1, 2 Pravin Adhav, 1 Prakash Chhattise, 1 Babasaheb Diwate, 1 Sandesh Mutkule, 1 Akshada Hande, 1 Kakasaheb Mohite, 3 Vasant Chabukswar, 1*
1Department of Chemistry, Nowrosjee Wadia College 19, Bund Garden Road, V. K. Joag Path Pune- 411001. India 2Bhartiya Jain Sanghatana’s ASC College,Nagar Road, Wagholi, Pune-412 207, India 3Dean, Faculty of Science, Savitribai Phule Pune University. Pune-411005, India Email- [email protected]
Abstract:
In recent years magnetic nano particles have attracted much attention of researcher because of their good electrical, optical, magnetic and catalytic activity in organic synthesis. Ferrites are a large group of oxides with remarkable magnetic properties and having great applications. We have developed eco-friendly method for the synthesis of iron oxide (Magnetite) nanoparticles at ambient temprature in aqueous media. Magnetic iron oxide (Fe3O4) nanoparticles are synthesized in single step by one pot co-precipitation method [1] using ferrous and ferric salts in presence of mild base. The size of synthesized nano particles was controlled by using surface complexing agents such as starch. The morphology of nanoparticles was characterized by using UV, IR, XRD and SEM [2]. The magnetite synthesized by this method shows super magnetism at room temperature.
Keywords: Magnetism, Magnetite, Nanoparticles, Co-precipitation, Mild base.
References:
[1] Maria Cristina Mascolo and et al, Materials, 6, 5549-5567, 2013 [2] H.El Ghandoor and etal, Int. J. Electrochem. Sci., 7, 5734 – 5745, 2012
P-390: Dinuclear Copper (II) Helicates and its Chiroptical Applications E. Chinnarajaa,b and P.S. Subramanian*
a) Discipline of Inorganic Materials and Catalysis, CSIR-Central Salt and Marine Chemicals Research Institute, Bhavnagar-364002, Gujarat, India. b)Academy of Scientific and Innovative Research, New Delhi.
Abstract
The term “helicate” was introduced by Jean Marie Lehn 1987 for metal complexes that contain one or more ligand strands wrapped around the two or more metal centers. Helicate thus formed gained chiral property due to the helical arrangement of the ligands. This intrinsic chiral property in helicate chemistry is considered in parallel to the chirality associated with asymmetric chiral carbon in organic chemistry. Further chiral ligand upon coordination to the metal center transfer chirality to the metal center and thus the metal center gains chirality. Thus the chirality transfer is considered potential to promote some smart chiroptical devices and enantioselective catalysts, etc. The synthesis of new enantiopure chiral helicates is considered to play potential role in the area of catalysis, material science and pharmaceuticals. The best way for the synthesis of enantiopure metal complexes is by the use of pre-programmed chiral ligands that are known to be efficiently transferring their chirality to the metal or molecular assembly. With this mind we have synthesized enantiomerically pure macrocyclic ligands LRRRR and LSSSS with four in-built chiral centers. These enantiopure ligands were prepared from the chiral 1, 2-diphenyl ethylene diamine and 3, 3’-methylenebis (5-(tert-butyl)-2-hydroxybenzaldehyde). Both these ligands were characterized by NMR, UV -Vis, FT-IR, Elemental analysis and MS spectra. Further the chiroptical properties were extensively investigated by Circular dichroism spectroscopy. The chiroptical studies Illustrates that these ligands are effectively involves in chiral transfer from ligand to the Cu(II) metal center and produce ∆∆ and ΛΛ enantiomers by LRRRR and LSSSS respectively. The associated chiral amplification process observed in the CD analysis will also be presented.
2 1 120 100 80 L-RRRR 60 40 20 0
CD mdegCD -20 -40 -60 -80 -100 L-SSSS 300 400 500 600 700 800 Wavelength (nm)
Figure 1. CD spectra of ligands and their respective complexes were recorded in THF (1x10-4 M)
References
1 J.Crassous Chem Commun., 2012, 48, 9684-9692. 2. A. Das, R.I. Kureshy, N. Ch. Maity, P. S. Subramanian, N. H. Khan, S.H. R. Abdi, E. Suresh and H. C. Bajaj, Dalton Trans 2014, 43, 12357.
P-391: DNA binding and BSA binding studies of pyridine based New unsymmetrical Schiff base macrocyclic Zn(II) complexes Vedavalli Sairaj and Muthusamy Kandaswamy*
Department of Inorganic Chemistry, University of Madras, Guindy Campus,
Chennai, 600 025, India.
E-mail: [email protected]
*Corresponding Author: [email protected], (Prof.Dr. M.kandaswamy)
Ph.No: +91-44-22202796 Fax: + 91 44 2230 0488
1-3 Abstract- A new series of binuclear Zn(II) complexes[Zn2L ].2ClO4 with new unsymmetrical binucleating macrocyclic ligands were synthesized by cyclocondensation between N,N’-bis(3-formyl-5-methylsalicylidene) alkane diimines (PC1-3 and 3,4 -diamino – pyridine) in the presence of Zinc (II) acetate and Zinc (II) perchlorate (1:1:1:1 molar ratio). Characterisation of these complexes was carried out using FT-IR, electronic and mass spectral studies and also by elemental analysis. The interactions of the complexes with DNA have been measured by spectroscopic and viscosity measurements. Absorption spectroscopic investigation reveals that the Zn (II) complexes bind with DNA by intercalative binding 4 4 4 -1 mode, with binding constants(Kb) 2.3x10 , 3.6x10 and 4 x10 M for the complexes 1-3 respectively. Fluorescence spectroscopic measurement shows that the Zn (II) complexes can 6 displace ethidium bromide and bind to DNA, with binding constants(Kapp) of 3.6x10 , 4.2x106and 5.3x106 M-1 for the complexes 1-3 respectively. The interaction of the complexes with BSA has been studied by UV-Vis absorption and fluorescence spectroscopic techniques. The results indicate that the complexes have a quite strong ability to quench the fluorescence of BSA and the binding reaction is mainly a static quenching process. The complexes exhibit good binding propensity to BSA showing relatively high binding constant values. Keywords:Unsymmetrical binucleating macrocyclic ligands;Zn(II) complexes; DNA and BSA binding properties.
CH3
NH2 Zn(OAc)2 H2O + R DMF /600C NH2
O OH O
P-392: “Development of NHC-Phosphine Ligated Iridium Complexes for Alkylation of Amines” Vijay Singh Parihar1,2, Pher G. Andersson2* and Dilip D. Dhavale1* 1Garware Research Centre, Department of Chemistry, Savitribai Phule Pune University, Pune - 411007, India 2Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, SE-106 91, Stockholm, Sweden [email protected]
Alkylation of amines has raised considerable attention, whilst alkyl halides are traditional alkylating agents for amines, they can be toxic and mutagenic. As an alternative, the alkylation of amines by alcohols has been achieved using various transition-metal catalysts, where a metal catalyst “borrows” hydrogen from an alcohol to give more reactive an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C–C bonds where the only by-product is typically water. The overall process has been termed “borrowing hydrogen,” strategy (Fig.-1).
Fig.1: Borrowing hydrogen strategy in the alkylation of amines with alcohols
Fig.2: Alkylation of amines catalyzed by newly developed Iridium catalysts. The first homogeneously catalyzed alkylation of amines with alcohols was described by Grigg et al. [1] (rhodium catalyst) and Watanabe et al. [1] (ruthenium catalyst) in 1981. To date, a number of metal catalysts, including complexes of ruthenium, rhodium, palladium, silver, osmium, copper, iron and iridium, have been evaluated in this transformation [2]. More recently research in this area mainly focused on the iridium and ruthenium based catalysts [3]. Recently our group has developed an efficient NHC-phosphine ligated iridium catalyst for N-alkylation of amines with alcohols [4]. In the continuation of our efforts in this area here we have synthesized three NHC- phosphine ligated iridium complexes (i), (ii) and (iii) (Fig.-2) which were screened for alkylation of aniline at mild reaction conditions.
References 1. a) R. Grigg, et al, J. Chem. Soc. Chem. Commun., 611-612, 1981; b) Y. Watanabe, et al, Tetrahedron Lett. 22, 2667-2670, 1981. 2. S. Bähn, et al., ChemCatChem., 3, 1853-1864, 2011. 3. a) I. Cumpstey, et al., Chem. Commun., 7827-7829, 2011. b) S. Bähn, et al., Chem. Eur. J., 16, 3590-3593, 2010. 4. Pher G. Andersson et al., Chem. Commun., 49, 6131—6133, 2013.
P-393: Level of Scrambling in Porphyrin-Forming Reactions Using Electron Deficient Dipyrromethanes: Synthesis, Characterization and Quantitative Crystal Structure Analysis
Fasalu Rahman Kooriyaden, Subramaniam Sujatha and Chellaiah Arunkumar*
Bio-inorganic Materials Research Laboratory, Department of Chemistry, School of Natural Sciences, National Institute of Technology Calicut, Kozhikode, Kerala − 673 601, India.
E-mail: [email protected]
MacDonald type condensation of dipyrromethane with an aldehyde has been accepted for the synthesis of a wide variety of trans-A2B2 meso-substituted porphyrins [1]. In addition to trans-porphyrin, scrambling process leads to the formation of other porphyrins such as A4, A3B cis-A2B2, AB3 and B4. The acid catalyzed fragmentation of polypyrrane breaks into pyrrolic and azafulvene, recombination of these components leads to cis-porphyrin. The other porphyrins are formed due to undesired fragment recombination [2]. Herein, we report the various level of scrambling in the reaction of less sterically hindered electron deficient dipyrromethanes (5- benzonitrile, 5-pentafluorophenyl and 5-carboxymethyl dipyrromethanes) with their corresponding aromatic aldehydes in presence of acid catalysts such as BF3⋅OEt2 and TFA [3]. The copper(II) complexes of all derivatives were also synthesized upon metal insertion reactions using copper(II) acetate. Synthesized porphyrins were characterized by UV-Visible, 1H NMR and mass spectroscopic techniques as well as by single crystal X-ray diffraction analysis. To quantify the various intermolecular interactions present in the porphyrins [4], the quantitative crystal structure analysis were done by Hirshfeld surface analysis using Crystal Explorer 3.1.
References:
1. J. S. Lindsey et al., J. Org. Chem., 64, 1391, 1999 2. (a) B. J. Littler et al., J. Org. Chem., 64, 2864, 1999 ; (b) G. R. Geiger III et al., J. Chem. Soc., Perkin Trans. 2, 701, 2001 3. F. R. Kooriyaden et al., J. Fluor. Chemistry, 2014 (Under revision). 4. (a) R. Soman et al., J. Fluor. Chemistry, 16, 163, 2014; (b) R. Soman et al., Eur. J. Inorg. Chem. 2653, 2014
P-394: Design, Modulations and Rational Synthesis of Metallophosphates Aijaz Ahmad Dar and R. Murugavel* Department of Chemistry, Indian Institute of Technology Bombay, Powai 400076, India E-mail: [email protected]
The discovery of phosphate analogues of aluminosilicate zeolites with open framework structures in 1981 has boosted the research activity in the field of metal phosphates.1 Since then these compounds have found applications as catalysts, ion exchangers and conductors, optical and laser materials, etc. However, even after more than three decades of extensive research, the synthetic design of these extended solids is not understood, necessitating further research.2 Herein we report the structural variations in zinc phosphate cluster chemistry by careful selection of phosphate ligand source, ancillary ligand and reaction solvent medium, resulting in the isolation of a series of molecular, supramolecular, and extended zinc phosphates. Single-4-Ring (S4R), Double-4-Ring (D4R) and Double-8-Ring (D8R) units which are important Secondary Building Blocks have been isolated and characterized. The insight into the solid-state structures of these compounds provides vital details about the mechanism involved in the buildup of higher extended solids. Further, the utility of D4R based zinc phosphates has been explored in fields of gas storage, fluoride encapsulation and molecular recognition.
Scheme 1. Synthesis and structural modulations in molecular zinc phosphates
References 1. S. T. Wilson, B. M. Lok, C. A. Messina, T. R. Cannan and E. M. Flanigen, J. Am. Chem. Soc. 1982, 104, 1146. 2. (a) A. C. Kalita, N. Gogoi, R. Jangir, S. Kuppuswamy, M. G. Walawalkar, and R. Murugavel, Inorg. Chem., 2014, 53, 8959. (b) A. C. Kalita, C. Roch-Marchal and R. Murugavel, Dalton Trans., 2013, 26, 9755. (c) A. C. Kalita and R. Murugavel, Inorg. Chem., 2014, 53, 3345.
P-395: Rhodium Catalyzed ortho C-H bond Activation of Anilines for the Synthesis of 3-substituted Quinolines Sunita K. Gadakh and Arumugam Sudalai* Chemical Engineering and Process Development Division, National Chemical Laboratory, Pashan Road, Pune 411008, INDIA.
Abstract: An approach to the synthesis of the 3-substituted quinolines [1] via rhodium catalyzed ortho C-H bond activation of anilines using formic acid and alkyl propiolates. Present methodology deals with the synthesis of 3-substituted quinolines with good yields upto 90% and high selectivity.
Fig.1: Rh-catalyzed ortho C-H activation of anilines.
Reference 1. M. Nicholas et al., J. Org. Chem., 68, 6427-6430, 2003.
P-396: Synthesis of two distinct heterocycles by combined use of an Ugi four-component reaction and metal catalysts Mrityunjaya Asthana, 1 R. M. Singh *1 1Department of Chemistry, Banaras Hindu University, Varanasi 221005, India E-mail: [email protected] *Corresponding author: [email protected]
Nitrogen-containing heterocyclic compounds are the privileged structures of several natural products.[1] The development of efficient, rapid and versatile routes for the synthesis of aza-heterocycles has become a key area of research. Isocyanide-based multicomponent reactions (IMCRs) because of their high degree of atom economy, convergence and productivity have become efficient tools to efficiently generate drug-like nitrogen heterocycles.[2] Among IMCRs there has been growing interest in Ugi reaction [3] along with palladium- or copper-catalyzed reactions for subsequent secondary transformations to increase scaffold and molecular complexity.[4] Among the N-heterocycles, benzo[b][1,6]naphthyridine and pyrrolo[2,3-b]quinolines are interesting skeleton as they exhibit wide range of biological activities.[5] Herein, we present one-pot two step efficient syntheses of 1,2-dihydrobenzo[b][1,6]naphthyridines [6] and pyrrolo[2,3-b]quinolines via sequential Ugi four-component and palladium/copper-catalyzed reactions respectively from cheap and easily available starting materials.
CN R2 CHO O + HO R1 N Cl NH2
MeOH, rt 10- 12 h O R2 R2 O NH O NH N O Pd(OAc)2 (5 %) O CuI (5 %) NaOAc (2 equiv) 1,0-phen (10%) N N OH DMF, 90 °C K2CO3 (2 equiv) N N DMF, 120 0C R1 N N Cl R2 R1 R1 65-75% 80-85%
R1= H, Me, OMe, Et, Cl, Br R2=t-butyl, n-butyl,cyclohexyl
References 1. B. Alcaide et al., Curr. Opin. Drug. Discov. Devel, 13, 685, 2010. 2. (a) H. Zhu et al., Multicomponent Reactions, Wiley-VCH, Weinheim, Germany, 2005; (b) R. V. A. Orru et al., Chem. Soc. Rev., 41, 3969, 2012. 3. (a) I. Ugi et al., Angew. Chem., 71, 386, 1959; (b) I. Ugi et al., Angew. Chem., 72, 267, 1960. 4. (a) A. Dömling et al., Org. Lett., 15, 639, 2013; (b) A. Dömling et al., Chem. Rev., 106,17, 2006. 5. (a) M. Kobayashi et al., Bioorg. Med. Chem., 11, 1969, 2003; (b) M. A. Khan et al., Heterocycles 6, 1229, 1977 and references cited therein. 6. R. M. Singh et al., Tetrahedron, 70, 7996, 2014.
P-397: Polynitro-substituted s-Triazine derivatives as energetic materials T. Vikranth, Pradeepta K. Panda * School of Chemistry, Advanced Centre of Research in High Energy Materials (ACRHEM) University of Hyderabad, Hyderabad 500046, India *E-mail: [email protected]
s-Triazine is an intriguing heterocycle, used as a building block for high energy materials and exhibits a high degree of thermal stability.1 Nitrogen-rich compounds derive their energy from the large number of energetic N-N and C-N bonds in the compounds. Endowed with interesting properties viz. high density, large positive heat of formation and thermal stability, nitrogen-rich compounds possess potential applications as explosives, smoke free pyrotechnics, gas generators, solid fuels in micropropulsion and precursors for energetic nano materials.2-3 In this direction, we have designed, synthesized and characterized several polynitro- substituted s-triazine derivatives. The density functional theory (Gaussian 09) is used to predict the geometries, heats of formation and other energetic properties.4-5 Among them, 3, 6 and 8 compounds show promising energetic properties.
Reference
1. L.Turker, T. Atalar, S. Gumus, Y. Camur, J. Hazard Mater., 167, 440, 2009. 2. C. Ye, H. Gao, J. A. Boatz, G. W. Drake, B. Twamley, J. M. Shreeve, Angew. Chem. Int. Ed., 45, 7262, 2006. 3. A. Fischer, M. Antonietti, A. Thomas, Adv Mater., 19, 264, 2007. 4. V. D. Ghule, S. Radhakrishnan, P. M. Jadhav, S. P. Tewari, E-J. Chem., 9, 583, 2012. 5. M. H. Keshavarz, K. Esmailpoor, M. K. Tehrani, Propellants. Explos. Pyrotech., 35, 482, 2010.
P-398: Synthesis and characterization of a new class of annelated 1,3- azaphospholes:bis-(alkoxycarbonyl)-1,3-azaphospholo[4,5- f]phenanthridines Deepika Singh1, Pragya Sinha1, Neelima Gupta2, R. K. Bansal*1 1Department of Chemistry, The IIS University, Jaipur 302020, India 2Department of Chemistry, University of Rajasthan, Jaipur 302055, India. E-mail: [email protected]
Keywords: Annelated 1,3-azaphosphole, 1,5-Electrocyclization, Bis(alkoxycarbonyl)-1,3-azaphospholo[4,5- f]phenanthridines, 31P NMR, 1H NMR
Abstract: The reaction of N-(alkoxycarbonyl)methylcycloiminium bromide with PCl3 In presence of Et3N in dichloromethane affords annelated 1,3-bis(alkoxycarbonyl)-1,3-azaphospholes through intramolecular 1,5- electrocyclization followed by 1,2- elimination.1 These compounds are particularly interesting as the >C=P functionality in these compounds is quite reactive and undergoes Diels- Alder reaction under mild conditions.2 It motivated us to extend this strategy to the synthesis of a new class of annelated 1,3-azaphospholes namely bis(alkoxycarbonyl)-1,3-azaphospholo[4,5-f]phenanthridines.
On treating a suspension of N-(alkoxycarbonyl)methylphenanthridinium bromide with PCl3 (0.5 eq.) and Et3N (2eq.) at room temp.(~250C) under nitrogen, bis(alkoxycarbonyl)-1,3-azaphospholo[4,5-f]phenanthridines were obtained in good yields. The compounds have been characterized on the basis of 31P NMR [δ= 175.51(R=OMe), 174.91(R=OEt)], 1H and 13C-NMR spectroscopy.
O PCl3(0.5 eq.), t BuOMe Et3N(2 eq.) BrCH2-C N r.t. N N COR R CH Cl , r.t. Br CH2 2 2 C P O ROC R R= OCH3, OCH2CH3, OCH(CH3)2, OC(CH3)3
References:
1. Bansal, R. K.; Surana, A.; Gupta, N., Tetrahedron Lett., 1999, 1565-1568. 2. Bansal, R. K.; Kumawat, S. K.; Tetrahedron, 10945, 64, 2008.
P-399: Direct versus conjugate addition of secondary amines and related compound to maleic anhydride: Experimental and theoretical results Manjinder Kour, Raakhi Gupta*, R. K. Bansal Department of Chemistry, The IIS University, Mansarovar, Jaipur 302 020, India
Keywords: Aza-Michael addition, Secondary amines, 1,2-Addition, 1,4-Addition, DFT studies
Abstract: In the Michael addition to the α,β-unsaturated enones, nucleophile may attack the carbon atom of the carbonyl group (direct or 1,2-addition) or the β-carbon atom (conjugate or 1,4-addition). Direct addition is found to be kinetically controlled whereas conjugate addition is thermodynamically controlled. Direct addition often competes with the conjugate addition and several reports have appeared about 1,2-versus 1,4-addition of enolates to enones.1 We have investigated direct versus conjugate addition of secondary amines to maleic anhydride experimentally and theoretically for the first time.
O O O H H
1 2 R R NH O O H O
H R1R2N O R1R2N OH OH
1,2-add.product 1,4-add.product
Me
1 2 R R = EtEt.,Me N O Me NN , H , , , ,
As expected, 1,2-addition predominates at low temperature,(ca. -15˚C) whereas at higher temperature ( ca. 40˚C), 1,4-addition product is the main product. Theoretical studies at the DFT(B3LYP/6-31+G**) level show that 1,3-prototropic shift in the initially formed 1,4-addition product occurs through the formation of the reactant complex. Furthermore, nucleophilic indices of the secondary amines relative to maleic anhydride have been calculated to explain their behavior.
References: 1. Schultz,A.G.; Yee,Y. K.; J. Org. Chem., 1976, 41, 4045. 2. Jaramillo,P.; Perez,P.; Contreras,R.; Tiznado,W.; Fuentealba,P.; The Journal of Physical Chemistry A, 2006, 110(26), 8181.
P-400: New Process for the Preparation of Aromatic Ketones from Arenes and Carboxylic acids over P2O5 Rupali G. Kalshetti, Madhura Gandhe, Vishal Valse, Sanjay P. Kamble*, Gurunath Suryawanshi, Arumugam Sudalai*, CEPD Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune- 411008 Ph # 020 25902174; Fax: 020 25902676 E-mail: [email protected]
Abstract: Aromatic ketones, such as 4-hydroxyacetophenone, are valuable fine chemicals for the synthesis of variety of pharmaceutical substances 4-hydroxyacetophenone derivatives shows trypanocidal and antifungal property.1 Friedel-Crafts acylation of phenol derivatives and Fries rearrangement of acyloxy benzenes are major pathways for preparation of hydroxyaryl ketones.2 A new synthetic route is developed for acylation of aromatic compounds with carboxylic acids in the presence of P2O5 as catalyst/dehydrating agent. The methodology is demonstrated at laboratory scale for acylation of phenol which gave 4-hydroxyacetophenone with conversion of 100% and p-selectivity to >98%. The process is eco-friendly and product isolation was made easier by simple filtration.
Scheme 1: Acylation of aromatic compounds with carboxylic acids over P2O5
References:
1. A.M. Nascimento et al., J.Pharm Pharmacol . 56,663-9, 2004 . 2. (a) M. M. Khodaei et al., Bull. Korean Chem. Soc., 32, 1785, 2011. (b) H. Eshghi et al., J. Chem. Research (S), 763– 764, 2003.
P-401: Synthesis and DNA binding study of some novel Molecular Tweezers S. Selvarani and P. Rajakumar*
Department of Organic Chemistry, University of Madras, Maraimalai campus, Chennai– 600 025, INDIA
Email: [email protected]
Abstract
Thiophene amide based dendrimers are an interesting way to prepare surface to be used in many branches of the synthetic chemistry. Dendrimers are large and complex molecules were synthesized by divergent or convergent plausible method. Dendrimers are attractive devices, enormous various applications in many fields such as catalysis, energy transfer, molecular recognition, organic electronic devices,1 electronics, photonics, and biotechnology.2 Dendrimers and cyclophane can be early achieved from molecular tweezers by suitable synthetic transformation. Thiophene derivatives show diverse optoelectronic properties3 and biological activities.4 Hence we wish to investigate thiophene amide based dendrimers were synthezised with two or four dendrons around the core via 1, 2, 3-triazole units as well as the dendrimers with zeroth and first generation dendrons have been prepared by using a both convergent and divergent approach. The compounds synthesized and characterized by spectral and elemental analysis. The optoelectronic properties of molecular tweezers thiophene amide functionality are investigated by UV-vis spectroscopy, DNA binding properties. The interactions of Molecular tweezers with calf thymus DNA were studied by absorption and fluorescence spectroscopic technique.
References:
1. Stefan, H.; Johannes, K..; Kookheon, C.; Heeje, W.; Andreas F.M.; Kilbinger, Marcomol. Rapid Commun.2009, 30, 1249. 2. William J. M.; Nikos Kopidakis, Garry , R.; David, S.; Ginley and Sean, E.; Shaheen, J. Mater. Chem., 2005, 15, 4518. 3. Stefanie, P.; Amaresh, M.; and Peter Bauerle,Beilstein J. Org. Chem. 2012, 8, 683 4. Basa Reddy, S. Mohan, Jahirul I. Talukdar, Int. J. Chem Tech Res. 2013, 5
P-402: Tetraoxa/tetrathia[22]porphyrin(2.1.2.1)s: Novel materials for organic field-effect transistors Tarunpreet Singh Virk and Kamaljit Singh*
Organic Synthesis Laboratory, Department of Chemistry, UGC-Centre of Advance Studies-I, Guru Nanak Dev University, Amritsar 143005, India E-mail: [email protected], [email protected]
In the course of development of cyclic conjugated chemical entities, structural variations of tetrapyrrolic porphyrinoids by replacing pyrrole with other heterocyclic species and/or changing the topology of the macrocycle in a manner that π-electron conjugation pathway is maintained, has led to the synthesis of a variety of neutral and charged heteroannulenes. We have disclosed the electronic structure and demonstrated the use of meso-aryl tetraoxa[22]porphyrin(2.1.2.1)[1] and slightly puckered tetrathia[22]porphyrin(2.1.2.1)[2] as thin film organic field-effect transistors (OFETs). These molecules showed moderate to high current on/off ratio along with a high reproducible bulk-like carrier hole mobility. Further a structure-electrical charge transport relationship has been obtained in the later class of molecular electronic materials. [3] The tetrathia annulenes also showed weak interaction with the electron accepting TCNQ as shown by X-ray crystal structure. Such a molecular level heterojunction, showed air stable ambipolar charge transport behaviour. [4] Single crystal structures of three meso-substituted tetrathia[22]annulenes were determined by X-ray diffraction & their electrical properties were investigated by single crystal transistor characterization and quantum simulations. [5] The details of designs of macrocyclic entities, structure, physical properties, charge mobility characteristics as well as chemosensing behaviour shall be presented.
References:
1. Kamaljit Singh, Tarunpreet Singh Virk, Jing Zhang, Wei Xu and Daoben Zhu, Chem. Comm., 2012, 48, 121–123.
2. Kamaljit Singh, Tarunpreet Singh Virk, Jing Zhang, Wei Xu and Daoben Zhu, Chem. Comm., 2012, 48, 12174-12176.
3. Tarunpreet Singh Virk, Kamaljit Singh, Yunke Qin, Wei Xu and Daoben Zhu, RSC Adv., 2014, 4, 37503-37509.
4. Jing Zhang, Hua Geng, Tarunpreet Singh Virk, Yan Zhao, Jiahui Tan, Chong-an Di, Wei Xu, Kamaljit Singh, Wenping Hu, Zhigang Shuai, Yunqi Liu and Daoben Zhu, Adv. Mater., 2012, 24, 2603-2607.
5. Jing Zhang, Zhiying Ma, Qian Zhang, Tarunpreet Singh Virk, Hua Geng, Dong Wang, Wei Xu, Zhigang Shuai, Kamaljit Singh, Wenping Hu, and Daoben Zhu, J. Mater. Chem. C, 2013, DOI: 10.1039/C3TC30776J.
P-403: Nucleophilic Reactions of Hetereocyclic compounds with Dibenzoylacetylene Tariq A. Shah and M. Muneer* Department of Chemistry, Aligarh Muslim University, Aligarh – 202002, India Email:[email protected]
Nucleophilic addition reaction on dibenzoylacetylene has been reported in a number of studies earlier[1-2]. In the present study, mode of reaction of various substrates viz, imidazole, thiazole, triazole and isoxazole derivatives with dibenzoylacetylene have been investigated. Reaction of amino derivatives of imidazole/thiazole/triazole with DBA gave five membered cyclic adducts[3]. 2-amino derivatives of benzimidazole with DBA in presence of triphenylphosphene gave six membered cyclic product while as 2- aminoisoxazole derivatives with DBA gave predominantly Z-isomeric adduct. All the reactions were carried out at room temperature and the procedure was applied to a series of substrates to examine the extension and limitation of the methodology. The structure of the products were characterized by IR, 1H NMR, 13C NMR, Mass spectrometry and single crystal X-ray analysis.
Keywords:Imidazo[2,1-b]thiazole; Benzo[d]thiazolo[3,2-a]imidazole; Dibenzoylacetylene
Reference 1. B.B. Lohray et al ., J. Org. Chem, 49, 4647- 4656, 1984. 2. S. Lahiri et al., Tetrahedron, 33, 3159 -1170, 1977. 3. Niyaz A. Mir, Tariq A. Shah et al., Tet. Lett , 55, 1706–1710, 2014.
Correspondence: Prof. M. Muneer, Department Of Chemistry, Aligarh Muslim University, Aligarh, India, 202002. Email: [email protected] Phone: +91-9897279787
P-404: Asymmetric Transfer Hydrogenation of Imines in Water by Varying the Ratio of Formic Acid to Triethylamine
Vaishali S. Shende*, Sudhindra H. Deshpande, Savita K. Shingote, Ashutosh A. Kelkar CEPD Division, National Chemical Laboratory, Pune 411008, India *E-mail: [email protected]
Keywords: Asymmetric catalysis, formic acid, pH, water
Asymmetric transfer hydrogenation (ATH) of imines is a powerful alternative to asymmetric hydrogenation for production of chiral amines [1]. ATH of imines is frequently carried out in the azeotropic mixture of formic acid (F) and triethylamine (T), where the F/T molar ratio is 2.5 with ruthenium and rhodium catalysts and TsDPEN(p-toluenesulfonyl-1,2-diphenyl ethylene diamine) as a ligand [2]. F-T ratio variation was performed for ATH of ketones [3] but ATH of imines with F-T ratio variation left unexplored. Herein we report ATH of imine 1a catalyzed by Rh-TsDPEN to examine the effects of the F/T ratio using a simply mixed F-T solution at different initial F/T molar ratios in water (Scheme 1). Figure 1 shows the turnover frequency (TOF) as a function of the starting pH values in the range of F/T ratio from 0.5 to 1.5. This study shows that the F/T ratio affects both the reduction rate and enantioselectivity, with the optimum F/T ratio being 1.1/1 in the ATH of imine 1a with the Rh-TsDPEN catalyst. Under such conditions, a range of substrates have been reduced using methanol as a co-solvent and it affords high yields (95-99%) and good to excellent enantioselectivities (88-95%) to chiral amines.
Scheme1: ATH of imine 1a with Rh-TsDPEN with F/T ratio (0.5/1.0 to 1.5/1.0)
750.0 Initial pH vs TOF 600.0
450.0
TOF hr / 300.0
150.0
0.0 3 4 5 6 7 8 9 10 11 pH
Figure 1: TOF against initial solution pH values for the reduction of imine 1a by HCOOH–NEt3 in water (2 mL total volume) with Rh–(S,S)-Ts-DPEN at 40°C.
References: 1. (a) S. Kobayashi and H. Ishitani, Chem. Rev., 1999, 99, 1069–1094; (b) J.M. Brunel, Recent Res. Dev. Org. Chem., 2003, 7, 155–190; (c) C. J. Cobley and J. P. Henschke, Adv. Synth. Catal., 2003, 345, 195–201, (d) R. Noyori, S. Hashiguchi, Acc. Chem. Res. 1997, 30, 97, (e) G. Zassinovich, G. Mestroni, S. Gladiali, Chem. Rev. 1992, 92, 1051. 2. a) N. Uematsu, A. Fujii, S. Hashiguchi, T. Ikariya, R. Noyori, J. Am .Chem. Soc. 1996, 118, 4916-4917; b) J. M. Mao, D. C. Baker, Org. Lett. 1999, 1, 841-843; c) G. D. Williams, R. A. Pike, C. E. Wade, M. Wills, Org. Lett. 2003, 5, 4227-4230; 3. (a) X.F. Wu, X.G. Li, F. King, J.L. Xiao, Angew. Chem. Int. Ed. 2005, 44, 3407–3411; (b) X.F. Wu, J.K. Liu, D. Di Tommaso, J.A. Iggo, C.R.A. Catlow, J. Bacsa, J.L. Xiao, Chem. Eur. J. 2008, 14 , 7699–7715. (c) Xiaowei Zhoua, Xiaofeng Wu, Bolun Yang, Jianliang Xiao, J. Mol. Catal A, 2012, 357, 133– 140
P-405: Structural and Functional Stability of Cellulase in Aqueous- Biamphiphilic Ionic Liquid Surfactant Solution Pankaj Bharmoria,1,2 Mohit J Mehta,2 Imran Pancha1,2 and Arvind Kumar*1,2 1Academy of Scientific and Innovative research 2Salt and Marine Chemical Discipline, CSIR-Central Salt and Marine Chemicals Research Institute, Bhavnagar, Gujarat 364002, India. *E-mail: [email protected] . In sight of exploring the potential of a biamphiphilic ionic liquid surfactant as enzyme stabilizer in detergents, we have investigated the structural and functional stability of cellulase upon interaction with 3-methyl-1- octylimidazolium dodecylsulfate, [C8mim][C12OSO3] in aqueous medium at pH 4.8. Adsorption and binding isotherms determined from tensiometry and isothermal titration calorimetry indicated that [C8mim][C12OSO3] interacts with cellulase distinctly at the three critical concentrations, viz. aggregation, C1, saturation, C2 and vesicular, C3. Fluorescence (at λex=280 nm), far UV-circular dichroism spectra and dynamic light scattering results have shown that [C8mim][C12OSO3] alters the tertiary and secondary structure of cellulase with a slight initial unfolding in monomeric regime (up to C1), refolding in the aggregation regime (up to C2), followed by unfolding in the shared aggregation regimes (below C3), and stabilizes the altered conformation in the post vesicular regime with an overall variation of hydrodynamic diameter from 4.12 to 7.19 nm. Dinitrosalicylic acid sugar assay test showed excellent functional stability of cellulase with an activity≥1 of unit/mg in all the concentration regimes. A very good surface activity of the concerned ionic liquid investigated by Rao et al. [1] complied by present results vindicate the candidature of [C8mim][C12OSO3] as a potential replacement of mixed micelles or non-ionic surfactants for cellulase stabilization in detergent industries [2].
Fig.1: (A) ITC thermograms of [C8mim][C12OSO3] aggregation in buffer, cellulase solution and binding isotherm with cellulase. Inset shows the differential power (dP) plot of [C8mim][C12OSO3] binding with cellulase at sequential injection (B) Cellulase activity in different concentration regimes of cellulase- -1 [C8mim][C12OSO3] interaction. Numbers over the pillar are signifying the concentration (mmol.L ) of the [C8mim][C12OSO3].
Reference 1. K. S. Rao et al., J. Phys. Chem. B, 116, 14363, 2012. 2. P. Bharmoria et al., J. Phys. Chem. B, 118, 9890, 2014.
P-406: Structural, absorption and transport properties of silver particles embedded tricalcium phosphate Brajendra Singh1*, Samayendra Kumar3, Bikramjit Basu4, Rajeev Gupta2,3
1Centre of Material Sciences, University of Allahabad, Allahabad 211002, India 2Department of Physics, Indian Institute of Technology Kanpur, Kanpur208016, India 3Materials Science Programme, Indian Institute of Technology Kanpur, Kanpur 208016, India 4Materials Research Centre, Indian Institute of Science, Bangalore 560012, India *E-mail:[email protected]; [email protected]
Bone is a mixture of inorganic calcium phosphate component and organic component that mainly consists of collagen, water, proteins, polysaccharides and lipids. Tri calcium phosphate and hydroxyapatite are widely recognized as potential bio ceramics for both dental and orthopaedic applications among other calcium phosphates due to their close chemical similarity with the inorganic component of bone and tooth mineral. In this study, we report the synthesis of silver particle embedded sintered tri calcium phosphate (TCP) using wet chemical methods. Raman spectra show the characteristics peaks of tri calcium phosphate, presence of Ag-O bond and absence of O-H bond. The optical absorption spectroscopic analysis confirms (a) the presence of silver nano particles in 800oC sintered tricalcium phosphate and (b) Ag+ ions in 1200oC sintered TCP. Scanning electron microscopy observation confirms the presence of micro sized cubes of silver in wet chemically synthesized tricalcium phosphate. Apart from antimicrobial property, an increase of two orders of magnitude in ionic conductivity has been observed for silver embedded tricalcium phosphate in comparison to hydroxyapatite.
Fig. 1. Micron sized Silver particles embedded 800oc sintered calcium phosphate
References:
1. Brajendra Singh et al., Mater. Sci. Eng. C, 31, 1320, 2011.
2. S. Kannan et al., J. Am. Ceram. Soc. 91, 1, 2008.
3. Brajendra Singh et al., Mater Lett. 95, 100, 2013.
4. R. L.Williams, et al. Crit. Rev. Biocompat. 5, 221, 1989.
5. Brajendra Singh et al., Bull. Mater Sci 2014 (accepted)
Keywords: Silver Particles, absorption and transport properties
*Corresponding Author: Phone: 9451545392 E mail: [email protected]; [email protected] P-407: Structural studies of CaMn1-xFexO3-δ (0 ≤ x ≤ 0.5)
Brajendra Singh* Centre of Material Sciences, University of Allahabad, Allahabad - 211002 *E-mail: [email protected]; [email protected]
Mn and Fe based perovskite oxides are known for its rich physical and chemical phenomenon, and its possible use as sensors, memory devices, catalysts and electrode in solid oxide fuel cells. Mn mixed valencies in bivalent atoms doped at A site in perovskite [La(Ca, Pb, Sr)MnO3] play a vital role to bring magnetic, electronic transport, magneto resistance and catalytic properties. The end members CaMnO3 (CMO) and LaMnO3(LMO) of La1-xCaxMnO3 show antiferromagnetic behavior while Ca doped composition (x=0.33) show ferromagnetic and colossal magnetoresistive properties. With the increase of Ca content in LaMnO3, unit cell show structural transformation and end member [CaMnO3] unit cell turn into orthorhombic. These structural transitions are related to the ratio of Mn+3(0.645Å) /Mn+4(0.53Å). Similarly when lower size atom Ca+2 (1.34Å) +2 doped at Sr (1.44Å) site in Sr1-xCaxMnO3, orthorhombic-tetragonal-cubic phase transformation has been observed. In this study, we have shown the structural transformation in CaMn1-xFexO3-δ (0 ≤ x ≤ 0.5) due to the +4 doping of Fe ions at Mn (0.53Å) site in CaMnO3. Synchrotron X-ray diffraction patterns show the change in space group at room temperature with Fe doping in CaMnO3. Magnetization data show competition between antiferromagnetic and paramagnetic magnetic states (kink ~100K in magnetization data). The kink is shifted towards lower temperature and finally x=0.3 composition show paramagnetic behavior. Temperature dependent Synchrotron X-ray diffraction patterns show the change in structure near the magnetic transition temperatures in parent and Fe doped composition.
References: 1. Brajendra et al., Mater Lett. 65, 2029, 2011. 2. Q. Zhou et al. J. Solid State Chem 179, 3568, 2006. 3. K. Vijayanandhini et al. J Mater Sci: Mater Electron 20, 445, 2008. 4. X. J. Liu et al. Solid State Commun. 142, 525, 2007.
Keywords: Perovskite, structural transformation, Synchrotron X-ray diffraction *Corresponding Author: Phone: 9451545392 E mail: [email protected]; [email protected]
P-408: Electrochemical Synthesis of Cu-PPy composites from binary solvent medium using double pulse chronoamperometry: Effect of potential, anion and supporting electrolyte on their morphology Aravindan. N, M.V.Sangaranarayanan* Department of Chemistry, Indian Institute of Technology Madras, Chennai-600036, Tamilnadu, India. Email : [email protected]
Abstract
Metal-polymer composites prepared from an aqueous solution containing both the monomer and the metal salt are bound by the problem of depositing metal in the form of hydroxides [1, 2]. This problem can be overcome by using a binary miscible aqueous and non-aqueous solvent system. Here, the Copper-Polypyrrole (Cu-PPy) composites were prepared from the binary solvent medium of water - methanol containing both metal precursor and pyrrole monomer using double pulse chronoamperometry. The PPy was first anodically deposited at 0.8 V and the cathodic deposition of metallic copper was carried out from -0.2 V to -0.8 V subsequently on a Stainless Steel (SS) electrode. The PPy and Cu-PPy composites prepared by changing the potential, anion and supporting electrolytes were characterized by Scanning Electron Microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), Powder X-Ray Diffraction Spectroscopy (XRD), Fourier Transform - Infrared Spectroscopy (FT-IR) and Energy Dispersive Analysis of X-Ray (EDAX). The SEM image of the composites prepared under various conditions is given in Fig.1.
Fig.1: SEM image of Cu-PPy composites prepared from a 1:1 (v: v) water – methanol binary solvent by changing (a, b) potential applied for metal deposition (-0.2 V and -0.8 V respectively with CuSO4 as metal precursor), (c) anion of the metal precursor (CuCl2.2H2O), (d) supporting electrolyte (HNO3). In (a), (b), and (c) the supporting electrolyte used was H2SO4. In all the cases, the PPy was deposited at 0.8 V.
Reference 1. K. S. Hoffmann et al., J. Phys. Chem. C, 113, 8556, 2009. 2. P. Sozzani et al., J. Am. Chem. Soc., 125, 12881, 2003.
P-409: Synthesis and characterization of new macrocyclic trinuclear Cu (II) complexes: Electrochemical, DNA binding and cleavage studies
M.K.Bappithaa, K.R.Krishnapriya and M. Kandaswamy*
Department of Inorganic Chemistry, University of Madras, Chennai, Tamilnadu
E-mail-id: [email protected] Abstract
A new series of unsymmetrical macrocyclic tricopper (II) complexes has been synthesized by Schiff base condensation of tricompartmental complexes with various diamines like 1,2- diaminoethane(R), 1,3-diaminopropane(R) , 1,4-diaminobutane(R). The complexes were characterized by elemental and spectral analysis. Redox, catalytic, DNA binding and DNA cleavage properties were studied. The binding ability and mode of binding of the complexes with CT-DNA were studied using absorption, fluorescence spectral titrations and viscosity measurements. The cyclic voltammogram of trinuclear Cu (II) complexes exhibit three quasi-reversible reduction waves in the range of 0V to -1.4V. The first reduction potential in the range from E1pc = - 0.20 V to -0.50 V, the second reduction potential in the range from E2pc = -0.60 V to -0.80 V and the third reduction potential in the range from E3pc = -1.02 V to -1.25 V versus Ag/AgCl in DMF. The binding constant obtained from the absorption spectral titrations for 1-3 complexes are 2.1 x 104, 3.5 x 104 and 5.2 x 10 4M-1 respectively. Viscosity measurements have been carried out to find out the mode of binding of the complexes with CT-DNA.
+ CH3 4 - 4(ClO4 )
N N N O N Cu Cu Cu R
N N N O N
CH 3
R = -(CH2)2- , -(CH2)3- , -(CH2)4- P-410: Photocatalytic degradation of organic dyes using Indian Edible Chuna as a Green Photocatalyst S. A. Sawant1, S. P. Somani2, S. K. Omanwar3, P. R. Somani2 1Smt. Kashibai Navale College of Engineering, Vadgaon-Bk, Pune - 411041, Maharashtra, India. 2Applied Science Innovations Pvt. Ltd., Pune – 411041, Maharashtra, India (www.applied-science-innovations.com) 3 Department of Physics, Sant Gadge Baba Amravati University, Amravati, India.
Abstract:
Photocatalytic degradation of two organic dyes (methylene blue and crystal violet) has been studied using Indian Edible Chuna as a photocatalyst due to its easy availability, low cost, and environment and user friendly nature [1, 2]. Physico-chemical characterization of Indian Edible Chuna indicates that it is calcium oxide (in dry state) or a mixture of calcium oxide and hydroxide (in wet state).
Photocatalytic degradation of methylene blue (MB) dye in sea/saline water was observed to be very slow, as compared to that in distilled water. This is due to the fact that presence of salts hinders in making a direct contact with the dye. This observation suggests that the process might be very slow in actual field conditions (say textile industry waste water). It is observed that crystal violet (CV) dye undergoes chemical (in dark) as well as photocatalytic (in presence of light) degradation in presence of Indian Edible Chuna. The process of chemical degradation of the CV dye is observed to be fast and gets activated in presence of light. Further, degradation of CV dye is observed to be very fast as compared to MB dye.
The ability of the calcium hydroxide to yield hydroxyl ions and the importance of the hydroxyl radicals in the photocatalysis process indicates the importance of calcium oxide/hydroxide as a photocatalyst.
Keywords: Indian Edible Chuna, Photocatalysis, calcium oxide, calcium hydroxide, crystal violet dye, methylene blue dye. Corresponding Author E-mail : [email protected] / [email protected]
References
1 P. R. Somani, et.al , Journal of Green Science and Technology 1 (2013) 2 – 5. 2 P. R. Somani, et.al , Advanced Science, Engineering and Medicine (ASP) 6/2 (2014) 227 – 230.
P-411: Structural and Functional Studies on Two-Dimensional Ternary Coordination Polymers Y. Rachuri,1,2 K.K. Bisht1,2 and E. Suresh1,2* 1 Analytical Discipline and Centralized Instrument Facility, 2 Academy of Scientific and Innovative Research (AcSIR), CSIR–Central Salt and Marine Chemicals Research Institute, (CSIR-CSMCRI), G. B. Marg, Bhavnagar 364 002, Gujarat, India. *E-mail: [email protected]
The synthesis of Coordination polymers (CPs/MOFs) have been attracted attention of the researchers due to their versatile structural features such as porous structures, gas adsorption and potential applications in heterogeneous catalysis[1], magnetism and sensing[2] and photo degradation of hazardous dyes. Moreover controlled capture and release of various analytes in MOFs has been another interesting feature in recent times. Encapsulation molecular iodine in CPs [3] is a promising application towards momentous effects of iodine on conductivity, magnetism and luminescence properties, and capturing of hazardous radioactive isotope 129I, in nuclear reactors. In general CPs constructed by the judicious choice of metal nodes (or clusters) with adaptable coordination geometry and organic ligands possessing exo-dentate coordination sites. Ligands afford a wide variety of linking sites with tuned binding strength, directionality and flexibility. We have synthesized three ternary CPs comprising of neutral Schiff base ligands L1PMZ (N,N-bis-pyridin-4-ylmethylene-hydrazine), L3PMZ (N,N-bis-pyridin-3-ylmethylene-hydrazine), flexible dicarboxylate 1,3-ADA (1,3-adamantane diacetate) and metal nodes (M = Cu2+, Co2+ and Zn2+). Thus, three novel Coordination polymers; namely, [Cu(1,3-ADA)(LIPMZ)]n (1), [Co(1,3-ADA)(LIPMZ)]n (2), {[Zn2(µ-H2O)(1,3-ADA)2(LIPMZ)2] (H2O)}n (3) have been synthesized by diffusion method. Crystal structures of these complexes revealed 2D pillar layer networks of CPs 1 and 2 whereas 1D chain structure was observed for 3. Comprehensive characterization, structural analysis and photoluminescence of 3 will be discussed in detail. Complex 1 and 2 will be explored for the application of iodine encapsulation and photo degradation of organic dyes.
Fig.1: (a) The depicted picture explains its pillar layer structure of 1 along bc plane and (b) space fill figure along ab plane.
Reference
1. Y. Cui et al., Adv. Mater, 122, 4112, 2010. 2. S. K. Ghosh et al., Chem. Commun., 50, 8915, 2014. 3. T. M. Nenoff, Chem. Mater., 25, 2591, 2013.
P-412: Probing Molecular Chirality: Transfer, Control and Rationalization
Sk. Asif Ikbal, Avinash Dhamija and Sankar Prasad Rath* Department of Chemistry, Indian Institute of Technology, Kanpur Kanpur-208016. Email: [email protected]
Supramolecular chirality is a growing multidisciplinary field of modern research and attracts much attention from the scientific community because of its vital importance in many areas including studies on the origin of the homochirality of life, various biomimetic systems, materials and polymer sciences, enantioselective catalysis, nonlinear optics, chiral memory, molecular recognition and the determination of absolute configuration[1-4]. In recent times, porphyrinoids have been widely used for studying the processes involved in supramolecular chirality induction because of their distinct spectral properties such as intense Soret band and tunable physico-chemical properties. These intriguing properties of the porphyrin have got much attention for being used as chirality probes upon forming chiral host-guest assemblies through covalent/non-covalent interactions. An overview of the on-going research in our laboratory will be presented here.
REFERENCES [1] Ikbal, S. A.; Brahma, S.; Rath, S. P. Chem. Commun. 2014, 50, 0000. [2] Ikbal, S. A.; Brahma, S.; Rath, S. P. Chem. Commun. 2014, 50, 14037. [3] Brahma, S.; Ikbal, S. A.; Dhamija, A.; Rath, S. P. Inorg.Chem. 2014, 53, 2381. [4] Brahma, S.; Ikbal, S. A.; Rath, S. P. Inorg.Chem. 2014, 53, 49. [5] Brahma, S.; Ikbal, S. A.; Dey, S.; Rath, S. P. Chem. Commun. 2012, 48, 4070.
P-413:Thiosemicarbazone Based Highly Selective Fluorescence Enhancement Sensor For Persulfate Anion
Pooja S. Badekar, Anupa A. Kumbhar*, Soniya Rao and S. P. Gejji
Department of Chemistry, Savitribai Phule Pune University, Pune – 411 007. E-mail : [email protected]
Abstract:
Ureas, thioureas, calyx[4]pyrroles, sapphyrins, and amides are typical hydrogen-bonding sites used in chromogenic or fluorogenic chemosensors. Panda and et al, Sessler and et al [1]. Among them, the urea or thiourea groups have often been focused as anion binding sites, due to their strong hydrogen-bonding ability resulting in quite stable complexes with biologically important anions such as acetate, phosphate or chloride, and can be easily synthesized from commercially available reagents by a single-step procedure. Kondo and et al, Kang and et al [2]. In order to develop a sensor for detection of persulfate anion, we synthesized anthracene thiosemicarbazone (ATSC) with anthracene as fluorogenic signaling unit and thiosemicarbazone as bonding site. The receptor was characterized by 1H NMR, IR, UV-Vis, fluorescence and mass spectroscopy. Fluorescence emission studies showed that the receptor, effectively and selectively, recognized the persulfate anion from other anions such as F-, Cl-, Br-, I-, acetate, carbonate, nitrate, perchlorate, hydrogen sulfate, dihydrogen phosphate, adenosine mono-, di- and triphosphates and interefering cations like Na+, K+, Ba2+, Ca2+, Mg2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Ag+, Pb2+, Cd2+, Hg2+ and Al3+ in DMSO. Further, feature of the binding mode is predicted on the basis of density functional calculations.
12
10
8
O 6 I / 4
2
0 - - - -2 ------Cl 2- F 4 4 I 3 O 8 ADP ATP Br 4 PO NO none AMP COO ClO 3 HSO S 2 3 CO H 2 CH
References :
1. Panda, P. K.; Lee, C.-H., J. Org. Chem., 70, 3148, 2005 (e) Sessler, J. L.; An, D.; Cho, W.-S.; Lynch, V.; Marquez, M. Chem.—Eur. J., 11, 2001, 2005
2. (a) Kondo, S.-i.; Hiraoka, Y.; Kurumatani, N.; Yano, Y. Chem. Commun., 1720, 2005 (b) Kang, S. O.; Linares, J. M.; Powell, D.; VanderVelde, D.; Bowman-James, K. J. Am. Chem. Soc., 125, 10152, 2003.
P-414: Preparation of multiferroic mixed valent pervoskite by auto combustion methods using glycine route Shashikalajaiswar*,K.D.Mandal Department of chemistry, Indian Institute of Technology (BHU) Varanasi-221005 Email: [email protected]
In this study we report a new multiferroic material the CaMn7O12 which simultaneously shows ferroelectric and cooperative magnetism and in which both properties intercoupled called magneto electric effects. Such properties are interesting because it allows the manipulation of the magnetic response with an external electric field and the tuning of the dielectric behavior as a function of the magnetic field in new multifunctional materials. Below 409K CaMn7O12 have trigonal symmetric space group R3 which is a mixed oxide that experiences charge ordering (CO) i.e. mixed valent compound in which the metal ions in different oxidant states order in specific lattice sites giving rise to charge localization. In the recent� research work the multiferroic ferroelectric materials have attracts the research works due to its magnetic as well as electric behavior. In the above research we like to attribute the pure CaMn7O12 which is a ferroelectric with giant dielectric properties. The precursor powder is prepared by auto combustion methods. And the advantage of this is that the particle size is found to be smallthat is 23nm which is much smaller than that prepared by sol gel. The single phase formation is confirmed by XRD matching of a calcined powder using JCPDF file. The particle size is calculated through DebyeSherrerformula. Indexing≈ of xrd pattern is done with cell software and the value of their lattice parameter a=10.441A0, c=6.344A0 with cell volume V=598.9(A0)3. Also it require less soaking duration that 15hrs at 10000C which is smaller than 48hrs to 60hrs at the same temperature range. The dielectric measurement is taken using LCR meter. The dielectric constant is found in the range of 105 which can be in used as good capacitor memory storage devices. The activation energy is found to 0.61eV, 0.57eV, 0.53eV and 0.51eV at 100Hz, 1 KHz, 13 KHz and 100 KHz respectively. Low frequency dispersion ≈obeying the power law n feature (σac α ω ) changes in the slope governed by n. The frequency at which the change in slope takes place is known as “hopping frequency (ωn)”. The value of n is obtained to be 0.34, 0.39, 0.44, and 0.45 at 1750C, 2000C, 2250C and 2500C respectively. Hence AC conductivities increase successively with temperature. Impedance studies attribute the contribution of both grain and grain boundary and with temperature resistance decreases and hence conductivities increase, the value of resistance of grain and grain boundary is 3.397×105 and 2.575×105, 1.309×105 and 9.354×105, 5.117×104 and 3.121×105, 3.948×104 and 1.247×105 at 1750C, 2000C, 2250C and 2500C respectively. Thus shows NTCR type of character proves its semiconducting behavior.The composition and morphologicalstudies is done by SEM EDX. The thermal treatment is done as per TGA/DTA peaks due to weight loss by decomposition of organic matter and energy changes through heat absorption or release that are either endothermic or exothermic.
P-415: In situ synthesis of Ru Nanoparticles to catalyze hydrogenation of CO2 to Formic acid
Praveenkumar Upadhyay, Vivek Srivastava*
Basic Sciences: Chemistry, NIIT University, NH-8 Jaipur/Delhi Highway, Neemrana (Rajasthan)
Pin Code: 301705, Contact Number: +91-1494302475
email id: [email protected]
Abstract
The reduction of CO2 emission into the atmosphere is an urgent necessity since this gas is as a major factor responsible for the greenhouse effect. The catalytic transformation of CO2 in other chemicals is an important alternative for CO2 fixation. It is well documented that Ru (II) compounds can promote the partial hydrogenation of CO2 to formic acid in the presence of functionalized ionic liquid that capture the acid formed and thus shift the equilibrium. Imidazolium ionic liquids (ILs) possess pre-organized structures, mainly through hydrogen bonds that induce structural directionality, as opposed to classical salts in which the aggregates display charge-ordering structures.
We are reporting conventional as well as in situ generation of Ru nanoparticles (Ru NPs) followed by decomposition of hydrogen reduction of bis(2-methylallyl)(1 5-cyclooctadiene)ruthenium (II) in the functionalized ionic liquids. We synthesized two functionalized imidazolium based ionic liquids such as 1,3- di(N,N-dimethylaminoethyl)-2-methylimidazolium trifluoromethanesulfonate ([DAMI][TfO]) and 1,3-di(N,N- dimethylaminoethyl)-2-methylimidazolium bis (trifluoromethylsulfonyl) imide ([DAMI][NTf2]) containing amino groups that may capture partial CO2 hydrogenated products and thus control the selectivity of this reaction (Figure 1). Use of ionic liquid also offers easy catalyst isolation and catalyst recycling steps during the reaction.
Figure 1: Results for Hydrogenation of CO2 to formic acid using Ru nanoparticles in functionalized ionic liquid
Keywords
Ru nanoparticles, functionalized ionic liquid, formic acid, carbon sequestration, carbon dioxide
Acknowledgement The work is financially supported by DST Fast Track (SB/FT/CS-124/2012).
P-416: Synthesis of Biodegradable Polyacrylic acid@zeolitic imidazolate framework-8 Nanoparticles for Cyanide sensing in aqueous media
Anshu Kumar1,2, Madhuri Bhatt1,2, Gaurav Vyas1, Parimal Paul*1,2 1Analytical Discipline and Centralized Instrument Facility, Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, India 2Academy of Scientific and Innovative Research, Central Salt and Marine Chemicals Research Institute, Bhavnagar-364002, India. * E-mail: [email protected]
Over the past decades the reliable detection of target species takes a great attention to discovery of new analytical method1. The real-time monitoring of cyanide ion concentration in environment, water, and food as well as its quantitative determination across a large concentration range is of vital importance for various environmental and health-care issues2. Several strategies have been reported on cyanide detection using recognition-transduction schemes based on the optical read-out of a luminescent or colorimetric signal or costly instruments3-4. Here we demonstrate how the analyte-induced degradation of a hybrid host material with embedded Na-PAA@ZIF8 nanoparticles can be efficiently used as an extremely sensitive signal transduction mode with cyanide out of large number of anions, it exhibited high selectivity and sensitivity towards cyanide in aqueous media (Fig. 1). It is thus anticipated that our new recognition-transduction mechanism contributes to the development of optically encoded chemosensors and hence for the sensitive visualization of specific host-guest interactions. Metal-organic frameworks (MOFs), also known as porous coordination polymers ZIF8, have attracted great interest in the last decade as a new class of highly porous materials ideally suited for applications in gas adsorption, separation processes5 and chemical sensing6.
Fig.1: Synthesis of polyacrylic acid@zeolitic imidazolate frame work-8 NPs and its sensing Application
Reference 1. M. Schferling et al., Angew. Chem. Int. Ed. 51, 3532, 2012. 2. J. Yoon et al., J. Chem. Soc. Rev. 39, 127, 2010. 3. W. C. Blackledge et al., Anal. Chem. 82, 4216, 2010. 4. B. A. Logue et al., Crit. Rev. Anal. Chem. 40, 122, 2010. 5. K. Sumida et al., Chem.Rev. 112, 724, 2011. 6. L. E. Kreno et al., Chem. Rev. 112, 1105, 2012.
P-417: Chemically Induced Synthesis of Nanoparticle and Dimensional Reduction as a Tool for the Introduction of Valence Transition and Magnetism in Nonmagnetic YbPb3 Udumula Subbarao, Sumanta Sarkar, Rajkumar Jana, Sourav S. Bera, Sebastian C. Peter* New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore, 560064, India Email:[email protected]
Abstract: This paper presents the controlled synthesis of YbPb3 nanoparticles in different morphology using solvothermal method. The morphology of the nanoparticles was controlled in presence and absence of surfactants. The formation of different morphology has been explained by proposing a mechanism in connection with the crystallography. The phase and purity were characterized by powder X-ray diffraction and the microstructure analyses performed by scanning electron microscopy and transmission electron microscopy (TEM) suggest that the compound YbPb3 can be synthesized as nanomaterial of particle size down to about 16 nm spheres in the absence of surfactant and 50 nm thick rods in the presence of surfactants Polyvinylpyrrolidone (PVP) and Cetyl trimethylammonium bromide (CTAB). The temperature dependent magnetic measurements showed that the induced magnetism associated with the valence transition from divalent diamagnetic Yb in bulk material to trivalent Yb in nanomaterials. The surfactant free YbPb3 also showed paramagnetic behaviour ruled out the magnetic contribution from the surfactant and confirms the particle size reduction is the inherent part for the origin of magnetism in YbPb3. The valence transition of Yb from divalent to trivalent was confirmed by X- ray absorption near edge spectroscopy (XANES).
Figure 1. Surfactant directed morphological evolution in the formation of YbPb3 nanoparticle. unit cell of YbPb3, (a) three dimensional structure of YbPb3 in the absence of any surfactant (b) TEM image of spherical nanoparticle without surfactant after 24 hrs (c) and 48 hrs (d), surfactant assistaed dimensional reduction to one dimensition crystal structure of YbPb3 (e) and TEM images of PVP (f) and CTAB (g) assited growth of nanorods of YbPb3. Keywords: Intermetallics, Nanoparticles, Magnetism, Valence Transition
*Corresponding author. Phone: 080-22082998, Fax: 080-22082620 [email protected] (S. C. Peter)
Reference
1. U. Subbarao et al., manuscript submitted, 2014
P-418: Phosphoric Acid Loaded Covalent Organic Frameworks as Proton Conducting Materials Suman Chandra, Tanay Kundu and Rahul Banerjee*. Physical Chemistry Division, CSIR-National Chemical Laboratory, Pune 411008, India. E-mail id: [email protected].
Two new chemically stable functional crystalline covalent organic frameworkds (COFs) (Tp-Azo and Tp-Stb) were synthesized using the Schiff base reaction between triformylphloroglucinol (Tp) and′ 4,4 -azodianiline (Azo) or 4,4′ -diaminostilbene (Stb), respectively. Both COFs show the expected keto-enamine form, and high stability towards boiling water, strong acidic, and basic media. H3PO4 doping in Tp-Azo leads to immobilization of the acid within the porous framework, which facilitates proton conduction in both the hydrous (σ = 9.9×10 −4 Scm−1) and anhydrous state (σ = 6.7×10 −5 Scm−1). This report constitutes the first emergence of COFs as proton conducting materials.
(a) Schematic of H3PO4 doping in COFs. Proton conductivity of PA@Tp-Azo in (b) anhydrous and (c) hydrous conditions. (d) Proton conductivity of PA@Tp-Stb in hydrous conditions. (e) Arrhenius plot for PA@Tp-Azo in hydrous conditions.
References (1) Kandambeth, S.; Mallick, A.; Lukose, B.; Mane, M. V.; Heine, T.; Banerjee, R. J. Am. Chem. Soc. 2012, 134, 19524. (2) Chandra, S.; Kundu, T.; Kandambeth, S.; BabaRao, R.; Marathe, Y.; Kunjir, S.M ; Banerjee, R. J. Am. Chem. Soc. 2014, 136, 6570. (3) Xu, H.; Jiang, D. Nature Chemistry.2014, 6, 564.
P-419: Fabrication and Assessment of Silk Fibroin Biomaterial Scaffolds for human Mesenchymal Stem Cell Adhesion Proliferation and Differentiation Shivaprasad Manchineella, T. Govindaraju* Bioorganic Chemistry Laboratory, New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P. O., Bengaluru, Karnataka, India. E-mail: [email protected]
Tissue engineering and regenerative medicine finds potential applications in repairing or replacing the malfunctioning tissues or organs, as well as increasing the life expectancy. Stem cell-based tissue engineering primarily involves the cell proliferation or differentiation of stem cells into specific cell lines, tissues or organs in engineered biomaterial constructs. Physical factors such as stiffness, wettability, and electro-active properties of scaffolds dictates the fate of in vitro cultured cells when combined with other optimal cell culture additives including soluble growth factors. Silk fibroin (SF) extracted from silkworm cocoons is a fibrous protein material which has good mechanical properties along with low immune response both in vitro and in vivo [1]. Silk fibroin with its unique property of controlled biodegradability is gaining interest in recent years as biomaterial for addressing the limitations associated with the use of synthetic polymer substrates during cell culture [2]. We had extracted silk fibroin from Bombyx mori silkworm cocoons and processed the regenerated silk fibroin into hydrogels, porous sponges, transparent films, random and aligned elctrospun fibre matrices for cell culture applications. Functionalizing biomaterial surface with extra cellular matrix (ECM) proteins creates a cellular mimicking microenvironment in vitro thereby promoting cell adhesion and survival. Among the several ECM proteins, laminin is thought to be playing a major role in cell adhesion, differentiation and migration. In this context, we have prepared laminin derived peptide and its analogues using solid phase peptide synthesis and functionalized them on silk fibroin films. Silk fibroin films were functionalized in two ways, one through physical adsorption and second through covalent chemical modification using peptide coupling and the functionalized SF films were evaluated for the response of human mesenchymal stem cells in vitro. SF films are biocompatible and fluorescein diacetate (FDA), picogreen assays showed improved cell adhesion and proliferation compared to control substrates making the films ideal 2D scaffolds for cell culture and tissue engineering applications [3].
Reference
1. C. Vepari et.al, Prog. Polym. Sci., 32, 991, 2007.
2. X. Zhang et.al, Adv. Drug Deliv. Rev., 61, 988, 2009.
3. S. Manchineella et.al, (unpublished results).
P-420: Nano copper ferrite (CuFe2O4) prepared from metal precursors derived from electronic waste printed circuit boards
Krishnan Muthukumar, A. B. Boricha, H. C. Bajaj* Discipline of Inorganic Materials and Catalysis, Council of Scientific and Industrial Research (CSIR), Central Salt and Marine Chemicals Research Institute (CSIR-CSMCRI), G. B. Marg, Bhavnagar, Gujarat 364 002, India. Fax: +91-278-2566970 extension 7000. E- mail: [email protected]
The nano ferrites are used in the wide range of applications such as magnetically recovery heterogeneous catalyst, biomedical applications and energy storage device.1, 2 Ferrite have attracts the research interest of many research due to their ease of preparation, size control and cheaper cost. The size (>20nm) and mono dispersion are essential for high sensitive application. 1 Solvothermal decomposition of metal salt is one of the way to prepare the tailor made nano ferrites.3 Here we used the metal precursors derived from the electronic waste printed circuit board by a greenery process. Cu & Fe contain precursors (1:2 mole ratio) were dissolved in methanol and stirred for 10min at 60°C than transferred to 75ml autoclave(2/3 filled) and heat in air oven at 200° C for 5h. The prepared copper ferrites characterized by PXRD, and it exactly matches with the early reported method. The particle size of the prepared ferrite was in the range 35-50 nm calculated using scherrer equation. Further the studies are going to optimize the parameters to prepare nano ferrites less than 20nm diameter size and their applications in heterogeneous catalysis.
Key words: nano copper ferrite, electronic waste
400 CuF-1
300
200 Intensity(cps)
100
0 10 20 30 40 50 60 70 80 2theta(deg) Reference
1. S. Sun, H. Zeng, D. B. R. S. Raoux, P. M. Rice, S. X. Wang and G. Li, J. Am. Chem. Soc. 2001, 2004, 126, 273-279 2. K. Swapna, S. N. Murthy, M. T. Jyothi and Y. V. Nageswar, Organic & biomolecular chemistry, 2011, 9, 5989-5996. 3. M. M. Rashad, R. M. Mohamed, M. A. Ibrahim, L. F. M. Ismail and E. A. Abd, Advanced
Powder Technology 2012, 23, 315-323.
P-421: Synthesis, Crystal Structure and Photophysical properties of Novel Dinuclear Complexes Anoop Kumar Saini, 1 Ajeet Singh, 1 Shaikh. M. Mobin *1 1Discipline of Chemistry, School of Basic Sciences, Indian institute of Technology Indore, Indore, India. *E-mail: [email protected]
Condensation of 2-hydroxy-1-napthaldehyde and 2,4,6-trimethylbenzene-1,3-diamine in methanol yields new Schiff' base ligand (H2L). H2L was characterized by microanalytical, spectral and X-ray diffraction studies. The deprotonation of the H2L by base and its subsequent reactions with metal nitrate salts [Co(NO3)2.6H2O, Cu(NO3)2.3H2O, Zn(NO3)2.6H2O] yield dimeric structures (1-3) with 1:1 ligand to metal ratio. 1-3 show square planar geometry in symmetric dimeric unit. Interestingly, complexes 1-3 show a cavity size of ∼7.366 x 3.104Å. Interesting photophysical property for 1 was observed whose fluorescent is quenched after metallation. The structure of complexes 1-3 are confirmed by microanalytical studies and further authenticated by single crystal X-ray crystallography. The structural analysis reveals an extended C-H…π interactions in these complexes leading to different three dimensional networks.
Fig. 2. Synthesis of Dinuclear Metal Complexes Fig. 2. Molecular Structure of 1-3
1.6
1.4
1.2 H2L 1 1.0 2 3 0.8
0.6
Absorbance 0.4 0.2 0.0 300 400 500 Wavelength(nm)
Fig. 3. UV-visible spectra of H2L(1) and dinuclear metal complexes.
P-422: Photo-activated anticancer activity of polypyridyliron(II) complexes
Aditya Garai, Uttara Basu , Imran Khan , Ila Pant , Akhtar Hussain , PaturuKondaiah Akhil R. Chakravarty* Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore 560 012, India. E-mail: [email protected]
Abstract.Photodynamic therapy is a non-invasive technique for treatment of cancer [1]. Iron(II) complexes of polypyridyl ligands (B), viz. [Fe(B)2]Cl2 (1 and 2) ofN,N,N-donor 2-(2-pyridyl)-1,10-phenanthroline (pyphen in 1) and 3-(pyridin-2-yl)dipyrido[3,2-a:2',3'-c]phenazine (pydppz in 2),are prepared as metal based photocytotoxic agents. The 1:2 electrolytic complexes arediamagnetic in nature exhibiting metal to ligand charge transfer (MLCT) band near 570 nm in DMF. The complexes are avid binders to calf thymus DNA giving binding 6 -1 constant (Kb) values of ~10 M suggesting significant intercalative DNA binding of the complexes due to presence of planar phenanthroline bases. Complex 2 exhibits significant photocytotoxicity in immortalized human keratinocyte HaCaTcells and breast cancer MCF-7 cells giving IC50 values of 0.08 and 13 µM in visible light (400-700 nm). Complex 2 shows only minor dark toxicity in HaCaT cells but is non-toxic in dark in MCF- 7 cancer cells. The light-induced cellular damage follows apoptotic pathway on generation of reactive oxygen species (ROS) as evidenced from the dichlorofluoresceindiacetate (DCFDA) assay.
1. R. Bonnett, Chemical Aspects of Photodynamic Therapy, Gordon & Breach, London, UK, 2000.
P-423: Trans-porphyrins as chemosensors for Fe2+ / Cu2+ ion detection Ramesh Jagadeesan, Subramaniam Sujatha and Chellaiah Arunkumar*
Bioinorganic Materials Research Laboratory, Department of Chemistry, School of Natural Sciences, National Institute of Technology Calicut, Kozhikode, Kerala − 673 601, India.
E-mail: [email protected] Abstract:
Porphyrins are the attractive molecules as fluorescent cationic sensors in the literature. Here, we report the synthesis, structural, spectral and sensing properties of 5,15-bis(pentafluorophenyl)-10,20-bis(4- bromophenyl)porphyrin [1] and their metal complexes (Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) shown in Figure 1. All the synthesized porphyrins were characterized by UV-Visible, Fluorescence, 1H NMR spectroscopic and mass spectrometric methods. The porphyrin free ligand and Zn(II)-derivative are known to exhibit as fluorescent behavior and their cationic sensing studies were examined towards different metal ions (Na+, Ca2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+ ) [2, 3]. The compound, 1 was found to be selectively sensing Cu2+ and Fe2+ ions respectively in different solvents.
a b c d
Figure 1. a) Molecular structure of porphyrins b) Fluorescence spectra of porphyrin derivatives c) Cu2+ ion detection using free base porphyrin d) Responses of 1 in CHCl3 (3.4 µM) to different metal ions in methanol (100 µM). The excitation was at 415 nm, and the emission was at 646 nm.
References:
1. H. Xiang et al., Inorg. Chem., 51, 5208, 2012. 2. Y. Q. Weng et al., Inorg. Chem., 46, 7749, 2007. 3. Y. Chen et al., Org. Biomol. Chem., 10, 4782, 2012.
P-424: SELF ASSEMBLIES OF FUNCTIONALIZED 2° AMINES, CS2 AND METAL IONS: SYNTHESES AND CHARACTERIZATION OF BIMETALLIC-DTC MACROCYCLIC COMPLEXES BEARING POLAR SUB-UNITS IN THE LINKER Vineeta Pillai and Vinay K. Singh* [email protected] Department of Chemistry, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara-390002 (Gujarat) India.
The metal directed self-assembly of polydentate ligands provides a facile route to novel supramolecular architectures based on metal-coordinate interactions[1]. With the help of multidentate ligands and judicious choice of transition metal ions, a number of fascinating molecular architectures including helicates [2], cages, ladders, racks, grids and tubes [3] have been constructed. Dithiocarbamate (dtc) ligand is an attractive structural moiety for self- assembly because its coordination chemistry with a wide variety of transition metals offers plenty of opportunity for introducing different metals into the supramolecular array. Polymetallic assemblies containing appropriately designed host cavities have allowed the binding of cationic, anionic and neutral guest species to be investigated [3]. We have selected 4,4’-diamino diphenyl sulphone as a lead compound to design and 1 4 synthesize a novel series of 2° amine precursors L -L . In a single pot reaction using basic reaction condition these 2° amines reacts with CS2 to give the corresponding dithiocarbamtes in situ which on further reaction with various transition metal ions Cu(II), Ni(II), Co(II), Zn(II) yielded a series of binuclear bis-dithiocarbamte macrocyclic complexes as illustrated in Scheme-1.
Scheme 1: Preparation of bimetallic bis-dtc complexes bearing dapsone amide linker.
All the new compounds have been studied by relevant spectroscopic methods such as FT IR, 1H, 13C, UV –Visible and fluorescence. The TGA/DTA analysis of these complexes were performed in the temperatures ranging from room temperatures to 550°C under nitrogen atmosphere. These compounds are further investigated for their potential applications as antitumor agents against some human cancer cell line.
REFRENCES [1] P. J. Stang and S. R. Seidel, Acc. Chem. Res., 2002, 35, 972. [2] F. M. Tabellion, S. R. Seidel, A. M. Aril and P. J. Stang, Angew. Chem., Int. Ed., 2001, 40, 1529 [3] G. Hanan, C. Arana, J.M. Lehn and D. Fenske, Angew. Chem., Int. Ed. Engl., 1995, 34, 1122. ______ACKNOWLEDGEMENT VVP acknowledge C.C Schroff and M. S. University for providing for fellowships and VKS acknowledge CSIR, New Delhi for financial support.
P-425: Investigation of diorganotin(IV) complexes: Synthesis, characterization, in vitro DNA binding studies and cytotoxicity assessment of di–n–butyltin(IV) complex Shipra Yadav, Sartaj Tabassum* Department of Chemistry, Aligarh Muslim University, Aligarh–202002, India *Corresponding author. Tel.: +91 9358255791. E–mail address: [email protected] (S. Tabassum).
Diorganotin(IV) complexes of general formula R2SnL (R = Me, 1; Bu, 2; Ph, 3) with tridentate ONO donor Schiff base ligand have been synthesized and structurally characterized by adopting various spectroscopic (IR, 1H 13C and 119Sn NMR, UV–vis, ESI MS, XRD) and analytical techniques. In vitro DNA binding profile of 1–3 were carried out by various biophysical methods viz., UV–vis titrations, fluorescence, circular dichroic and viscosity measurements which revealed the electrostatic mode of interaction via phosphodiester backbone of 3 4 DNA duplex. The intrinsic binding constant Kb values of L and 1–3 were found to be 7.53 x 10 , 2.98 x 10 , 5.74 x 104 and 3.64 x 104 M–1, respectively suggesting the higher binding propensity of 2, di–n–butyltin(IV) complex as compared to 1 and 3. Further, the computer–aided molecular docking technique was carried out to validate and rationalize the observed binding affinities towards the molecular target DNA. The resulting binding energies of docked complexes were found to be –212.2, –317.8 and –286.0 KJ mol–1, respectively. In addition, complex 2 was found remarkably effective against U373MG (CNS), PC3 (prostrate), Hop62 (lung), HL60 (leukemia), HCT15 (colon), SK–OV–3 (ovarian), HeLa (cervix) and MCF7 (breast) cancer cell lines with GI50 values < 10 µg/ml.
P-426: (DHQD)2PHAL Ligand-Accelerated Cu-Catalyzed Azide-Alkyne Cycloaddition Reactions in Water at Room Temperature Abdul Aziz Ali,1 Mitali Chetia,1 Prakash J. Saikia2 and Diganta Sarma*,1 aDepartment of Chemistry, Dibrugarh University, Dibrugarh-786004, Assam, India bAnalytical Chemistry Division, CSIR-North East Institute of Science & Technology, Jorhat- 785006, Assam, India E-mail: [email protected]; [email protected]
Herein, we have described, a ‘click chemistry’ protocol for the rapid synthesis of 1,2,3- triazoles in water. (DHQD)2PHAL has been found to be an excellent accelerating ligand for the copper(I)-catalyzed azide-alkyne cycloaddition reaction under air. The procedure is simple, efficient, environment-friendly and the products were isolated in excellent yields with high purity.
(DHQD)2PHAL, CuI NN R N R 1 3 2 R N 1 R2 H2O, rt, 5-30 min
References:
1. A. Chanda and V. V. Fokin, Chem. Rev., 2009, 109, 725–748. 2. S. Kobayashi and K. Manabe, Acc. Chem. Res., 2002, 35, 209-217. 3. M. G. Finn and V. V. Fokin, Chem. Rev., 2010, 39, 1231-1232 4. A. A. Ali, M. Chetia, P. J. Saikia and D. Sarma RSC Adv. 2014 (Accepted for publication)
P-427: Synthesis of Glycerol carbonate from transesterification of glycerol with dimethyl carbonate using solid catalyst
S.M.Gade1, M.K.Munshi1, V.H.Rane1 and A.A.Kelkar1*
Chemical Engineering and process development division, National Chemical Laboratory, Pune, India.
S.M.Gade, Email ID: [email protected] Phone no: +91-020-25902392/97
Keywords: Glycerol, Glycerol carbonate, perovskite, DMC
Abstract: Glycerol is one of the renewable feedstock that is being produced in large amount during biodiesel production. The effective utilization of glycerol is a key factor to promote biodiesel commercialization and future developments. This has led to the development of catalysts for the synthesis of value added products from glycerol as evidenced by number of review articles published [1-3]. Among various products, glycerol carbonate is important product with many applications in the field of pharmaceuticals and fine chemical industries. In this work we report our resuls on transesterification of dimethyl carbonate with glycerol using perovskite as catalysts. Catalysts were prepared and characterized by TPD, TEM and XRD spectroscopy. Synthesis of glycerol carbonate with 96% glycerol conversion and high selectivity (95%) has been achieved using (Sr-Ti containing) STR perovskite as a catalyst at 90°C. Effect of various reaction conditions on the activity and selectivity has been investigated in detail.
O OH H C CH + 3 O O 3 HO OH
Dimethyl Carbonate Glycerol
References:
1. G. W. Huber, S. Iborra, and A. Corma. Chem. Rev. 106 (2006) 4044 -4098.
2. M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi, and C. D. Pina, Angew. Chem. Int. Ed.
46 (2007) 4434 – 4440. 3. Y. Zheng, X. Chen and Y. Shen. Chem Rev. 108 (2008) 5253-5276.
P-428: Synthesis of indole fused N,S-heterocycles via ring closing metathesis
M. D. Senthil Kumar, S. Muthusamy* School of Chemistry, Bharathidasan University, Tiruchirappalli-24 Email: [email protected]
Indole nucleus is a prominent structural subunit present in numerous natural products and synthetic compounds with vital medicinal value.[1] Indole annulated heterocyclic compounds are important due to their biological activity.[2] Among the wide variety of heterocycles, N,S containing heterocycles are very important and useful classes of compounds which are widespread in nature. There are several examples for the synthesis of 1,2-fused indole moieties, while those of their sulphur-containing analogs are rare. A literature survey revealed that there are only a few reports are available for the synthesis of indole fused N,S-containing heterocycles. Ring-closing metathesis using the Grubbs’ catalyst is one of the best efficient methods for C=C bond formation and has received a great deal of attention for the synthesis of medium[3] size molecules as well as macrocycles.[4] Synthesis and studies of the indole fused heterocyclic compounds are impressive in organic chemistry due to their biological properties. We herein present the successful synthesis of indole fused N,S-containing ring systems having different sizes from simple oxindoles via ring-closing metathesis process.
References
[1] (a) Faulkner, D. J. Nat. Prod. Rep. 1999, 16, 155. (b) Lounasmaa, M.; Tolvanen, A. Nat. Prod. Rep. 2000, 17, 175. [2] Takada, S.; Makisumi, Y. Chem. Pharm. Bull. 1984, 32, 872. [3] Deiters, A.; Martin, S. F. Chem. Rev. 2004, 104, 2199. [4] Furstner,A.; Muller, C. J. Chem. Soc., Chem. Commun. 2005, 5583.
P-429: Oxidative Rearrangement of Vinyl Bromides to α-Bromoketones and Direct Synthesis of α, α -Dibromoketones from Alkynes using HBr/H2O2 System Venkatanarayana Pappula, R.C. Reddy and Subbarayappa Adimurthy* Academy of Scientific & Innovative Research, CSIR–Central Salt & Marine Chemicals Research Institute, G.B. Marg, Bhavnagar-364 002. Gujarat (INDIA). *Corresponding authors; Ph. No.: +91-278-2471686, E-mail: [email protected]
α-Bromoketones and α,α-dibromoketones are an important precursors for the synthesis of various heterocycles and biological active compounds[1]. The direct syntheses of α-bromoketones from vinyl bromides are rarely reported in the literature [2]. Moreover, the use of catalytic reagent systems for the oxidative rearrangement of vinyl bromides to α-bromoketones has not been explored in the literature.The synthesis of α -bromoketones through oxidative rearrangement of vinyl bromides is described. This oxidative rearrangement has been initiated with catalytic BrOH generated in-situ using 20 mol% HBr and H2O2 as oxidizing agent. The BrOH reacts with π electrons of vinyl bromides to provide intermediate 1,2-dibromophenyl ethanols. Elimination of HBr from this intermediate yields stable α - bromoketones. In this fashion HBr acts as a good catalyst for facilitating the rearrangement of vinyl bromides to α-bromoketones. Using HBr-H2O2 system, good yields of α, α- dibromoketones was obtained directly from alkynes.
Reference [1] K. Kim et al., J. Chem. Soc., Perkin Trans. 1, 253, 1995. [2]M. P. Van brunt et al., J. Org. Chem., 68, 3323, 2003.
P-430: Metal-free Oxidative C-O Bond Formations for theSynthesis of 2,5- Substituted Oxazoles. SupravatSamantaand SubbarayappaAdimurthy * Academy of Scientific & Innovative Research, CSIR–Central Salt & Marine ChemicalsResearch Institute, G.B. Marg, Bhavnagar-364 002. Gujarat (INDIA). *Corresponding authors; Ph. No.: +91-278-2471686, E-mail: [email protected]
Oxazolemoietiesarenot only important for drug discovery research but also in the agrochemicals,fluorescentdyes, polymer industries and serve as ligands invarious metal-catalyzed reactions. Many reported strategies for the synthesis of substituted oxazolesare by the conversion of acyclic precursors into oxazole rings. Recently, our group was reported solar photo-thermochemical synthesis of 2,5-substituted oxazoles from N-arylethylamides using three equivalent of NBS, but ended up with 4-bromo-2,5-substituted oxazoles. In this context, we report herewith the synthesis of desired product 2,5-substituted oxazoles with catalytic amount of halogen (Br2/I2) in presence of oxidant. The present strategy not only eliminates eliminate the use of NBS, but also applicable for wide range of substrate scope.
References [1] S. Rachwaet al.,Chem. Rev.,110, 1564,2010. [2] S. Kim., et al., Org. Biomol. Chem., 9, 4429,2011. [3] S. L. Buchwald et al., Org. Lett., 9, 5521, 2007.
P-431: Synthetic DNA-compacting peptides derived from basic region of HIV-1 TAT protein sequence for efficient gene delivery
G. S. Bhosle, 1 S. Kumar, 2 S. Maiti, *2 M. Fernandes *1 1Organic Chemistry Division, National Chemical Laboratory, Pune 411008, India 2 Proteomics and Structural Biology Unit, Institute of Genomics and Integrative Biology, CSIR, Mathura Road, New Delhi 110007, India. *E-mail: [email protected]
Biophysical characterisation of DNA complexes with peptides is the basic requirement for understanding the gene delivery process. In this work we have studied the interactions between calf thymus DNA and linear cationic peptides derived from basic region of HIV-1 TAT peptide. The series of cationic HIV-1 TAT modified peptides were synthesised using standard Fmoc based solid phase peptide synthesis. UV-visible spectroscopy, isothermal titration calorimetry, Ethidium bromide dye exclusion, Gel Electrophoresis, Circular Dichroism results suggested that HIV-1 TAT derived cationic peptides efficiently bind to calf thymus DNA. Circular Dichroism studies indicate conformational changes that occurring in the DNA:Peptide complexes which result in to DNA condensation.
Sr. Code Peptide sequence Mass (MALDI-TOF) No Calculated Observed 1 TAT 1C Ac-FGRKKRRQRRModgβ-Ala-NH2 1710.06 1714.26 2 TAT 1M Ac-FGRKKModgRQRRRβ-Ala-NH2 1710.06 1714.06 3 TAT M3 Ac-FGModgKKRModgQRRModgβ-Ala-NH2 1820.14 1817.69 4 TAT M4 Ac-FGModgKKRModgQModgRModgβAla-NH2 1875.18 1874.64 5 TAT M3wg Ac-FGModKKRModQRRModβ-Ala-NH2 1694.08 1691.49 6 TAT M4wg Ac-FGModKKRModQModRModβ-Ala-NH2 1707.10 1705.39 7 Control TAT Ac-FGRKKRRQRRR-NH2 1583.98 1582.68
01:00 10 300000 1.0 01:01 ctDNA 50uM M4 280000 Buffer 5uM EtBr 01:02 100uM M4 8 50uM ctDNA 01:03 150uM M4 260000 12.5uM TATM3 200uM M4 25.0uM TATM3 0.8 250uM M4 240000 37.5uM TATM3 6 300uM M4 50uM TATM3 220000 62.5uM TATM3 0.6 4 75uM TATM3 200000 87.5uM TATM3 100uM TATM3 180000 112.5uM TATM3 2 125uM TATM3 0.4 160000 150uM TATM3 200uM TATM3 0 140000 250uM TATM3 Absorbance
0.2 mdeg 120000 -2 100000 fluroscence intensity 80000 0.0 -4 60000 -6 40000 -0.2 20000 -8 0 40 50 60 70 80 90 100 -20000 Temperature -10 220 240 260 280 300 500 550 600 650 700 750 800 Wavelength (nm) Wavelength (nm)
Fig.1 Schematic drawing of γ-arginine modification and peptide DNA interaction monitored by UV Melting, CD Spectroscopy, EtBr Exclusion Experiments
Refrence
1) Patil, K. M.; et al. Bioorg. Med. Chem. Lett. 24, 4198- 4202 , 2014,
2) Ferrer-Miralles N.; et al. Trends Biotechnol ; 26 :267–75. 2008
P-432: Synthesis and biological evaluation of constrained analogs of (+)- erythro-9-(2’s-hydroxy-3’s-nonyl)adenine [(+)-EHNA] as adenosine deaminase inhibitors
Sachin Kandalkar, Parimi Atchuta Ramaia#, Manoj Joshi, Atul Wavhal, Yogesh Waman, Amol Raje, Ashwini Tambe, Vishal Pathade, Ramana Jinugu, Shariq Ansari, B. Srinivasa Reddy, Siddhartha De, Anil Deshpande, Venkata P. Palle, Kasim Mookhtiar, and Dinesh Barawkar*
Drug Discovery Unit, Advinus Therapeutics Ltd (A TATA Enterprise), Quantum tower, Plot no. 9, International Biotech Park, Infotech Park, Phase I, Hinjewadi, Pune 411057, India. #Department of Organic Chemistry, Andhra University, Visakhapatnam-530003, India.
Adenosine deaminase (ADA) catalyzes the hydrolytic deamination of adenosine and 2'-deoxyadenosine to inosine and 2'-deoxyinosine, respectively. Inhibition of ADA activity has significant physiological consequences due to the accumulation of these substrates, which are important mediators of physiological signals through cell surface receptors, and thus offering therapeutic potential in various diseases [1]. From recently available crystal structure (PDB ID: 2Z7G) of ADA complexed with (+)-EHNA (1) a known inhibitor of ADA [2], it has become clear that differences in inhibitor activity at the enzyme level are derived from interactions in the adenine binding site and the hydrophobic pocket. In particular, the hydrophobic pocket seems to play an important role in this aspect [3]. We have modeled a series of derivatives of (+)-EHNA involving hydrophobic pocket interactions, and found that these interactions does make significant contributions to inhibitory activity (Figure I-II). Based on this finding, and other considerations, a series of nonyl chain modified (+)-EHNA derivatives were designed and docked into ADA. Selected analogs were then synthesized for inhibitory studies. A complete account of these modeling studies, synthesis of new analogs and their biological evaluation will be presented.
1. (+)-EHNA (Ki = 1.13 nM)
Figure I Figure II References: 1. Cristalli G.et al;. Med. Res. Rev. 2001, 21 (2), 105-128 and references cited therein. 2. Kinoshita T. et al; Biochemical and Biophysical Research Communications 2008, 373, 53-57. 3. Palle V. P. Pragnacharyulu, et al; J. Med. Chem. 2000, 43, 4694-4700.
P-433: Design and synthesis of macrocyclic aza-polyquinanes by Fischer indolization and ring-closing metathesis as a key steps Ajay Kumar Chinnam and Sambasivarao Kotha*
Department of Chemistry, Indian Institute of Technology-Bombay, Powai, India, Fax: 022-2572 7152; E-mail: [email protected]
We have developed a simple and an efficient synthetic route for the synthesis of aza-polyquinane derivatives involving Fischer indolization under low melting mixture conditions. We have also developed a simple methodology for the construction of aza-polyquinanes involving as Fischer indolization and ring-closing metathesis (RCM) as key steps.
Reference 1. Kotha, S.; Chinnam, A. K.; Tiwari, A. Beilstein J. Org. Chem. 2013, 9, 2709. 2. Kotha, S.; Chinnam, A. K. Synthesis 2014, 46, 301. 3. Kotha, S.; Chinnam, A. K. Heterocycles (accepted). 4. Kotha, S. Chinnam, A. K. Ali, R. (manuscript submitted).
P-434: Diversity-Oriented Approach to Carbocycles and Heterocycles through Ring-Rearrangement Metathesis, Fischer Indole Cyclization, and Diels–Alder Reaction as Key Steps Ongolu Ravikumar and Sambasivarao Kotha* Department of Chemistry, Indian Institute of Technology-Bombay, Powai, Mumbai-400076, India, Fax: +91(22)-2572 7152; E-mail: [email protected].
Readily available norbornene derivatives were subjected to ring-rearrangement metathesis in the presence of ruthenium catalysts to deliver various fused polycycle frames containing carbocycles, oxacycles and azacycles. Enyne ring-rearrangement metathesis of norbornene ring systems with propargyl moiety produced diene containing oxa-bowls, suitable for further expansion by Diels–Alder strategy.
O H H
H H H H H H
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e
t
s N R H H H 5 H s H H O 6 ep ste H st R H ps 6 H 7 H s ps te te p s s s R 8 p
e H t O
s H O H H H 5 R H H H H H H H H H H O
Publication details: (I) Kotha, S.; Ravikumar, O. Eur. J. Org. Chem.2014, 5582-5590
(II) Kotha, S.; Ravikumar, O. Tetrahedron Lett. 2014, 55, 5781-5784
P-435: Syntheses of platinum group metal complexes containing a polydentate ligand system based on dipyridyl amine and 1,3,5 trimethylene benzene. Aradhyula Basava Punna Rao and Kollipara Mohan Rao* Department of Chemistry, North Eastern Hill University, Shillong-793 022, India. Email: [email protected]
ABSTRACT:
6 5 The compounds [(η -arene)Ru(µ-Cl)Cl]2{arene= Benzene, p-cymene} and [(η -Cp*)M(µ-Cl)Cl]2{M= Rh/ Ir} (Justus Tönnemann et al) [1] reacts with a polydentate N,N’-donor ligand viz N-(1,3,5-tris(di pyridyl amino)methyl benzene) (Tdpamb) (Chao Tu et al) [2] in methanol to afford the mononuclear complexes of the 6 5 type [(η -arene)Ru(Tdpamb)Cl]BF4 {arene= Benzene(1), p-cymene(2)} [(η -Cp*)M(Tdpamb)Cl]BF4 {where 6 M= Rh (3); Ir (4)}, dinuclear complexes of the type [(η -arene)2Ru2(Tdpamb)Cl2](BF4)2 {arene= Benzene(5), p- 5 cymene(6)} [(η -Cp*)2M2(Tdpamb)Cl2](BF4)2 {where M= Rh (7); Ir (8)} and trinuclear complexes of the type 6 5 [(η -arene)3Ru3(Tdpamb)Cl3](BF4)3 {arene= Benzene(9), p-cymene(10)} [(η -Cp*)3M3(Tdpamb)Cl3](BF4)3 {where M= Rh (11); Ir (12)} respectively [3]. All these cationic complexes have been isolated as tetrafluoroborate counter ion and are characterized by FT-IR, UV-Vis, Mass and NMR spectroscopic methods. The molecular structure of the complexes 6, 8 and 12 are established by single crystal X-ray diffraction studies.
Fig: Synthetic representation of the complexes.
References:
1. Justus Tönnemann et al. Eur. J. Inorg. Chem. 4558, 2013. 2. Chao Tu et al Inorg. Chem., 42, 5795, 2003. 3. K. Mohan Rao et al Journal of Organometallic Chemistry., 696, 2014, 2011.
P-436: Cascade Synthesis of 2-pyridones using Acrylamides and Ketones Sunil Kumar Rai, Shaziya Khanam and Ashish Kumar Tewari*
Department of Chemistry (Center of Advanced Studies), Faculty of Science, Banaras Hindu University, Varanasi 221005, India. E-mail: [email protected]
The literature reveals that 2-pyridones are found in a wide range of compounds including natural products and medicines1 having a broad spectrum of biological activity like vasodilatory, antimalarial, antiasthma, antiepilepsy, antidiabetic, antimicrobial, antioxidant and antiviral activity etc.2 The development of their efficient synthesis is an important target in current organic synthesis.3 So far, various methods have been developed for the synthesis of substituted 2-pyridone.4 In this work, we have developed a new route for their synthesis through enolate mediated Michael-type addition to acrylamide followed by oxidative cyclization, that produce 2-pyridones in good to excellent yield. However, Unsymmetrical ketones produce two regioisomeric enolates, therefore thermodynamic and kinetic products of butan-2-one and pentan-2-one have been isolated and fully characterized.
References: 1. (a) M. E. Wall, M. C. Wani, C. E. Cook, K. H. Palmer, A. T. Mcphail, G. A. Sim, J. Am. Chem. Soc.1966, 88, 3888. (b) T. Hanada, Y. Hashizume, N. Tokuhara, O. Takenaka, N. Kohmura, A. Ogasawara, S. Hatakeyama, M. Ohgoh, M. Ueno, Y. Nishizawa, Epilepsia 2011, 52, 1331-1340. 2. (a) M. T. Cocco, C. Congiu, V. Onnis, Eur. J. Med. Chem. 2000, 35, 545–552. (b). V. P. Litvinov, Russ. Chem. Rev. 2003, 72, 69–85. (c) T. Murray, S. Zimmerman, Tetrahedron Lett. 1995, 36, 7627–7630. 3. (a) M. Torres, S. Gil, M. Parra, Curr. Org. Chem. 2005, 9, 1757. (b) L. Carles, K. Narkunan, S. Penlou, L. Rousset, D. Bouchu, M. A. Ciufolini, J. Org. Chem., 2002, 67, 4304-4308. (c) J. H. Rigby, Synlett 2000, 1-12. 4. (a) For a review of 2-pyridone synthesis, see: P. A. Keller, In Science of Synthesis Black, D., StC., Ed.; Georg Thieme Verlag: Stuttgart New York, 2005; Vol. 15, pp 285-387. (b) L. Chen, Y. L. Zhao, Q. Liu, C. Cheng, C. R. Piao, J. Org. Chem. 2007, 72, 9259. (c) W. Pan, D. Dong, K. Wang, J. Zhang, R. Wu, D. Xiang, Q. Liu, Org. Lett. 2007, 9, 2421. (d) H. Imase, K. Noguchi, M. Hirano, K. Tanaka, Org. Lett. 2008, 10, 3563. (e) S. Chikhalikar, V. Bhawe, M. Jachak, M. Ghagare Eur. J. Org. Chem. 2011, 6085–6091.
P-437: PAN-PVDF Blend Ultrafiltration Membrane: Optimization of Membrane Properties and Performance V. Polisetti1, N. Bansal2 and P. Ray1* 1Reverse Osmosis Membrane Discipline, CSIR- Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar 364002, Gujarat, India 2Dissertation student at CSIR-CSMCRI Email:[email protected]
Abstract:Synergy in the properties is the main target in making a polymer blend. The present work relates to the development of Polyacrylonitrile (PAN) – Polyvinylidene fluoride (PVDF) blend (ratio varies as 90:10, 70:30, 50:50, 30:70 and 10:90 w/w) ultrafiltration (UF) membranes to improve the fouling resistance and mechanical strength of PAN membranes and to reduce its molecular weight cut-off values. Flat sheet UF membranes were prepared by phase inversion technique using water as the gelling medium. It is observed that increase in PVDF content in the blend increases the contact angle, surface roughness (fig 1) and mechanical strength (fig 2) of the membranes. With increase in PVDF content from 0 to 90 % the rejection of polyethylene oxide (MW 200kDa) increased from 69% to 98% indicating a reduction in the pore size and fouling decreased from 81% to 50 % (fig3).The optimum balance in membrane performance (flux and rejection) was achieved for 70:30 PAN: PVDF blend membrane.
Fig.1: Surface morphology of PAN (A) and PAN: PVDF 50:50 (w/w) (B) blend ultrafiltration membranes.
Fig.2 Stress vs. Strain graphs for PAN, Fig.3 Rejection of PEO (200kDa) by PVDF and PAN-PVDF blend membranes PAN-PVDF blend membranes
Acknowledgement: Financial assistance as research grant in project CSC0104 from Council of Scientific & Industrial Research (CSIR)is gratefully acknowledged.
Reference
1. Y.Xiuli et al., J. Membr. Sci., 146, 179, 1998. 2. M .Yang., T.Liu, J. Membr. Sci., 226,119, 2003. 3. T. Liu et al.,Polym. Adv. Technol., 16, 413, 2005.
P-438: Photocatalytic degradation of Drimaren Black dye using Indian Edible Chuna Nidhi R. Bogam 1 Savita P. Somani 2, Prakash R. Somani 1, 2
1 Department of Physics, Banasthali Vidyapith, Banasthali, Rajasthan, India.
2Applied Science Innovations Pvt. Ltd., Pune – 411041, Maharashtra, India (www.applied-science-innovations.com)
Photocatalytic degradation of Drimaren Black (DB) dye used in textile industry is studied using Indian Edible Chuna as a photocatalyst. Somany Evengreen Knits Ltd., Solapur is acknowledged for donating the dye sample used in their industry. Physico-chemical characterization of Indian Edible Chuna indicates that it is calcium oxide (in dry state) or a mixture of calcium oxide and hydroxide (in wet state). Aqueous solution of DB dye in distilled water - typically of 0.01 mM, 500 ml was used. Studies were carried out by sampling the dye solution at a regular time interval of 15 mins. and noting its visible absorption spectra, varying the catalyst concentration, reaction condition such as pH (in acidic, neutral and basic condition). At pH=7, the time taken for complete photocatalytic degradation (discolaration) of dye was observed to be 330 min. In acidic medium, the dye degradation rate was observed to be fast and degradtaion was completed in 90 min. time. Considering the easy availability, low cost, environment-friendly nature; Indian Edible Chuna seems to be a promising photocatalyst material.
References
1 Liotta,et.al, J. Hazard. Mater., 162(2-3), (2009), 588-606 2 P. R. Somani, et.al , Journal of Green Science and Technology 1 (2013) 2 – 5. . Corresponding Author E-mail : [email protected]
P-439: Dissolution and processing of DNA in sustainable solvents with long term chemical and structural integrity Chandrakant Mukesh and Dr. Kamalesh Prasad*
Marine Biotechnology and Ecology Discipline, CSIR-Central Salt & Marine Chemicals Research Institute, G. B Marg, Bhavnagar-364002 (Gujarat), India, Email: [email protected] Newly designed bio-based ionic liquids namely choline indole-3-acetate (chol- IAA) and choline indole-3- butyrate (Chol-IBA) were employed to dissolve DNA (Salmon testes) upto 3.5% w/w at room temperature in 6 hours.1 The chemical and structural stability of DNA were characterized using various analytical instrumentals such as FT-IR, UV-Vis, CD, 31P NMR and gel electrophoresis. It was observed that DNA maintained its chemical and structural integrity in chol- IAA for six month upon storage at room temperature, while the integrity was lost in Chol-IBA. Further, improved solubility of the same DNA over wide range of pH and better thermal stability of the biomolecule was achieved in bio-deep eutectic solvents namely choline chloride : ethylene glycol (1:2) and choline chloride : glycerol (1:2) with 5.5% w/w and 2.5% w/w solubility respectively. 2 The ionic liquids and DES were recycled and used successfully in the subsequent dissolution processes.
Scheme: Dissolution of DNA in bio-ionic liquid.
Ref:
1. C. Mukesh, et. al., Chem. Commun., 2013, 49, 6849. 2. D. Mondal, et.al.,Chem. Commun., 2013, 49, 9606—9608.
P-440: Recovery and Utilization of graphite and polymers materials from waste lithium-ion batteries (LIBs)for synthesizing polymer-graphite nanocomposite thin film Natarajan S, 1D.Shanthana Lakshmi, 2H.C.Bajaj* 1, Divesh N.Srivastava3 1Discipline of Inorganic Materials and Catalysis (DIMC) 2Reverse Osmosis Membrane 3Analytical Discipline and Centralised Instrument Facility (ADCIF) CSIR-Central Salt and Marine Chemicals Research Institute (CSIR-CSMCRI), G.B.Marg, Bhavnagar–364002, Gujarat, India. *E-mail: [email protected],Fax: +91 278 2567562/2566970. Tel: +91 278 2471793, Ext.7000.
Keywords: E-Waste, waste lithium-ion batteries, polymer, graphite, nanocomposites
Polymer-graphitenanocomposites (PGRC) have attracted great attention due to their potential conductive and mechanical properties [1,2]. Recently disposal of used Lithium-ion batteries (LIBs) is increasing and causing serious concerns to environment [3].Proper disposal of LIBs is important to minimize the hazardous effect and reutilize the waste LIBs constituents for various applications[3,4].In this present work, graphite (GR) and polymers (polypropylene (PP) and polyethylene (PE)) were recovered from waste LIBs and utilized for synthesis ofPGRC thin film (PE/GRx and PP/GRx) using solution intercalation method.Characterisation was done by XRD, FT-IR, TGA and DSC analysis. Result revealed that ~10 times increase in mechanical stability of thin films was observed after graphite incorporation (Fig.1). Electrical property analysis revealed that specific conductance of composite thin film was increased to 5-6 order as compared to neat polymer films. Results established that recovered graphite and polymers may be a good replacement for commercial graphite and polymers.
Fig 1: Tensile strength of (a) Waste PP and PP/GRxnanocomposite thin films (b) Waste PE and PE/GRxnanocomposite thin films.
References 1. C.F. Fabiana et al., J. Polym. Sci.Part A., 48, 692-698, 2009. 2. E.V. Kuvardina et al., J. Appl. Polym. Sci., 128, 1417-1424, 2013. 3. M.Vanitha et al., Environmental Technology Reviews.,2, 101-115, 2013. 4. E. Gratz et al., J.Power sources.,DOI: 10.1016/j.jpowsour.2014.03.126., 2014.
P-441: Surfactant sensitized fluorescence sensing of Zn2+ in water using a modified bipyridine complex Shweta Pawar, Amit Nag*
Department of Chemistry, Birla Institute of Technology and Science Pilani, Hyderabad Campus, Hyderabad 500078, India
Email: [email protected]
Zn2+ is the second most abundant transition metal ion in the body and is involved in many biological activities and neurological functions [1]. Therefore, in the past decade fluorescent sensors for Zn2+ have attracted great attention. The receptor used for sensing zinc should satisfy high biocompatibility and bio imaging capacity. Since, majority of Zn2+ sensors have poor water solubility, our present work is a promising approach to overcome this limitation with development of targeting colloidal transport system such as micelles. This work demonstrates the excellent performance of 4-(pyridine-2-yl)-3H-pyrrolo [2,3-c] quinoline (PPQ) [2] as a fluorescent sensor for sensing Zn2+ in aqueous micellar solution. Entrapment of PPQ has been attempted in different micellar microenvironments of anionic sodium dodecyl sulphate (SDS), non ionic Tween80 and cationic cetyltrimethylammonium bromide (CTAB). Moreover, PPQ can act as a dual sensor for both biologically important zinc and hazardous cadmium (figure 1).
Fluorescence intensity Fluorescence
Ba Cd Co Cu Fe Pb Li Mn Hg Ni Ag Zn PPQ
Metal ions
Fig. 1: Fluorescent response (λex=340nm) of PPQ in SDS solution, to various metal ions.
Reference 1. C. J. Frederickson, Int. Rev. Neurobiol., 31, 145, 1989. 2. Mahesh akula et al, RSC Adv., 4, 25605, 2014.
P-442: Volumetric and Acoustic Studies of Amino Acids in Aqueous 1- Hexyl-3-Methylimidazolium Chloride Ionic Liquid Solutions at T = (288.15 to 308.15) K Harsh Kumar Manchanda*, Chanda Chadha Department of Chemistry, Dr B R Ambedkar National Institute of Technology, Jalandhar - 144011, Punjab, India E-mail: [email protected]; [email protected]
Apparent molar volumes and apparent molar isentropic compressions have been determined for glycine, L- alanine, glycylglycine and phenylalanine in (0.00, 0.01 and 0.03) mol kg-1 aqueous solutions of 1-hexyl-3- methylimidazolium chloride ([C6mim][Cl]) solutions by measurements of densities and speeds of sound at 0 different temperatures. Apparent molar volumes Vφ, partial molar volumes Vφ , partial molar volumes of 0 transfer ∆Vφ and hydration number, nH are evaluated using density data. Apparent molar isentropic 0 compression κφ,s, partial molar isentropic compression κφ ,s , partial molar isentropic compression of transfer 0 ∆κφ ,S , and hydration number, nH have been calculated using ultrasonic speed data. The behavior of these parameters has been interpreted in terms of solute-solute and solute-solvent interactions.
KEYWORDS: 1-Hexyl-3-Methylimidazolium Chloride; Apparent molar volume; Apparent molar Isentropic Compression; Hydration number
P-443: Synthesis and photophysical studies of heteroaryl substituted- BODIPY derivatives for biological applications Karthika. J. Kadassery, Dipti Lakhe, Madhura Pradhan, Uma Ladiwala and Neeraj Agarwal * Chemistry Department, UM-DAE Centre for Excellence in Basic Sciences, Mumbai 400098, India. E-mail: [email protected]
Mono and di-heteroaryl derivatives of 4,4'-difluoro-8-(aryl)-4-bora-3a,4a-diaza-s-indacene (BODIPY) (1-5) were synthesized using slightly modified Suzuki-Miyaura coupling conditions. Hetero aryl substitution on 3- or 3,5- positions caused large bathochromic shifts (up to ~150 nm) in absorption (569-652 nm) and emission maxima (586-679 nm) of these compounds in comparison to classical BODIPY, with quantum yield values as high as 0.65. Absorption in therapeutic window, large molar absorption coefficients and high fluorescence quantum yield of compounds 4 and 5 suggested their application as potential photodynamic therapy (PDT) reagents. Singlet oxygen production activities of these compounds were studied by monitoring the absorbance quenching of 1, 3-diphenylisobenzofuran, on exposure to light (> 600 nm). Cellular uptake of compound 4 was demonstrated using cervical cancer cells and fibroblast cell line and was confirmed by the images obtained using confocal microscope.
Keywords: BODIPY dyes, Photodynamic therapy, Absorption, Emission, Suzuki-Miyaura coupling. *Corresponding author; Tel.: +91 22 26530227; fax: +91 22 26524982; email: [email protected]
Fig.1: Structure of compounds 1-5
Fig.2: Normalized absorption and emission spectra of compounds 1-5
Reference 1. D. Lakhe et al., Tetrahedron Lett, (article in press, DOI: 10.1016/j.tetlet.2014.11.004)
P-444: Experimental validation of theory for EC' reaction on the rough platinum electrode
Ratnesh Kumar and Rama Kant* Department of Chemistry, University of Delhi, Delhi Email: [email protected] URL: http://people.du.ac.in/~rkant
The first order homogeneous catalytic chemical reaction coupled with an electron transfer (EC') in which an electroactive species is regenerated by homogeneous catalytic reaction has attracted great deal of interest in electrosynthetic reactions, organometallic catalysis and biological systems. These processes are ubiquitously influenced by electrode roughness and electrochemical surface heterogeneities. We have developed the theory for chronoamperometry of EC' reaction at rough electrode under single potential step perturbation. Here we experimentally validate our theoretical model for potassium ferrocyanide in the presence of the ascorbic acid at rough Pt electrodes. In this reaction, ascorbic acid is used to catalyze the electrogenerated ferricyanide near electrode-electrolyte interface. Morphological characterization of the rough platinum electrodes and their power spectra of roughness are obtained using hybrid CV-SEM method. Effect of surface roughness on current response in theory enters through the power spectrum of electrode surface. The presence of electrode roughness enhance the EC' reaction current. The experimental data analysis and its comparison with theory explain both steady state and non-steady state diffusion limited chronoamperometric current response. Steady state kinetic control current shows a dependence on mean square thickness of the electrode and pseudo-first order rate constant of homogeneous reaction. Intermediate and short time regime current depends on the roughness factor and other roughness feature of the electrode. Rate constant of the electroactive species is estimated by the experimental chronoamperometric response will regularly belie the true complexities until the roughness is accounted. Finally, experimental data of the EC' reaction is in good agreement with the power spectrum based theory of EC' reaction.
References:- [1] N. Winograd, H. N. Blount, T. Kuwana, J. Phys. Chem. 73 (1969) 3456. [2] R. Kant, Phys. Rev. Lett. 70 (1993) 4094. [3] G. Che, S. Dong, Electrochim. Acta. 39 (1994) 87. [4] R. Kant, S. K. Rangarajan, J. Electroanal. Chem. 368 (1994) 1. [5] S. K. Jha, (2008) Ph.D. Thesis University of Delhi, Delhi. [6] S. K. Jha, R. Kant, Electrochim. Acta. 55 (2010) 7266. [7] K. Kumar, R. Kant, J. Phys. Chem. C 113 (2013) 19558. [8] S. Srivastav, S. Dhillon, R. Kumar, R. Kant. J. Phys. Chem. C 117 (2013) 8594. [9] S. Dhillon, R. Kant, Appl. Surf. Sci. 282 (2013) 105. [10] R. Kant, Md. M. Islam, J. Electroanal. Chem. 713 (2014) 82. [11] S. Dhillon, R. Kant. Electroanalysis. 26 (2014) 2305. [12] Parveen, R. Kant. J. Phys. Chem. C. (2014) DOI 10.1021/jp510469b. ASAP.
P-445: Theoretical studies on size selected hydrated clusters of carboxylic acids: Understanding towards certain macroscopic properties
Dilip Maity Bhabha Atomic Research Centre and Homi Bhabha National Institute Mumbai
Small size molecular systems encapsulated in solvent clusters of different size are considered as model system for studying the influence of solvation on various fundamental molecular properties and processes. We will talk on structure, stability, vibrational and photoelectron spectroscopic properties of carboxylic acids in different size hydrated clusters. In macroscopic description, a strong acid means an acid that ionizes fully in aqueous solution whereas a weak acid does not ionize completely in such an environment. Thus, the ability to transfer a proton to a water molecule is the key to the characteristic feature of an acid. In the context of microscopic description of strength of an acid, one may ask a fundamental question: how many water molecules are required to ionize an acid molecule? In this presentation, we plan to quest for answers of such queries based on a case study on carboxylic acids. Once these acids are dissociated in water environment, they form negatively charged ions. We will also discuss on a new general relation derived for size dependent detachment energy of negatively charged finite size clusters based on a microscopic theory and its performance to predict bulk detachment energy of such acids.
P-446: π-Conjugated Polymer Anisotropic Organogel Assemblies for Photonic Switches Karnati Narasimha and Manickam Jayakannan* Department of Chemistry Indian Institute of Science Education and Research (IISER) Dr. Homi Bhabha Road, Pune 411008, Maharashtra, India. E-mail: [email protected]
Photonic switches (or photonic wave plates) are materials that are capable of transforming the wavelength of light or trafficking optical information for doing specific job or storage. Commercial photonic wave plates are made up of silica (quartz) or inorganic crystals and they are routinely employed as half wave plates (λ/2) or quarter wave plates (λ/4) with respect to their function and applications. To demonstrate the first π-conjugated photonic switch concept; new classes of semi-crystalline and segmented π-conjugated polymers designed with rigid aromatic OPV π-core and flexible alkyl chains. These polymers found to be self-assembled as semi-crystalline or amorphous with respect to the number of carbon atoms in the alkyl units. These semi-crystalline polymers produce Organogels having nano- fibrous morphology. The polymer organogel aligned in a glass capillary and this anisotropic gel device is further demonstrated as photonic switches. The glass capillary device behaves as typical λ/4 photonic wave plates upon the illumination of the plane polarized light. The λ/4 photonic switching ability found to be maximum at θ = 45° angle under the cross-polarizers. The orthogonal arrangements of the gel capillaries produce dark and bright spots as on-and- off optical switches. The organic photonic switch concept can be adapted to large number of other π-conjugated materials for optical communication and storage.
Figure 1. Approaches to develop the first organic Photonic Switches based on segmented π-conjugated polymer anisotropic organogel.
References: 1. Jayakannan, M. et al., ACS Applied Materials & Interface, 2014, 6, 19385-19396
2. Jayakannan, M. et al., Macromolecules, 2014, 47, 2592-2603
P-447: Biosynthesis of Ag and Au nanoparticles using pedicellamide and its application
Chandan Tamulya, Moushumi Hazarikaa, Manabjyoti Bordoloib*
a Natural Product Chemistry Section, CSIR-North East Institute of Science and Technology. Branch Itanagar Arunachal Pradesh-791110, India b Natural Product Chemistry, CSIR-North East Institute of Science and Technology. Jorhat, Assam- 785006, India
The synthesis of silver (Ag), gold (Au) nanoparticles using by an alkaloid pedicellamide (A) isolated from Piper pedicellatum C.DC leaf extract is demonstrated here. The rapid formation of stable Ag and Au nanoparticles has been found using ‘A’ in aqueous medium at normal atmospheric condition. These nanoparticles will be characterized by Transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV-Visible spectrophotometer. The compound ‘A’ is act as a reducing, stabilizing and capping agent. Photocatalytic property of the Ag and Au nanoparticles is investigated by degradation of Methyl red dye under UV light. The kinetic, reaction mechanism and rate constant of photocatalytic degradation of Methyl red was evaluated. The results show that Ag and Au nanoparticles have suitable photocatalytic activity for the degradation of Methyl red dye.
P-448: Development of ion-imprinted polymer for selective removal/detection of Cadmium ion Anuradha Baghel andBeer Singh*
Process Technology Development Division, Defence R&D Establishment, Jhansi Road, Gwalior 474002, India. *Corresponding author. Tel.: +91-751-2341 l960; fax: +91-751-2341 148.E-mail address: [email protected]
Abstract:Molecular imprinted polymers(MIPs) are a group of compounds, where the functional and crosslinking monomers are copolymerised in the presence of a target analyte (imprint molecule), which act as a molecular template.MIPs are employed for preconcentration, solid phase extraction, removal of toxicants,liquid chromatography, recognition of chemical warfare agent, and many more. Recently, we have also contributed in the development of MIPs for heavy metal ion (copper ion) and natural toxicant like ricin. In present study, we focused on the selective removal as well as detection of Cd(II) from aqueous solution. Synthesized polymers (MIPs) were characterized by the techniques such as surface area, FTIR, AAS, TGA, SEM, and EDX, and compared with non-imprinted polymer (NIP) and polymer with cadmium (CdP). SEM analysis of Cd(II)-IIP indicated the changes in surface morphology after imprinting in comparison with NIP and CdP. BET surface area of Cd(II)-IIP (68 m2/g) was found to be more than that of NIP and CdP. TGA analysis showed less char yield for Cd(II)-IIP than NIP. Cd(II)-IIP was further explored for the fabrication of ion selective electrode (ISE), which on binding with Cd(II) gave higher potential than NIP-ISE. Interference study was also performed using Cd(II)-IIP as such and with fabricated ISE with various heavy metals such as Pb(II), Zn(II), Mn(II), Hg(II), and we found that imprinted polymer showed better selectivity for Cd(II) in aqueous solutions.
References
1. AnuradhaBaghel, M Boopathi, Beer Singh, PratibhaPandey, T H Mahato, P K Gutch, K Sekhar,BiosensBioelectron2007,22, 3326-34. 2. SantwanaPradhan, M Boopathi, Om Kumar, AnuradhaBaghel, PratibhaPandey, T H Mahato, Beer Singh, R VijayaraghavanBiosens,Bioelectron2009, 25, 92-8.
P-449: In-situ Synthesis of Magnetic Nanoparticles and their Use as Sustainable Draw Solutions for Forward OsmosisApplications A.Mahto, D. Mondal, K. Prasad* and S.K. Nataraj*
CSIR-Central Salt and Marine Chemicals Research Institute, G.B. Marg, Bhavnagar- 634002, INDIA Corresponding Authors: [email protected]; [email protected] Abstract: Sustainable and energy incentive processes like forward osmosis (FO) process has been in focus in recent years capable of producing high rate of dewatering in a long term operation. Main advantage of FO is that it operates at very low hydraulic pressure, provided 1-4 suitable DS of high osmotic pressure. We have used Fe3O4 nanoparticles dispersed ingreen solvents with high osmotic pressure (π>300 atm) and low water activity (aw<0.1)to desalinate sea water and brackish water by Forward Osmosis (FO). In FO, osmotic gradient across the membrane is the driving force to achieve desalination. The major advantages of this draw solution are recyclability and reuse. In one step FO process, the diluted draw solution is chilled (-5ᶹC) and applied magnetic field to phase separate potable water in the form of ice
and concentrated draw solution (Tf=-66ᶹC) for continuous process.The applications of these draw solutions extend to protein and DNA enrichment, reclamation of potable water from dye solutions to name a few. (a) (b) Figure (a) TEM images of Fe3O4 nanoparticles synthesised in-situ, (b) Depression in effective osmotic pressure of DES with dilution, (c) Trend in conductance of draw solutions as a function of dilution, (c) (d) Feed NaCl (d)Specific flux over a period of 10
hours for CC-Gly-Fe3O4 and CC-
Eg-Fe3O4(1M NaCl feed solution.)
Provisional Patent Application Number: 2356DEL2014
References
1. Z. Liu, H. Bai, J. Lee, D. D. Sun, Energy Environ. Sci,.2011, 4, 2582-2585. 2. J. R. McCutcheon, R. L. McGinnis, M. Elimelech, Desalination, 2005, 174, 1-11. 3. R. L. McGinnis, M. Elimelech, Desalination, 2007,207, 370-382. 4. Q. Ge, M. Ling, T-S. Chung, J. Membr. Sci., 2013,442, 225–237.
P-450: MPA Capped CdSe QDs and PANI composite for biosensor application Maumita Das Mukherjee,a* Kumar Rakesh Ranjan,a Drishti Khandelwala , Disha Jain a and Pratima R. Solanki b
a Department of Applied Chemistry, Amity Institute of Applied Sciences, Amity University, Noida, U.P., India. bSpecial Centre for Nanosciences, Jawaharlal Nehru University, New Delhi, India.
Abstract
In the past two decades, semiconductor nanocrystals especially quantum dots (QDs), have received substantial attention as the QDs whose radii are smaller than the bulk exciton, Kalasad and et al [1]. Among them cadmium selenide (CdSe) is one of the most important nanocrystals due to its high optical absorption coefficient and narrow band gap of 1.74 eV, Kim and et al [2]. Further, it has been observed that introducing CdSe on polymer enhances the charges on polymer backbone thus resulting conformational changes in structure of polyaniline (PANI) which becomes expanded from its compact coiled form, Hu and et al [3]. 3- mercaptopropionic acid (MPA) (C3H6O2S) capped CdSe quantum dots (QDs) and PANI have been synthesized using aqueous route and miceller polymerization respectively. It has been observed that the size of the CdSe QDs can be tuned by varying the temperature and the molarities of Cd2+ and Se2- ions in solution with MPA as the capping ligand. These are characterized using AFM, UV-Visible and Photoluminescence spectra. The synthesized CdSe QDs emits green fluorescence (Fig.1) with particle size of ~ 2 nm. MPA capped CdSe QDs- PANI composite film has been fabricated onto indium-tin-oxide (ITO) coated glass plate for the biosensor application.
70k Excited at 284 nm 60k
50k
40k
30k 20k Photoluminescence (a.u) 10k 0 -10k 500 550 600 650 700 750 Wavelength (nm)
Fig.1 shows peak at 575 nm indicating green luminescence
References
1. M. N. Kalasad, M. K. Rabinal and B. G. Mulimani, Langmuir 2009, 25, 12729-12735. 2. T. N. Kim, D. Li, B. Parijat, M. Xing, L. Zhaona, Z. Liangliang, G. George, X. Qihua and Z. Yanli, ACS Appl. Mater. Interfaces 2013, 5, 8105−8110. 3. X. W. Hu, C. Mao, J. Song, H. Niu, S. Zhang and H. Huang, Biosensors and Bioelectronics, 2013, 41, 372–378.
P-451: Metal derivatives of organophosphorous ligands: From molecular model for zeotype SBUs to single molecule magnets Sandeep K. Gupta and R. Murugavel* Organometallics and Materials Chemistry Laboratory, Department of Chemistry, IIT Bombay
Organophosphorous based metal complexes have been extensively investigated over the last few decades because of theirapplicationsascatalysts, phosphors, nonlinear optical materials and flame retardants, apart from their more recent use in the fields of adsorption, proton conductivity, and magnetism. Our group has extensively investigated the use of phosphonic acids and phosphate esters to build smaller molecular models for several zeotype SBUs in recent years.1
Herein we report the synthesis, characterization and properties of both 3d and 4f metal complexesof organophosphate esters and organophosphonicdiamidesand also on their possible applications. In particular, we will present the first molecular model for zeotype D8R secondary building unit based on anorganophosphate, selective CO2 adsorption by cobalt-phosphate hybrid 3D framework, gadolinium based organophosphates clusters and polymers as magnetic coolants andorganophosphonicdiamides based SMMs.
Molecular model for zeotype D8R SBU based on zinc organophosphate
A 3D cobalt organophosphate framework showing selective CO2 capture
1. R. Murugavel, A. Choudhury, M. G. Walawalkar, R. Pothiraja and C. N. R. Rao, Chem.Rev. 2008,108, 3549-3655.
P-452: Rapid, One-Pot Exfoliation of Hexagonal Boron Nitride by Supercritical Fluids Processing P. Thangasamy and M. Sathish* Functional Materials Division, CSIR-Central Electrochemical Research Institute, Karaikudi – 630006, INDIA. E. mail: [email protected]; [email protected]
Recently, supercritical fluids (SCFs) processing rekindles attention in material synthesis owing to their unique reaction medium. Attempts have been made to exfoliation and functionalization of graphite and graphene nanosheets, respectively [1, 2]. The SCFs with gas-like diffusivity and liquid-like solvent properties along with low viscosity facilitates the rapid exfoliation and functionalization process more effectively. Exfoliation of layered 2D inorganic graphene analogous (IGAs) into few layer nanosheets is still a challenging issue in materials science. Among the various IGAs of layered materials, hexagonal boron nitride is an extremely attractive material for multiple technological applications due to its exceptional mechanical, thermal and electronic properties [3]. Here, we demonstrate a simple, rapid one-pot exfoliation of hexagonal boron nitride into few layer boron nitride nanosheets by supercritical fluids. Exfoliated boron nitride nanosheets were analyzed using various analytical techniques like powder X-ray diffraction, UV-visible, FT-IR, FE-SEM and Raman spectroscopy. The existence of few layers boron nitride nanosheets was confirmed using AFM and TEM analysis.
Fig 1. Structural and Morphological characterization of exfoliated h-BN nanosheets. (A). XRD, (B). Raman, (C). TEM. Reference 1µm 1. D. Rangappa, et al., Chem. Eur. J., 16, 6488, 2010. 300 nm 2. M. Sathish, et al., J. Mater. Chem. A, 2, 4731, 2014. 3. R. Arenal, et al., Adv.Phys. 59, 101, 2010.
P-453: Synthesis of indole fused N,S-heterocycles via ring closing metathesis
M. D. Senthil Kumar, S. Muthusamy* School of Chemistry, Bharathidasan University, Tiruchirappalli-24 Email: [email protected]
Indole nucleus is a prominent structural subunit present in numerous natural products and synthetic compounds with vital medicinal value.[1] Indole annulated heterocyclic compounds are important due to their biological activity.[2] Among the wide variety of heterocycles, N,S containing heterocycles are very important and useful classes of compounds which are widespread in nature. There are several examples for the synthesis of 1,2-fused indole moieties, while those of their sulphur-containing analogs are rare. A literature survey revealed that there are only a few reports are available for the synthesis of indole fused N,S-containing heterocycles. Ring-closing metathesis using the Grubbs’ catalyst is one of the best efficient methods for C=C bond formation and has received a great deal of attention for the synthesis of medium[3] size molecules as well as macrocycles.[4] Synthesis and studies of the indole fused heterocyclic compounds are impressive in organic chemistry due to their biological properties. We herein present the successful synthesis of indole fused N,S-containing ring systems having different sizes from simple oxindoles via ring-closing metathesis process.
References
[1] (a) Faulkner, D. J. Nat. Prod. Rep. 1999, 16, 155. (b) Lounasmaa, M.; Tolvanen, A. Nat. Prod. Rep. 2000, 17, 175. [2] Takada, S.; Makisumi, Y. Chem. Pharm. Bull. 1984, 32, 872. [3] Deiters, A.; Martin, S. F. Chem. Rev. 2004, 104, 2199. [4] Furstner,A.; Muller, C. J. Chem. Soc., Chem. Commun. 2005, 5583.
P-454: A Step Forward to Design the Habit modifiers for Rock-Salt Crystals: Empirical to Rational Approach Anik Sen, Sunirmal Barik, Ajeet Singh and Bishwajit Ganguly
∗ Computation and Simulation unit) Analytical Discipline and Centralized Instrument Facility, CSIR-Central Salt & Marine Chemicals Research Institute, Bhavnagar, Gujarat- 364002, (India), E-mail: [email protected]
The crystal facets engineering and their study have an intense interest from ages.[1] From the last few decades researchers have involved to visualize the proper growth mechanism of salt crystals precisely but it still remains a challenging task. Therefore, the knowledge of growth habits and morphological properties of the crystals is important in understanding and exploiting many of their physicochemical properties. Crystal growth morphology has diverse applications ranging from drug design [2] to explosives [3] and inverse gas chromatography data.[4] Several internal and external factors like temperature, super saturations, solvent and impurities[5,6] are responsible for the habit modification of salt crystal morphology. In this regard, the influence of additives on the crystal habit has received considerable attention.[7,8] It has been found that the additives can reduce crystal growth rate and alter morphology by binding to crystal faces and interfering with propagation steps. Here we are interested to find out a parameter that may can plays a crucial role for the description of an additive to behaves as habit modifiers or non habit modifiers. Otherwise it will remain still empirical as it was for last two centuries.
Urea
LogP= -2.11 Vmin = -56.17 Habit Modifier
Non-Habit Modifier NaCl crystal V = -17.02 LogP= 2.54 min
Toluene
References: 1. Dandekar, P.;Kuvadia,Z. B.;Doherty, M. F. Annu. Rev. Mater. Res., 2013, 43, 359–386. 2. Coombes, D. S.;Catlow, C. R. A.; Gale, J. D.;Hardy, M. J.;Saunders, M. R. J. Pharm. Sci., 2002, 91, 1652–1658. 3. Wang,D.;Chen, S.;Li, Y.;Yang, J.;Wei,T.; Jin, S. J. Energ. Mat., 2014, 32, 184–198. 4. Ho,R.;Wilson,D. A.;Heng, J. Y. Y. Cryst. Growth.Des.,2009, 9, 4907-4911. 5.Sen, A.; Ganguly, B. Angew. Chem. Int. Ed. 2012, 51, 11279–11283. 6.Khan, M. A. S.; Singh, A.; Haldar, S.; Ganguly, B. Cryst. Growth. Des.2011, 11, 1675–1682. 7. Singh, A.; Kesharwani, M. K.; Ganguly, B. Cryst. Growth. Des., 2009, 9, 77–81. 8. Khan, M. A. S.; Sen, A.; Ganguly, B. Cryst. Eng. Comm., 2009, 11, 2660-2667.
P-455: Non-phosphorus ligands for catalytic hydroformylation of olefins G. V. S. Rao, S. H. R. Abdi*, R. I. Kureshy, N. H. Khan, H. C. Bajaj. Academy of Scientific & Innovative Research, Discipline of Inorganic Materials and Catalysis, CSIR–Central Salt & Marine Chemicals Research Institute, G.B. Marg, Bhavnagar-364 002. Fax: +91-0278-2566970; E-mail: [email protected]. (Gujarat INDIA)
Abstract
Hydroformylation (HF) is an elegant strategy in the synthesis of synthones particularly when an aldehyde is produced in a single step by the reaction of an alkene, CO and H2 in a highly regioselective manner [1]. Hydroformylation is one of the important reactions among the homogenously catalyzed reactions used in industries. Oxo chemicals find use in the manufacturing of solvents, soaps, detergents, plasticizers and various intermediates for fine and perfumery chemicals [2]. This powerful 100% atom efficient process is very attractive at the same time very challenging as it requires simultaneous control of regioselectivity. A great deal of progress has been made in the past by developing highly reactive regioselective catalysts based on P or P and Nor O as coordinating hetero atom mainly with Rh [3,4]. However, the synthesis of most efficient ligands is multifaceted, and requires highly controlled multi- step synthesis due to the air-sensitive nature of the phosphine ligands which are major hurdles in the successful commercialization of this powerful strategy. Therefore, the present talk will outline the background of HF of olefins with Rh based catalysts looking beyond phosphorous based ligands.
Here highly regioselective hydroformylation of linear alkenes catalyzed by in situ generated rhodium complexes of non-phosphorus ligands. A set of synthetically easily accessible and air stable non-phosphorous ligands derived from amino acids were evaluated in the hydroformylation (HF) of linear alkenes that gave corresponding products with excellent selectivity regioselectivity.
References [1] a) Rhodium Catalyzed Hydroformylation (Eds.: C. Claver,P.W. N. M. van Leeuwen), Kluwer Academic Publishers,Dordrecht, 2000;
[2] S. Bizzari, M. Blagoev, A. Kishi., CEH Report, Oxo Chemicals, September 2006.
[3] (a) G. Consiglio, S. C. A. Nefkens, A. Borer, Organometallics1991,10, 2046. (b)J. E. Babin, G. T. Whiteker, WO 9303839, U.S. Pat. US 911518, 1992; Chem. Abstr. 1993, 119, 159872h.
[4] Regioselective hydroformylation of vinyl acetate catalyzed by rhodium complex of naphthyl-based monodentate bulky phosphine and phosphite ligands. Aasif A. Dabbawala, Hari C. Bajaj, Ganga V.S. Rao, Sayed H.R. Abdi, Applied Catalysis A: General 419– 420 (2012) 185– 193.
P-456: Unexpected effects of the alteration of structure and stability of myoglobin and hemoglobin in ammonium-based ionic liquids Indrani, Pankaj Attri and Pannuru Venkatesu* Department of Chemistry, University of Delhi, Delhi-110 007 Abstract The nature of solvent-biomolecule interactions is generally weak and non-specific, addition of ionic liquids (ILs), which emerged as novel and new class of solvents, strengthening the stability of some proteins whereas the same ILs weaken the stability of some other proteins. Although ILs are commonly used for the stabilization of biomolecules, the bimolecular interactions of their stabilization/destabilization is still an active subject of considerable interest and this approach has been limited. To reveal the impact of ILs on the stability of + protein, a series of protic ILs possessing tetra-alkyl ammonium cation [R4N] with hydroxide [OH]- anion were synthesized. In this study, we report structural stability of heme proteins such as myoglobin (Mb) and hemoglobin (Hb) in a series of ammonium-based ILs such as + − tetramethyl ammonium hydroxide [(CH3)4N] [OH] (TMAH), tetraethyl ammonium + − + − hydroxide [(C2H5)4N] [OH] (TEAH), tetrapropyl ammonium hydroxide [(C3H7)4N] [OH] + − (TPAH) and tetrabutyl ammonium hydroxide [(C4H9)4N] [OH] (TBAH) by fluorescence and circular dichroism (CD) spectroscopic studies. Our experimental results elucidate that less viscous IL carrying smaller alkyl chain such as TMAH is strong destabilizer of the heme proteins as compared to the IL carrying bulkier alkyl chain which is more viscous IL such as TBAH. Therefore, our results demonstrate that the addition of these ILs to the heme proteins decrease their thermal stability allowing the protein to be in unfolded state at lower temperature than their structure in their native state. Further, we describe the molecular structural interaction of the heme proteins with ILs (molecule like a ligand) by PatchDocking method.
P-457: Methane activation by non stochiometric ceria nano crystals with high Surface defects
Provas Pal,Chiranjit Sen, Subhash C. Ghosh, Asit B. Panda* Discipline of Inorganic Materials and Catalysis, Academy of Scientific and Innovative Research, CSIR- Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, Gujarat, India. E-mail:[email protected], [email protected]
Abstract: We report the highly crystalline Ni/CeO2 catalyst with varying amount of Ni content using ammonium carbonate complex solution of cerium (IV) at low temperature. The catalyst was characterized by XRD, XPS, BET-surface area, SEM, TEM. We have observed that during impregnation of 2.5% Nickle the maximum incorporation of nickel (substitution point defect) and increase in the amount of Nickel, create both the substituational and interstitial point defects. The synthesized catalysts showed catalytic activity for low temperature methane activation to form synthesis gas and facetted aggregates showed excellent activity due to its high surface area, Ce3+/Ce4+ ratio and surface defects due to the formation of Ni-O-Ce layer on the surface may be the possible reason for the high activity of the catalyst with Ni loading between 5-7 wt%.. The 7.5wt% Ni/CeO2 catalyst shows 98% conversion of methane with 72 % selectivity at 800°C without any deactivation till 50 h on time on stream.
(a) (b)
(c)(c) (d)(d)
Fig.1: (a) XPS ‘3s’ Oxygen Spectra of Ni-CeO2 Catalyst. (b) H2-TPR of synthesized Ni-CeO2. (c) CH4- conversion. (d) Selectivity of CO with temperature
Reference: 1. N. Sutradhar et al., J. Phys. Chem. C, 115, 7628, 2011. 2. X. Du et al., J. Phys. Chem. C, 116, 10009, 2012. P-458: Environmentally benign approach towards the synthesis of azaarene–substituted 3–hydroxy–2–oxindoles through sp3 C–H functionalization under microwave Kumkum Kumari, K. N. Singh* Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005 E-mail: [email protected]
The direct functionalization of C–H bonds in organic compounds has emerged as a powerful and ideal method for the construction of carbon–carbon and carbon–heteroatom bonds.1 A green, practical, and metal– free protocol for direct addition of α–and γ–alkylazaarenes to isatins has been developed via sp3 C–H functionalization in water under controlled microwave. This methodology provides a mild and fast access to biologically important azaarene–substituted 3–hydroxy–2–oxindoles in good to excellent yields. Interest in 3- substituted-3-hydroxy-2-oxindoles has increased rapidly as this core structure is present in a number of potential drug candidates for the treatment of proliferative diseases.2 The direct addition of benzylic C–H bonds of α- alkylazaarenes to isatins for the synthesis of azaarene-substituted 3-hydroxy-2-oxindoles represents the most simple and straightforward method to construct such motifs. In light of above we reported the TBAF–catalyzed sp3 C–H functionalization of α/γ–alkylpyridines and α–alkylquinolines in water under controlled MW (Scheme).
Scheme: Functionalization of α–and γ–alkyl
Reference 1. J. Yamaguchi, A. D. Yamaguchi and K. Itami, Angew. Chem., Int. Ed., 51, 8960, 2012. 2. P. Sozzani et al., J. Am. Chem. Soc., 125, 12881, 2003. S. Peddibhotla, Curr. Bioactive Compounds, 5, 20, 2009
P-459: Synthesis, Structure, Spectral and Sensing Properties of Alkyne Functionalized BODIPYs Dijo Prasannan, Subramaniam Sujatha and Chellaiah Arunkumar* Bioinorganic Materials Research Laboratory, Department of Chemistry, School of Natural Sciences, National Institute of Technology Calicut, Kozhikode, Kerala − 673 601, India.
E-mail: [email protected] Abstract: BODIPYs (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) have emerged as fascinating class of dyes which has attracted remarkable research interest because of its excellent physico-chemical properties with potential applications. The present work aimed at the synthesis of meso-alkyne functionalized BODIPYs as sensors [1, 2]. All the synthesized molecules were characterized by UV-Visible, IR, 1H NMR spectroscopic and mass spectrometric methods. The compounds were further confirmed by single crystal X-ray diffraction analysis. Hirshfeld surface analyses (HSs) were done and the 2D fingerprint plots (FPs) were generated in order to quantify the intermolecular interactions present in the crystals using Crystal Explorer 3.1. The cation sensing properties [3,4] of alkyne-functionalized BODIPYs were tested towards various metal ions (Hg2+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Na+, Ca2+, Cd2+ and Pb2+) and other metal ions are in progress. An overall schematic representation is shown in figure 1. R R Y R Z (i) DDQ Z X Z (ii) Et3N Br, K CO / DMF Pyrrole / TFA 2 3 (iii) BF3 OEt2 O RT, N2 DCM, RT 80 C, N2 O O NH HN N N B F F Compound 1, X= H, Y= OH, R= OCH2CCH, Z= H Compound 1-4
Compound 2, X= OH, Y= H, R= H, Z= OCH2CCH
Compound 3, X= H, Y= COOH, R= COOCH2CCH, Z= H
Compound 4, X= COOH, Y= H, R= H, Z= COOCH2CCH
140 PBODIPY 120 MBODIPY CBODIPY 100 CMBODIPY
80
-F 0 F 60
40
20
0 Ni 2+ Cu 2+ Co 2+ Cd 2+ Pb 2+ Hg2+ Mn 2+ Ca2+ Zn2+ Na 2+ Fe 2+ Fe 3+ Cations Figure 1. Synthesis of alkyne functionalized BODIPYs and their sensing properties towards various metal ions
References: 1. J. S. Lindsey et al., J. Org. Chem., 64, 1391, 1999. 2. D. Dolphin et al., Org. Biomol. Chem., 7, 2032, 2009. 3. J. Yoon et al., J. Org. Chem., 71, 2881, 2006. 4. D. Zhu et al., Org. Lett., 9, 2313, 2007.
P-460: Hydrophobically modified chitosan: Synthesis, Characterization and Application towards antimicrobial and anticancer activities
Kamaraj Sriram,1 Palanisamy Uma Maheswari,2 Arasagounder Ezhilarasu,3 Kader Mohamed Meera Sheriffa Begum1
1 Department of Chemical Engineering, National Institute of Technology, Tiruchirappalli - 620 015, Tamilnadu, India.2 Department of Chemistry, National Institute of Technology, Tiruchirappalli - 620 015, Tamilnadu, India.3 Department of Microbiology, Selvam Arts and Science College, Namakkal- 637003 Tamil Nadu, India *E-mail: [email protected]
The hydrophobic modification of chitosan enhances the affinity towards protein, lipid like macromolecular environment and forms typical hydrophobic core with hydrophilic shell nanospheres for transmembrane injection and intracellular delivery.1 The 1,10-phenanthroline-5,6-dione (phendione) modified chitosan (scheme 1) has more smoothened surface in comparison with the pure chitosan and is clearly observed by the AFM measurements. The Sq, Sp, Sv and the TSku- Kurtosis values in comparison with the pure chitosan demonstrates the smoothened surface of the biomaterial with asymmetric distribution of the peaks and valleys. The FTIR and 1H NMR characterizations of the modified chitosan clearly show the inclusion of the intercalator phendione to the –NH2 group of chitosan. The XRD pattern of the modified chitosan shows the orthorhombic pattern as that of the pure chitosan with a new peak around 23˚may be due to the planar phendione modification in the amino groups. The phendione chitosan shows antibacterial, antifungal and anticancer activities as that of the free ligand phendione showing the ability of intra-cellular distribution and antagonist activation towards cellular stimuli.2
Scheme 1. The NH2 group modification of chitosan using phendione ligand to 1,3,2-dioxazole with phenanthroline intercalator.
Reference 1. Stern, R.; Jedrzejas, M. J.; Chem. Rev. 2008, 108, 5061 – 5085. 2. Roy, S.; Hagen, K. D.; Maheswari, P.U.; Lutz, M.; Spek, A. L.; Reedijk, J.; van Wezel. G. P. ChemMedChem 2008, 3, 1427 – 1434.
P-461: Second generation arginine-rich (R-X'-R)4-type cell-penetrating α-ω- α-peptides with constrained, chiral ω-aminoacids (X') for enhanced cargo delivery into cells Kiran M. Patil1, Amit K. Yadav1, Rangeetha J. Naik2, Manika Vij2, Vaijayanti A.Kumar1, Munia Ganguli2,*, Moneesha Fernandes1,* 1Organic Chemistry Division, National Chemical Laboratory, Pune 411008, India 2Structural Biology Unit, CSIR-Institute of Genomics and Integrative Biology, Mathura Road, New Delhi 110025, India E-mail: [email protected]
The indigenous property of cell-penetrating peptides to deliver therapeutic molecules (nucleic acids, drugs, imaging agents) to cells and tissues in a nontoxic manner indicated that they may be potential components of future drugs and disease diagnostic agents. 1Abes et al. reported that the spacing between the charge, hydrophobicity of the linker between the R residues and stereochemistry of the R units influenced intracellular biological activity of PMO conjugated to (R-X-R) peptide. We introduced a small change in amphipathicity of these oligomers by replacing the amide linkage by carbamates. This change significantly improved their properties, in term of cellular uptake, cargo delivery, and cytotocity. 2 Here we synthesized novel N-aminoalkyl proline-derived spacers (X') in polycationic (R- X-R) motif (where R is arginine amino acid ) cell-penetrating α-ω-α-peptides.These modified spacers were improved molecular transporters and their structural features were studied by CD, FACS analysis showed enhanced cellular uptake and confocal microscopy indicated predominantly cytoplasmic localisation.The chirality as well as the contribution to the hydrophobicity and flexibility derived from the spacer chain was found to have marked influence on the cell-penetrating and cargo delivery properties of the cell-penetrating peptides (CPPs). The oligomers were also efficient at transporting pDNA into cells. The peptides containing N-(3-aminopropyl)-D-proline spacers were found to be the best at cell penetration and cargo delivery in the CHO-K1 cell.3
S.No. Peptide Sequences Mass (MALDI-TOF)
Calcd. Obsd. 1 cf-(R-aeLP-R)4-NH2 (I) 2184.26 2185.03
2. cf-(R-aeDP-R)4-NH2 (II) 2184.26 2184.79
3. cf-(R-apLP-R)4-NH2 (III) 2240.32 2241.69
4. cf-(R-apDP-R)4-NH2 (IV) 2240.32 2241.60
5. cf-(R-X-R)4-NH2 (V) 2077.48 2078.07 6. Ac-Phe-(R-aeDP-R) -NH2 (VI) 2016.50 2020.86 4 7. Ac-Phe-(R-apDP-R)4-NH2 (VII) 2072.61 2076.71
8. Ac-Phe-(R-X-R)4-NH2(VIII) 1907.25 1907.33
Table 1 Synthesized peptides Reference 1. R.Abes et al., Nucleic Acids Res., 36, 6343, 2008. 2.K.M.Patil et al., J.Am.Chem.Soc., 134, 7196, 2012. 3.K.M.Patil et al., Bioorg. Med. Chem. Lett., 24, 4198, 2014 .
P-462: C-5 Arylation on 1,2,3-triazoles with Pd catalyst K. Durga Bhaskar yamajala and Shaibal Banerjee*
Department of Applied Chemistry, Defence Institute of Advanced Technology, (Deemed University), Girinagar, Pune-411025, India Email: [email protected], Ph: 020-2430-4164
1,2,3-Triazoles are five member aromatic heterocyclic compound. Triazole moiety has wide range of applications in medicinal, biological and other areas. So we have synthesized novel triazole molecules by arylation on triazole core with Pd catalysis. All the molecules were characterized by 1H NMR, 13C NMR and HRMS. The molecular structure was confirmed by single crystal XRD.
Generally 1,2,3-triazole were synthesizing by the addition of alkynes and azides in presence of Cu(I) catalysed medium[1,2]. But the choice of substituents were limited based on the feasibility of cycloaddition. So, an alternative we envisaged direct arylation on the triazole ring by Pd catalyst. These methods open view of modified triazoles.
Keywords: Arylation, triazoles, Pd-catalyst
References:
1). Hü isgen, R. In 1,3-Dipolr Cycloaddition Chemistry, Padwa, A., Ed., Wiley: New York, 1984: pp1-176.
2). Sharpless, K. B. et al., Angew. Chem., Int. Ed. 2002, 41, 2596
P-463: Azido esters as energetic plasticizers: Synthesis and studies
Sandeep Kumar and Shaibal Banerjee*
Department of Applied Chemistry, Defence Institute of Advanced Technology, (Deemed University), Girinagar, Pune-411025, India Email: [email protected], Ph: 020-2430-4164
The synthetic approach towards novel azido ester as energetic plasticizers has been discussed. Azido ester plasticizers[1,2] have been reported to have better stability and good compatibility with azido binder like Glycidyl Azide Polymer (GAP). They show high heat of formation and low Tg and low viscosity due to lack of restrictive interchain entanglement in contrast to most linear polymers. The Azido ester additives behave as lubricants during process and toughening agent in the final blend formulation [3]. These plasticizers having energetic group such as azido group and methodology is ecofriendly, cheap and scalable. These molecules were characterized by FTIR, 1H NMR, 13C-NMR and HRMS and thermal stability by using TGA and DSC and computational studies.
Keywords: Azido esters, Plasticizers, binders
1. Shaibal Banerjee, et al., Synthetic approach to novel azido esters and their utility as energetic plasticizers
2. S. Brä se and K. Banert, Organic Azides Syntheses and Applications, John Wiley & Sons, UK, 2010.
3. J. P. Agrawal et al., Organic Chemistry of Explosives, John Wiley & Sons, UK, 2007.
.
P-464: Synthesis and antimalarial activity of (+)-norepinephrine alkaloid syncarpamide and its analogues E. K. Aratikatla, T. R. Valkute and A. K. Bhattacharya* Division of Organic Chemistry, National Chemical Laboratory, Pune 411008, India E-mail: [email protected]
A new (+)-norepinephrine alkaloid syncarpamide (1) was isolated from the stem of Zanthoxylum 1,2 syncarpum. It showed antiplasmodial activity with IC50 values of 2.04 μM against Plasmodium falciparum D6 clone and 3.06 μM against P. falciparum W2 clone, respectively. Its synthesis was achieved using Sharpless dihydroxylation of 1,2-dimethoxy-4-vinylbenzene and its structural analogues were synthesized and tested for antiplasmodial activity.
Fig.1: Structure of syncarpamide (1) and their Oxygen (2) and Amino (3) analogues.
Various chiral oxygen and amino analogues of syncarpamide (60 analogues) were synthesized and among the tested analogues, 3 molecules showed promising antiplasmodial activity with IC50 values in the range of 3-4 μM against P. falciparum. The complete biological study of all the synthesized analogues and their structure activity relationship (SAR) is under progress. The chemistry and antimalarial activities of syncarpamide and its analogues will be discussed in detail.
Fig.2: Synthesized analogues of Syncarpamide exhibiting antiplasmodial activity.
Reference 1. Ross, S. A.; Sultana, G. N.; Burandt, C. L.; ElSohly, M. A.; Marais,J. P. J.; Ferreira, D. J. Nat.Prod.2004, 67, 88- 90. 2. Ross, S.A.; Al-Azeib, M. A; Krishnaveni, K. S.; Fronczek, F. R; Burandt, C. L. J. Nat. Prod. 2005, 68, 1297-1299.
P-465: A Convergent Synthesis of (+)-Osmundalactone and epi-(+)- Osmundalactone Using Tri-O-acetyl-D-glucal Tharun K. Kotammagari1, Rajesh G. Gonnade2 Asish K. Bhattacharya*1 1Division of Organic Chemistry, CSIR-National Chemical Laboratory 2Centre for Material Characterization,CSIR-National Chemical Laboratory Dr. Homi Bhabha Road, Pune-411 008 E-mail: [email protected]
Lactone rings are a structural feature of many natural products. Most particularly, those bearing a 5, 6- dihydropyran-2-one moiety are relatively common in various types of natural sources. These pyrones shows wide range of pharmacological activities due to the presence of an α,β-unsaturated δ-lactone [1] moiety as an important structural feature. α,β-Unsaturated δ-lactone functionality is presumed to be responsible for biological activities as a result of its ability to act as a Michael acceptor in the presence of protein functional groups [2]. Because of their manifold biological properties, medicinal as well as organic chemists have turned their attention to develop short and stereoselective synthetic routes for their synthesis.
(+)-Osmundalactone was isolated from Paxillus atromentosus by Buchanan et al [3]. Paxillus atrotomentosus belonging to the Paxillaceae family is a lignicolous mushroom with a large cap and frequently appears on decaying tree trunks. More recently in 2010 Chen et al [4] isolated the isomer of osmundalactone, (5R,6R)-5,6-dihydro-5-hydroxy-6-methyl-2H-pyran-2-one (4-epi-(+)-osmundalactone) from the Angiopteris esculenta.
As part of our continued interest in the exploitation of the reactivity and the usefulness of carbohydrate derivatives in organic synthesis, we have developed an efficient and expeditious synthesis of synthesis of (+)- osmundalactone and 4-epi-(+)-osmundalactone from the readily available glycal derivative tri-O-acetyl-D- glucal.
References:
1. Hoffmann, H. M. R.; Rabe, J. Angew. Chem., Int. Ed. Engl. 1985, 24, 94-110. 2. a). M. Kalesse, M. Christmann, Synthesis 2002, 981–1003; b). L. Bialy, H. Waldmann, Chem. Commun. 2003, 1872–1873.
3. M. S. Buchanan and T. Hashimoto, Phytochemistry, 1995, 40, 1251-1257.
4. Y. Chen, Y. Tao, X. Lian, L. Wang, Y. Zhao, J. Jiang,Y. Zhang.; Food. Chem 2010,1173-1175.
P-466: Efficient synthesis of Dimethyl carbonate via Transesterification of Ethylene carbonate with Methanol over Hydrotalcite as a catalyst N.T.Nivangune, A.A.Kelkar*, V.V.Ranade* Chemical Engineering and process development (CEPD) Division, National Chemical Laboratory, Pune 411008, India.
Abstract:
Dimethyl carbonate (DMC), is an important intermediate and is widely used in industry, due to its nontoxicity, good biodegradability, and excellent solubility. [1] It can replace phosgene, dimethyl sulfate, chloromethane, and methyl chloroformate as carbonylation, methylation, esterification reagent, and it can also be used as an additive for gasoline, flavoring agent of foodstuff, electronic chemical, etc. [2,3] Thus, the effective synthesis of DMC becomes more and more important.
Industrially DMC is synthesized by three routes 1) phosgenation of methanol 2) oxidative carbonylation of methanol [4] and 3) UBE process (using NO). [5] Phosgenation of methanol has been phased out because of the extreme toxicity of phosgene and by-product HCl causes serious corrosion. The oxidative carbonylation of methanol suffers from explosion hazards and need of corrosion resistant reactors.
Considering the social and environmental effects of pollution, it is importance to find out environmentally friendly routes for DMC synthesis. Significant amount of work being carried out by these ecofriendly routes: 1) [6] [7] The urea methanolysis 2) The direct synthesis of DMC from CO2 with methanol 3) The Transesterification of ethylene carbonate and methanol. [8]
Reaction scheme:
We have studied DMC synthesis by transesterification of ethylene carbonate with methanol using Hydrotalcite as a catalyst. Hydrotelcite (HT) is a clay miniral, non-toxic, easy to separate and recyclable catalyst which makes this process environmentally friendly. Different types of HT were prepared using co-precipitation method by varying combinations of bivalent (Ca, Mg, etc) and tri valent (Al, Cr, Fe,Ce etc) cations. All these materials were characterized in detail. All the Hydrotelcites are active among them Mg/Fe HT exhibited superior catalytic activity 83% EC conversion with 85% DMC Selectivity under mild reaction conditions. Parametric study and catalyst recyclability have been investigated in detailed.
Reference:
1) P. Tundo, M. Selva. Acc. Chem. Res. 35, 706 (2002). 2) M. A. Pacheco, C. L. Marshall. Energy Fuels 11, 2 (1997). 3) N. Keller, G. Rebmann, V. Keller. J. Mol. Catal., A: Chem. 317, 1 (2010). 4) W. Mo, H. Xiong, T. Li, X. Guo, G. Li. J. Mol. Catal., A: Chem. 247, 227 (2006). 5) H. Miyazaki, Y. Shimoi, S. Fujitsu, K. Masunaga, US4384133 (1983) 6) H. Y. Lin, B. L. Yang, J. J. Sun, X. P. Wang, D. P. Wang. Chem. Eng. J. 103, 21 (2004) 7) S. Fang, K. Fujimoto. Appl. Catal., A 142, L1 (1996). 8) Y. Zhao, L. N. He, Y. Y. Zhuang, J. Q. Wang. Chin. Chem. Lett. 19, 286 (2008).
P-467: Efficient synthesis of Dimethyl carbonate via Transesterification of Ethylene carbonate with Methanol over Hydrotalcite as a catalyst N.T.Nivangune, A.A.Kelkar*, V.V.Ranade* Chemical Engineering and process development (CEPD) Division, National Chemical Laboratory, Pune 411008, India. Abstract: Dimethyl carbonate (DMC), is an important intermediate and is widely used in industry, due to its nontoxicity, good biodegradability, and excellent solubility. [1] It can replace phosgene, dimethyl sulfate, chloromethane, and methyl chloroformate as carbonylation, methylation, esterification reagent, and it can also be used as an additive for gasoline, flavoring agent of foodstuff, electronic chemical, etc. [2,3] Thus, the effective synthesis of DMC becomes more and more important.
Industrially DMC is synthesized by three routes 1) phosgenation of methanol 2) oxidative carbonylation of methanol [4] and 3) UBE process (using NO). [5] Phosgenation of methanol has been phased out because of the extreme toxicity of phosgene and by-product HCl causes serious corrosion. The oxidative carbonylation of methanol suffers from explosion hazards and need of corrosion resistant reactors.
Considering the social and environmental effects of pollution, it is importance to find out environmentally friendly routes for DMC synthesis. Significant amount of work being carried out by these ecofriendly routes: 1) [6] [7] The urea methanolysis 2) The direct synthesis of DMC from CO2 with methanol 3) The Transesterification of ethylene carbonate and methanol. [8]
Reaction scheme:
We have studied DMC synthesis by transesterification of ethylene carbonate with methanol using Hydrotalcite as a catalyst. Hydrotelcite (HT) is a clay miniral, non-toxic, easy to separate and recyclable catalyst which makes this process environmentally friendly. Different types of HT were prepared using co-precipitation method by varying combinations of bivalent (Ca, Mg, etc) and tri valent (Al, Cr, Fe,Ce etc) cations. All these materials were characterized in detail. All the Hydrotelcites are active among them Mg/Fe HT exhibited superior catalytic activity 83% EC conversion with 85% DMC Selectivity under mild reaction conditions. Parametric study and catalyst recyclability have been investigated in detailed.
Reference: 1) P. Tundo, M. Selva. Acc. Chem. Res. 35, 706 (2002). 2) M. A. Pacheco, C. L. Marshall. Energy Fuels 11, 2 (1997). 3) N. Keller, G. Rebmann, V. Keller. J. Mol. Catal., A: Chem. 317, 1 (2010). 4) W. Mo, H. Xiong, T. Li, X. Guo, G. Li. J. Mol. Catal., A: Chem. 247, 227 (2006). 5) H. Miyazaki, Y. Shimoi, S. Fujitsu, K. Masunaga, US4384133 (1983) 6) H. Y. Lin, B. L. Yang, J. J. Sun, X. P. Wang, D. P. Wang. Chem. Eng. J. 103, 21 (2004) 7) S. Fang, K. Fujimoto. Appl. Catal., A 142, L1 (1996). 8) Y. Zhao, L. N. He, Y. Y. Zhuang, J. Q. Wang. Chin. Chem. Lett. 19, 286 (2008).
P-468: Semi rigid imidazolium carboxylate controlled structural topologies in zwitterionic coordination networks Paladugu Suresh, Chatla Naga Babu and Ganesan Prabusankar* Department of Chemistry, Indian Institute of Technology Hyderabad, ODF Campus, Yeddumailaram, Medak, TS, India-502205. *E-mail: [email protected]
The construction of functionalized coordination polymers (FCPs) have been subject of interest in last few decades due to their fascinating architectures and versatile applications in different fields [1-3]. The suitable organic spacers, metal precursors and synthetic methodologies are the essential criteria to design the FCPs with different physical properties [4,5]. Therefore, the choice of organic spacer is extremely important to fine-tune the structural and desired functional properties of FCPs through coordination mode or non-covalent interaction mode. Within these organic spacers, the imidazolium carboxylic acids are of special interest as they have [C−H]δ+ functional group (potential functional group for anion reorganization and post modification to generate N-heterocyclic carbene tethered catalytically active metal centers) along with excellent functional group tolerance at N-positions. The synthesis and spectral properties of zwitterionic coordination networks, [L2Mn(H2O)2]∞ (1), [L2Co(H2O)2]∞ (2), [L2Ni(H2O)4]∞ (3), [L2Cu]∞ (4), [L2Zn(H2O)2]∞ (5) and [L3Cd2(Br)2]∞ (6) will be discussed. Besides magnetic properties of 1, 2, 3 and 4 will also be discussed.
Fig.1: Molecular structure of 6.
Reference
1. L. J. Murray et al., Chem. Soc. Rev., 38, 1294, 2009. 2. J. Heine et al., Chem. Soc. Rev., 42, 9232, 2013. 3. M. Kurmoo, Chem. Soc. Rev., 38, 1353, 2009. 4. F. A. A. Paz et al., Chem. Soc., Rev. 41, 1088, 2012. 5. N. Stock et al., Chem. Rev., 112, 933, 2012.
P-469: Bio-based foam membranes for sustainable oil-water separation Jai Prakash Chaudhary, Sanna Kotrappanvar Nataraj*, Ramavatar Meena* Process Design & Engineering Cell, CSIR-Central Salt & Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, Gujarat, India.
E-mail: [email protected]; [email protected] Fax: +91-278-2567562; Tel: +91-278- 2567760 Abstract:
We have developed a low cost, high performance bio-based membrane technology to clean harsh wastewater streams sensitive to environmental sustainability. Novel foam membranes (FMs) have derived from agarose (Agr) and gelatin (Gel) in combination with a non-toxic fruit extract genipin (G). FMs were successfully tested for their oil-water separation efficiencies. Stable microporous foam membranes with nominal pore size covering the microfiltration and ultrafiltration range generated as high as >500 L.m-2.h-1 continuous flux with ~98 % pure product water. One of the advantages with FM, post oil-water separation is that it undergoes easy membrane cleaning process thereby retaining surface activity for long
term performance, and another hand FM is degradable under soil conditions.
References:
1) Chaudhary et al., Green Chem., 2014, 16, 4552.
2) Highlighted in CSIR News dated on Sept 14, 2014. (http://www.niscair.res.in/ScienceCommunication/RnDNewsLetters/csirnews2k14/csi rnews_sep14.pdf).
P-470: Design and Synthesis of a Class of Novel Heterocyclic Compounds as Potential Cyclooxygenase Inhibitor and to Study their Photophysics as well Jyotirmay Maiti, 1 Ranjan Das1, Suman Biswas*1 1West Bengal State University, Kolkata 700126, India. *E-mail: [email protected], Fax: (033) 2524 1977, Contact No: 033-2524-1975/76
Abstract: Cyclooxygenases (COXs; prostaglandin G/H synthases) catalyzes the first two steps in the biosynthesis of (PGs) [1]. COXs exist in two distinct isoforms, a constitutive form COX-1 and an inducible form COX-2. These two COXs are the targets of widely used nonsteroidal anti-inflammatory drugs (NSAIDs), which play a therapeutic role in the treatment of fever, pain and inflammation. Selective small molecule COX-2 (PDB-ID: 5COX) inhibitors are synthesized and characterized by 1H-NMR, 13C-NMR, HR-MS analysis. Molecular docking studies of each of them with COX-2 are done with Autodock vina [2] extensively using the Python script collection (Autodock Tools [3]). The visualization and binding site analysis is done by PyMOL [4]. Lowest binding energy of the complexes is calculated from YASARA [5]. Furthermore, the synthesized compounds exhibit different photophysical properties. Emission spectra and red-shift of λ-max respectively are in accordance with the fluorescence property and inclusion complex formation with cucurbit-uril and β, γ- cyclodextrins.
References: 1. Carol A. Rouzer and Lawrence J. Marnett, J. Lipid Res. 2009, 50: S29-S34 2. Trott O, Olson A (2010) AutoDock Vina: improving the speed and accuracy of docking with a new scoring function efcient optimization, and multithreading. J Comp Chem 31:455–461 3. Michel F. Sanner. Python: A Programming Language for Software Integration and Development. J. Mol. Graphics Mod., 1999, Vol 17, February. pp 57-61 4. DeLano WL (2002) ThePy MOL molecular graphics system. http://www.pymol.org 5. Elmar Krieger et.al., Center for Molecular and Biomolecular Informatics, Radboud University Nijmegen Medical Centre, Nijmegen, The Netherlands. http://www.yasara.org
P-471: Investigation on Reverse Water Gas shift Reaction catalyzed by Metal halogen carbonyl complexes: A Density Functional study
Ranga Santosh, Archita Sharma, Kolli Deepika and Subhas Ghosal *
Birla Institute of Technology and Science, Pilani, Hyderabad Campus, Jawahar Nagar, Hyderabad 500078 E-mail: [email protected]
The water-gas shift reaction (CO + H2O → CO2 + H2) (WGSR) is an important industrial process for removal of carbon monoxide and production of H2 catalyzed by carbonyl complexes of transition metal Fe, Ru, Ni, Rh etc.Typical mechanism for WGSR had been proposed in earlier studies [1-2]. We will present a theoretical study for a recent experiment [3] on the Reverse water gas shift reaction i.e. H2 + CO2→ CO + H2O (RWGSR) catalyzed by Ruthenium halogen carbonyls complexes.
The mechanism, energetics and possible transition states are calculated using Density Functional Theory (DFT).
Reference
1. Hannes Schulz, Andreas Gorling, and Wolfgang Hieringer.., Inorg, chem.2013, 52, 4786-4794.
2.. Nishamol Kuriakose, Shantanu Kadam, and Kumar Vanka., Inorg, chem, 2012, 51,377-385.
3. Kazuyoshi Tsuchiya, Jia-Di Huang, and Ken-ichiTominaga., ACS Catal,2013,3,2865-2868.
P-472: Do we need a probe for determination of cmc of Imidazolium based Surface Active Ionic Liquids through Spectrophotometry? Mudasir Ahmad Rather*, Sarwar Ahmad Pandit, Sajad Ahmad Bhat, Mohsin Ahmad Bhat and Ghulam Mohammad Rather
Department of Chemistry, University of Kashmir, Srinagar-190006, J&K, India.
Abstract
Investigations on the micellization behaviour of a series of freshly prepared[1-3] imidazolium based surface active ionic liquids [SAILs] viz 1-Octyl-3-methylimidazolium chloride [OMIM][Cl], 1-Octyl-3- methylimidazolium dodecylsulphate [OMIM][DS], 1-Octyl-3-methylimidazolium benzoate [OMIM][Bz], 1- Octyl-3-methylimidazolium salicylate [OMIM][Sc], 1-Octyl-3-methylimidazolium acetate [OMIM][Ac] through probe less UV-Visible spectrophotometry have been undertaken. The cmcs estimated through spectrophotometric method were found to be a close match to the value estimated through tensiometry for the investigated SAILs. The cmc for the investigated SAILs were found to vary as order [OMIM][Cl]>[OMIM][Ac]>[OMIM][Bz]>[OMIM][Sc]>[OMIM][DS] [4-8]. Also to the best of our knowledge the synthesis, characterisation and micellization behaviour of [OMIM][Bz] and [OMIM][Sc] which is the first report of such a kind will be presented.
KEY WORDS: Surface active ionic liquids, Probe less UV-Visible Spectrophotometry, Tensiometry, Micellization.
* e-mail; [email protected] Mobile no.; 9858960220
REFERENCES: 1. T. Welton, Chem. Rev. 991 (999) 2071. 2. Susan D. Arco, Rosalie T. Laxamana, Ofelia D. Giron and Judy M. Obliosca Philippine Journal of Science 138 (2009) 133. 3. Judy M. Obliosca & Susan D. Arco & Michael H. Huang. J Fluoresc 17 (2007) 613. 4. C. Junnickel, J. Luczak, J. Ranke, J.F. Fernandez, A. Muller, J. Thoming, Colloids Surf. A 316 (2008) 178. 5. H. Wang, J. Wang, S. Zhang, X. Xuan, J. Phys. Chem. B 112 (2008) 16682. 6. S. Manet, Y. Karpichev, D. Dedovets, R. Oda. Langmuir 29 (2013) 3518. 7. J. Jiao, B. Dong, H. Zhang, Y. Zhao, X. Wang, R. Wang, L. Yu. J. Phys. Chem. B 116 (2012) 958. 8. M. Akram, S. Yousuf, T. Sarwar, Kabir-ud-din. Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 281
P-473: Investigations on some perylene based donor – pi – acceptor systems for efficient dye sensitized solar cells using Density functional theory. Taniya Manzoor, Summera Asmi and Altaf Hussain pandith. Department of Chemistry, University of Kashmir, Srinagar, Kashmir, India-190006 Email id:[email protected] Abstract Theoretical studies on the perylene based dyes for efficient dye sensitized solar cells was carried out using Gaussian 03[1] using 6311-g (d,p) and B3LYP[2]. The extension of the framework was carried out in the donor -pi acceptor form with perylene as the donor, furan / pyrrole / thiopene as the pi-bridge and cyanoacrylic group as the acceptor. It was followed by Substitutions on the bay positions with different groups on the basic dye molecule. TDDFT studies were carried out for all the dye both in vaccum and solvent phase to study the UV absorption behaviour of these dyes for efficient dye sensitized solar cells(DSSC’s). Both the optical and photovoltaic properties of these dyes were studied. From the calculation of various vital parameters it was found that dye P7 exhibits a good balance of the various optical and photovoltaic properties thereby enhancing the efficiency of the DSSCs based on such systems. Keywords : DFT, HOMO-LUMO energy gap, free energy of electron Injection and Light harvesting efficiency.
Corresponding author info.: Mob. No:9906424293, email id: [email protected]
Fig. UV-Visible spectra of the dyes
References
[1] Frisch MJ, Trucks GW, Schlegel HB, Scuseria, GE, Robb MA, Cheeseman JR. Gaussian 03; 2004;Gaussian, Inc: Wallingford, CT. [2] Becke AD. Density-functional exchange - energy approximation with correct asymptotic behavior. Phys Rev A 1988;38:3098 - 3100.
P-474: Synthesis of atomically precise silver clusters using the miscibility principle Atanu Ghosh and Thalappil Pradeep* DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry Indian Institute of Technology Madras. * E-mail: [email protected]
Interesting structural, optical and electronic properties of quantum clusters as well as their potential applications in catalysis, biomedicine and nanoelectronics have made these systems important for chemistry and materials science as a whole. Systematic size evolution of these clusters leading to bulk materials allows the investigation of emergence of size-dependent properties. We have developed a new strategy to synthesize a diverse array of organic soluble, atomically precise silver clusters. The technique, based on the miscibility principle of solvents, uses no phase transfer agents which is a persistent impurity for the previously reported two phase methods and makes various clusters of masses 8.0, 13.4, 22.8, 29.2 and 34.4 kDa by changing the reactant compositions. Among the silver clusters formed, we have studied the new 13.4 kDa species with unique step- like features in the UV-vis spectrum in detail by mass spectrometry and other analytical techniques. The compound has been assigned as Ag68(SBB)34 which is reported for the first time. By time dependent studies, we have shown that the synthetic route follows the bottom up approach. The material forms microcrystals. We are expecting that the proposed synthetic strategy and the cluster synthesized will help to extend the area of atomically precise clusters.
Ag68(SBB)34
m/z
Figure 1. Phase diagram of the three-component system used for the experiments. Four different regions in the phase diagram are marked where the reactions were performed. Mass spectrum of the characterized product (Ag68SBB34) is shown.
References: 1. Mathew, A.; Pradeep, T. Part. Part. Syst. Charact. 2014, doi: 10.1002/ppsc.201400033.
2. Qian, H.; Zhu, M.; Wu, Z.; Jin, R. Acc. Chem. Res. 2012, 45, 1470-1479.
3. Ghosh, A.; Udayabhaskararao, T.; Pradeep, T. J. Phys. Chem. Lett. 2012, 3, 1997-2002. 4. Rao, T. U. B.; Nataraju, B.; Pradeep, T. J. Am. Chem. Soc. 2010, 132, 16304-16307.
P-475: Effect of gamma irradiation on photoluminescence properties of 3+ 3+ YPO4:Eu and YPO4:Dy Sudheer.G1, Anima S.Dadhich1, Abhijit Saha2 and Saratchandra babu Mukkamala1* 1Department of Chemistry, GIS, GITAM University, Visakhapatnam-530045, A.P. 2Department of Radiation Chemistry, UGC-DAE CSR Kolkata Centre, Kolkata-700098, W.B. Email: [email protected]
Abstract
Effects of γ-irradiation on nano phosphors is a growing area of interest in recent years due to its wide range of applications in diverse fields like medical imagining, drug delivery, industrial process, optical communications, lasers, solar cells, fluorescent lamps, light emitting diodes etc[1-3]. Eu3+and Dy3+ doped uniform hexagonal YPO4 nano phosphors with size ranging from 30-70 nm width and 220-300 nm length have been synthesized by hydrothermal technique. The prepared phosphors were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), transmission electron microscope (TEM), photoluminescence spectra 3+ 5 7 5 7 (PL) etc. YPO4: Eu gives three red emission peaks at 582, 587 and 610nm corresponds to D0- F0, D0- F1 and 5 7 3+ D0- F2 transitions, respectively. YPO4: Dy exhibits two emission peaks at 485 nm (blue) and 575 nm (yellow) 4 6 4 6 corresponding to F9/2- H15/2 and F9/2- H13/2 transitions, respectively. Moreover, quenching of 3+ 3+ photoluminescence was observed in both YPO4: Eu and YPO4:Dy phosphors at 5 and 300 k Gy radiation.
3+ 3+ 3+ Fig.1. TEM images of (a) YPO4:Eu , (b) YPO4:Dy , (c) Photoluminescence spectra of YPO4:Eu (1) 3+ unirradiated (2) γ-ray irradiated 5kGy (3) γ-ray irradiated 300kGy. (d) Photoluminescence spectra YPO4:Dy (1) unirradiated (2) γ-ray irradiated 5kGy (3) γ-ray irradiated 300kGy.
References
1. M.Devi et al., Appl. Phys.A, 106, 757, 2012. 2. T.Y.Liu et al., J.Magn.Mater, 310, 850, 2007. 3. L.Jun et al., Phys.Lett, 27,38104,2010.
P-476: Micellar Charge Selective Fluorescence Response of Amiloride withBiologically Important Metal Ion, Cu2+ VarshaGujar, and DivyaOttoor * Department of Chemistry, SavitribaiPhule Pune University, Pune, 411 007, India E-mail: [email protected]
Abstract: Interaction of antihypertensive drug Amiloride (AMI) with biologically important metal ion, Cu2+ in various micellar media (anionic SDS (Sodium dodecyl sulfate), nonionic TX-100 (TritonX-100) and cationic CTAB (Cetyltrimethyl ammonium bromide)) and at different pH is studied using fluorescence spectroscopy. It was observed that the fluorescence properties of AMI remain unaltered in the absence of micellar media with increasing concentration of metal ion. The enhancement in fluorescent intensity of AMI was observed in anionic micelle due to the switch of the aqueous surroundings of the fluorophore to the hydrophobic microenvironment provided by SDS micelles. Quenching of fluorescent intensity of AMI on addition of Cu2+was observed in anionic micelle, whereasno remarkable changes observed when AMI was present in cationic and nonionic micellar medium. The binding constant and bimolecular quenching constants were evaluated for the drug-metal complexes using Stern-Volmer equation and fluorescence lifetime values.
3500 4500 AMI+SDS A AMI+SDS B 4000 3000 2+ 2+ AMI+SDS+Cu (10-100ppm) 3500 AMI+SDS+Cu (10-100ppm) 2500 3000 2000 2500
2000 1500
1500 1000
FluorescenceIntensity 1000 AMI FluorescenceIntensity AMI 500 500
0 0 380 400 420 440 460 480 500 380 400 420 440 460 480 500 Wavelength(nm) Wavelength(nm)
Figure 1: Fluorescence emission spectra of AMI (1x10-6M) in presence of SDS (10 mM) with increasing Cu2+ concentration (10-100ppm) at A) pH ~7. B) pH ~2.
References:
1. A. K.Ghosh, A. Samanta and P.Bandyopadhyay, J. Phys. Chem. B. 115, 11823, 2011. 2. L. Ding, S. Wang, Y. Liu, J. Cao and Y. Fang, J. Mater. Chem. A. 1, 8866-8875, 2013.
P-477: Synthesis and Properties ofPyrazine functionalized hyperbranched Poly(p-PhenyleneVinylene) for light emitting diode application
S. Karpagam*and S. Sudha Organic Chemistry Division, School of Advanced Science, VIT University, Vellore -14. Tamil Nadu, India *Email: [email protected] Telephone: 91-416-2202334 Fax:91-416-2243092
Abstract:
Partially conjugated hyper branched pyrazinefunctionalizd poly(phenylenevinylene) (HPPV) was synthesized via Wittig route by using trimethylol propane as the core and 2,3- dimethyl substitutedpyrazinephenylenevinylene as the connecting unit. The structure of HPPV was confirmed by spectral studies viz., UV, FT-IR, NMR and GPC. It was found that the HPPV was highly soluble in common organic solvents. Absorption and photoluminescent property were studied with various solvents. The oxidation potential was studied by cyclic voltammetry. The clear morphology of the polymer was observed from AFM. Because of the HPPV is having excellent performance in photoluminescence which can be used as a good material in light emitting diodes(LEDs).
keywords:Hyperbranched Polymer;Photoluminescence; Wittig Reaction; Pyrazine; Poly(phenylenevinylene)
P-478: Ecofriendly sensor for selective detection of Hg2+ in aqueous medium
Faisal Kholiya, Jai Prakash Chaudhary, Nilesh Vadodariya, Ramavatar Meena*
Process Design & Engineering Cell, CSIR-Central Salt & Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, Gujarat, India.
*E-mail: [email protected]; Fax: +91-278-2567562; Tel: +91-278-2567760
Abstract:
We have developed carboxymethylagarose stabilized gold nanoparticles (CMA-AuNPs) generated through a rapid, cost effective and green route for the selective detection of Hg2+ in aqueous media. When CMA-AuNPs were exposed to an aqueous Hg2+, a blue shift for its localized surface plasmon resonance is observed along with color change of the solution. The probe enables to detect Hg2+ in the range of 0.01–100 ppm even in spiked lake water samples. This study opens a sustainable and eco-friendly route for selective detection of Hg2+ in aqueous solution and may find potential application towards water purification.
References:
1. Chaudhary et al., Carbohydrate Polymers 2015,117, 537–542. 2. Highlighted in Nature India http://www.natureasia.com/en/nindia/article/10.1038/nindia.2014.145.
P-479: Graphene quantum dots for bioimaging and drug delivery Gayatri Salunke,1Bhawna Bagra,1Mousami Sen Biswas,1 Pankaj Poddar* 1Physical and MaterialChemistry Division, National Chemical Laboratory, Pune 411008, India
Abstract : Graphene have potential to create a revolution in the field of biomedicine because of their low cytotoxicity and larger surface area to volume ratio [1,2]. In this study, we are exploring therapeutic as well as a diagnostic potential of graphene quantum dots (GQDs). GQDs are synthesized from ash as a carbon source using microwave. We obtained ~2-5nm particles with a charge of -8.44 mV. Moreover, FTIR spectroscopy showed three peaks at ~1078, ~1590, ~1321 cm-1 representing stretching vibrations of C-O, C=C, carboxyl or conjugated carbonyl group. The emission wavelengths of GQDs are 440 nm implying its use in FACs and confocal microscopy as a fluorescent probe. Also, it was observed that GQDs are not cytotoxic from a concentration of 20 – 200 mg/mL. GQDs are further employed for conjugation with protein and antibodies against Her2, a receptor overexpressed in breast cancer cell lines. Smar1 (scaffold/matrix associated region binding protein 1) used in the study is a tumor suppressor protein [3]. Thus, we hypothesize the theranostic approach employing GQDs/Smar1/Ab conjugation using approaches, linker molecules, coated GQDs.
SMAR1+Buffer
4 60 ex-480 ex-300 ex-320 50 ex-340 3 ex-360 ex-380 40 ex-400 ex-420 2 ex-440
30 ex-460 1
Intensity(a.u) 20
Absorbance(a.u) 10 0
0 300 350 400 450 500 550 -1 200 210 220 230 240 250 260 270 280 290 300 Wavelength(nm) Wavelength(nm) Figure 1. Photoluminescence spectra of GQDs. Figure 2. UV-visible spectra of Smar1.
Reference 1. X Sun et al., Nano Res., 1(3), 203–212, 2008. 2. Zhang L et al., Small., 6(4), 537–544, 2010. 3. R Kaul-Ghanekar et al., BMC Cancer, 9(50), 2009.
P-480: Synthesis and Characterization of Lignin supported Nickel Nanoparticles: Applications in hydrogenation of carbonyl compounds to alcohol Marulasiddeshwara M. B,Satheesh C E, Rajegowda H R, P. Raghavendra Kumar* Department of Studies and Research in Chemistry, Tumkur University, Tumkur-572103, Karnataka, India. *Corresponding author E-mailaddress:[email protected]; Ph. No. 91-9901511112 Keywords: Nickel,Nnanoparticles; Lignin, Biopolymer,Hydrogen transfer,Heterogeneous catalysis
A b s t r a c t Lignin supported nickel (0) nanoparticle was synthesized by reduction of Ni(II) salt successfully. The influence of the various parameters on the particle size of Ni nanopatrticles were studied. The morpology and size of the Ni nanopatrticles were characterized by UV Vis, FT-IR, SEM , PXRD and ICP.The compositions was determine by EDAX measurements and was found that 25% of Ni was loaded on lignin.This hereogeneous nano nickel catalysthave been used in the transfer hydrogenation of carbonyl compounds into alcohols.Short reaction time with good to excellent yields (85-95%) of the desired products represents the effectiveness of this catalyst for these reactions. The catalyst was reusable for several times in repeating cycles without considerable loss in its activity and the catalyst was recovered by simple filtration and reused for many times .The Nickel nanoparticles unveiled a superior behavior in comparison with commercially available nickel catalysts.
Lignin Lignin-Ni NPs
NiCl2.6 H2O
RT
SEM images of lignin and lignin supported nickel nanoparticles (NPs)
lignin Ni 500
450
400
350
300
250 INTENSITY
200
150
100 10 20 30 40 50 60 70 80 2Θ
XRD of Lignin @ Nickel nanoparticles
O OH
LIGNIN@NI NANOPARTICLE CH3 CH3 o HCOONH4,THF N2 25 C R R P-481: Design and synthesis of ‘Aggregation Induced Phosphorescence-AIP’ Active Platinum(II) Complex and a Facile Approach to Phosphorescent Mesoporous Silica
Sheik Saleem Pashaa, Parvej Alama, Amrit Sharmaa, Gurpreet Kaurb, Angshuman Roy Choudhuryb, Inamur Rahaman Laskara*
aDepartment of Chemistry, Birla Institute of Technology and Science, Pilani Campus, Pilani, Rajasthan, India, [email protected]; bDepartment of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Mohali, Sector 81, S. A. S. Nagar, Manauli PO, Mohali, Punjab, 140306, India, [email protected]
‘Aggregation Induced Phosphorescence-AIP’ Active Platinum(II) complexes are very rare. The strategic design and syntheses of these types of complexes has a great importance in the areas of biomedical and optoelectronic applications1. The various solid state applications and the solution phase many bio applications with luminescent materials are mainly suffering from ‘Aggregation Caused Quenching (ACQ)’1. The AIP is an anti ACQ phenomenon. The AIP complexes of Pt(II) having huge demand due to their very high quantum efficiency and strong luminescence in solid state. The syntheses of AIP active molecules are normally carried out through introduction, by using rotor type bulky group2. We have synthesized a novel molecule [Pt(ppy)(NH2CH2CH2NHCPh3)] which have no emission in solution, but shows strong emission in its aggregated form supporting its AIP nature. The mixing of this orange emitting complex with non-luminescent mesoporous silica3 is resulted a green color emission. We will demonstrate the change of this luminescence behavior.
Figure 1: AIP property of Pt(II) complex and its emission spectra with defferent ratio of MeOH and water (0-95%, v/v)
Refferences 1. P. Alam, P. Das, C. Climentc, M. Karanam, D.Casanovac, A. R. Choudhury, P. Alemany, N. R. Jana and I. R.Laskar, J. Mater. Chem C, 2014, 2, 5618; 2. P. Alam, M. Karanam, D. Bandyopadhyay, A. R. Choudhury and I. R. Laskar, Eur. J. Inorg. Chem. 2014, 23, 3710. 3. H. Zhou, X. Lv, L. Zhang, A. Gong, A. Wu, Z. Liang, G. Peng and H. Lin, J. Mater. Chem. C, 2014 DOI: 10.1039/C4TC02163K.
P-482: CuO-Nanoparticles-Catalysed [3+2] Cycloaddtion of Azide–Internal Alkyne in Aqueous Media S. Sagubar Sadik, T. Kiranmye, D. Gangaprasad, J. Paulraj, J. Elangovan* Department of Chemistry, B. S. Abdur Rahman University, Chennai 600048, India Email: [email protected]
The 1,2,3-triazole unit abounds in many biologically active nitrogen compounds exhibiting versatile activities such as antibacterial, anticancer, antiviral and antituberculosis [1]. This molecules can be accomplished by the conventional copper-catalysed azide-alkyne cycloaddtion (CuAAC) [2]. But this method is limited only to terminal alkynes. For internal alkynes, a few methods have been reported in the literature [3]. However cycloaddition of azide with internal alkynes still remains as a challenge. Here we report the efficient azide-internal alkyne cycloaddition using CuO nanoparticles under aqueous condition. Catalyst recyclability and base free condition are the salient features of this protocol.
CuO nanoparticles N N R R R + R1 N 3 1 N Water, reflux, 24h R R
Reference
1. K. Jozwiak et al., Chem. Rev., 2013, 113, 4905. 2. L. Micouin et al., Angew. Chem. Int. Ed., 2010, 49, 2607. 3. a) V. V. Fokin et al., J. Am. Chem. Soc., 2005, 127, 15998; b) H. Tanimoto et al., Org. Lett., 2013, 15, 5222; c) J. Sun et al., Angew. Chem., 2014, 126, 1908.
P-483: Synthesis of Indole Fused Heterocycles via Iodine Mediated Intramolecular Cyclisation and C-N Bond Formation B. Sindhura, V. Rajesh kumar and G. Sekar* Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India *E-mail: [email protected]
Indole moiety is widespread in various natural products, biologically important and pharmaceutically active molecules. Development of new chemical strategies for the functionalization of indole is always been area of interest.[1] However, C2 amination of indoles is very less explored. Pd/Cu catalyzed methodologies have been developed for C-N bond formation for C2 amination of Indole.[2] Complimentary to these metal mediated reactions, metal free, C2 amination of indoles have been reported by Yang et al.[3] However, these are intermolecular and some of these involve microwave irradiation.[4] Herein we have developed iodine mediated intramolecular C2 amination of Indoles to synthesize novel indole fused heterocycles (Scheme 1).[5] In this o strategy, C2 amination of indoles has been carried out by using iodine and Cs2CO3 in acetonitrile at 60 C. This reaction produced various highly substituted indole fused heterocycles in good yields.
Scheme. 1: Iodine mediated intramolecular cyclisation and C-N bond formation.
References 1. Sandro Cacchi et al., Chem. Rev., 111, 215, 2011. 2. [a] C. J. Li et al., Adv. Synth. Catal., 352, 632-636, 2010. [b] Y. M. Liang et al., Org. Lett., 13, 4196, 2011. 3. [a] Y. M. Liang et al., J. Org. Chem., 76, 744-747, 2011. [b] Y. M. Liang et al., Chem. Commun., 48, 2343, 2012. 4. P. L. Beaulieu et al., Org. Lett., 12, 2334, 2010. 5. B. Sindhura, V. R. Kumar and G. Sekar., (manuscript under preparation).
P-484: A Simple and Efficient Method for the Synthesis of chiral β-organo- telluroamines from chiral β-aminomethanesulfonate hydrochloride Rajegowda H R, Satheesh C E,Marulasiddeshwara M B and Raghavendra Kumar P* Department of Studies and Research in Chemistry, Tumkur University, Tumkur 572103, Karnataka, India *E-mail address: [email protected] No. +91-9901511112
Abstract: A simple and efficient method for the synthesis forchiral β-organotelluro amines(4a-c) has been developed from the freshly synthesized chiralβ-aminomethanesulfonatehydrochloride(2a-c)by the reaction of sodium aryltellurolate (ArTeNa, generated in situ by borohydride reduction of diorganoditelluride, Ar2Te2) (Method 2). This method gives directly pure and high yield (90-95%) of chiral β-organotelluroamines. These chiral β-aryltelluroamines(4a-c) also prepared by nucleophilic substitution of mesyloxy group by oranotellurolate (RTe-) in chiral n-boc β-amino methanesulfonates gave chiral n-boc β-organotelluro amides(3a- c), in 80-85 %. Ondeprotectionof bocin 3a-c in the presence of an acid afford chiral β-organotelluro amines (4a- c) with 45-55% yields (Method 1). The compounds 4a-cand 3a-cwere characterized by 1H,13C{1H} NMR, FT- IR spectroscopy and elemental analysis.
Key Words:Chiral amino alcohol, Ditelluride, β-Aminomethanesulfonatehydrochloride,Chiralβ-telluro amine
R
Boc NH TeAr 3a, 3b, 3c R Method 1
2NH OH Method 2 45-55%
R 90-95%
2NH TeAr 4a, 4b, 4c
References 1. Higashiura, H et al., J. Chem. Soc., Perkin. Trans. 1, 1989, 1479–1481. 2. K. J. Irgolic, et al., Reactions of Organotellurium Compounds in Organometallic Synthesis, Vol. 2, Eds., E. Becker, M. Tsutsui, John Wiley and Sons, Inc. 1971.
P-485: Novel bioactive eudesmanoid from Pogostemon parviflorus A.A.Chinchansure, 1 S.B. More, 1 D. Sarkar, 2 S.P. Joshi *1 1Organic Chemistry Division, National Chemical Laboratory, Pune 411008, India 2Combi-Chem Research Lab., National Chemical Laboratory, Pune 411008, India *E-mail: [email protected]
Phytochemical investigation of acetone extract of aerial parts of Pogostemon parviflorus (Family: Lamiaceae) afforded seven compounds including three new eudesmane sesquiterpenoids, 3β-acetoxy stemonolone (1), 5α- hydroxy-8α,15-diacetoxy-eudesma-1,3-diene-6-one (2) and 7α -hydroxy-eudesma-1,4-dien-3,6-dione (3) along with four known metabolites, stemonolone (4), spathulenol (5), stigmasterol (6) and 3β-hydroxy-D:B-friedo- olean-5-ene (7). Structures of new compounds were elucidated by detailed 1D and 2D NMR spectroscopic studies and XRD studies of compound 3. All isolates were evaluated for antiproliferative activity against human cancer lung cell line A549 adenocarcinoma and antimycobacterial activity against Mycobacterium tuberculosis
H37Ra. Compound 1 showed antiproliferative activity with IC50 9.5 µg/mL. Compound 3 exhibited antimycobacterial activity with IC50 3.22 µg/mL. Known compounds 4 and 7 also exhibited promising antimycobacterial activity with IC50 3.86 and 1.61 µg/mL.
Ortep diagram of compound 3
Fig.1: Isolated bioactive molecules from acetone extract of aerial parts of P.parviflorus
Reference 1. A. P. Phadnis et al., J. Chem. Soc. Perkin Trans. I, 937, 1984. 2. E. Cabrera et al., Phytochemistry, 27, 183, 1988. 3. C.Y. Ragasa et al., Chem. Pharm. Bull., 51,1208, 2003. 4. L.P. Duarte et al., Chemistry of Natural Compounds, 46, 686, 2010.
P-486: Decarboxylative Thioamidation of Arylacetic and Cinnamic Acids: A
New Approach to Thioamides
Tirumaleswararao Guntreddi, Rajeshwer Vanjari, and Krishna Nand Singh*
Department of Chemistry (Centre of Advanced Study), Faculty of Science, Banaras Hindu University, Varanasi 221005, India
Decarboxylation of carboxylic acids by loss of carbon dioxide has recently emerged as a powerful tool to form C-C or C−X bonds in organic synthesis [1]. However, most of the decarboxylative coupling reactions described so far requires transition-metal catalysts including palladium, copper, and other metals. Therefore, the direct oxidative decarboxylation routes under metal-free conditions to form new −CC or C−X bonds is of overriding value and challenging. Thioamides are vital structural motifs widely used as key intermediates and versatile building blocks for the construction of biologically important sulfur-containing heterocycles [2]. The most commonly used conventional methods are thionation of amides and Willgerodt−Kindler reaction involving aryl alkyl ketones, elemental sulfur, and amine [3]. However, these methods have limited applications because of the harsh reaction conditions, long reaction time, and low yields. Therefore, the development of new strategies for the synthesis of thioamides employing new, readily available, inexpensive, and environmentally benign starting materials is highly desirable. In the light of above fact, we describe herein for the first time an efficient, one-pot, metal-free decarboxylation reaction for the synthesis of thioamides by the reaction of arylacetic acid or substituted cinnamic acid, amines, and elemental sulfur without the need of any transition metal and oxidant (figure 1).
Figure 1. Metal and oxidant free decarboxylation
References:
1. Rodríguez, N.; Goossen, L. J. Chem. Soc. Rev., 40, 5030, 2011.
2. Iwata, M.; Yazaki, R.; Chen, I. H.; Sureshkumar, D.; Kumagai N.; Shibasaki, M. J. Am. Chem. Soc., 133, 5554, 2011.
3. Wegler, R.; Kuhle, E.; Schafer, W. Angew. Chem., 70, 351, 1958.
P-487: Biological evaluation of diorganotin(IV)–hydrazone complexes with CT DNA and Human Serum Albumin (HSA)
Sartaj Tabassum*, Mohd. Usman, Shipra Yadav Department of Chemistry, Aligarh Muslim University, Aligarh–202002, India *Corresponding author. Tel.: +91 9358255791. E–mail address: [email protected] (S. Tabassum).
Diorganotin(IV) hydrazones (1–3) derived from isoniazid and acetylacetone were synthesized and thoroughly characterized by analytical and various spectral techniques (UV-vis, IR, 1H 13C and 119Sn NMR, ESI-MS and elemental analyses). The molecular structure of diphenyltin(IV) analogue, 3 was ascertained by single X–ray crystallography. To get an insight into the possible mechanism of action, interaction studies of these complexes were investigated with CT DNA and human serum albumin (HSA) by using different biophysical methods such as UV–Vis spectroscopy, fluorescence spectroscopy, Fourier transform infra–red spectroscopy and circular dichroism spectroscopy. Notably, the complexes exhibited effective binding with calf thymus DNA through electrostatic interactions and cause static quenching of the human serum albumin (HSA) fluorophore. Mode of interaction of the complexes with DNA/protein has also been supported by molecular docking. In addition, cytotoxicity assay against U373MG (CNS), PC3 (prostrate), Hop62 (lung), HL60 (leukemia), HCT15 (colon), SK–OV–3 (ovarian), HeLa (cervix) and MCF7 (breast) cancer cell lines manifested significant anticancer activity of di-n-butyltin(IV) hydrazone.
Fig1. Ball and stick model of diphenyltin(IV) hydrazone, 3.
P-488: A Strategy for the Synthesis of Anthraquinone-Based Aryl‑C‑glycosides K. Upadhyaya1, N. Anand1, S. K. Shukla2δ, R. P. Tripathi*1δ
δAcademy of Scientific and Innovative Research, 1Division ofMedicinal & Process Chemistry, 2Sophisticated Analytical Instrumentation Facility, CSIR-Central Drug Research Institute, Sec. 10, JankipuramExtn., Sitapur Road, Lucknow-226031, Uttar Pradesh, INDIA.
C-aryl glycosides, both of synthetic and natural origins, are significantly important in medicinal chemistry owing to their stability toward enzymatic and chemical hydrolysis as compared to their O- and N- glycosides [1]. They are versatile chiral building blocks in pharmaceutics and have the potential to act as enzyme inhibitors and stable sugar mimics [2]. One class of medicinally important aryl glycosides, active against diabetes, and currently in late phase development are the SGLT-2 inhibitor [3]. The angucyclinegroup of glycosides with anthraquinone as aglycone part is endowed with anticancer, antiviral, enzyme inhibitory and platelet aggregation inhibition activities [4]. Therefore anthraquinone based C-aryl glycosides synthesis has attracted considerable interest.
Scheme1. Route for syntesis of anthraquinone-basedaryl‑C‑glycosides
In the work presented here, we provide an efficient and simple strategy for the synthesis of a diverse range of anthraquinone based C-aryl glycosides. Strategy involves the sequential Diels Alder reaction and oxidative aromatization with the performed glycosyldiene and dienophile. The synthesis of glycosyldienes from simple sugars was achieved by tandem one pot substitution and elimination reaction.
Reference
1. D. E. Levy et al., The Chemistry of C-Glycosides; ElsevierScience, Ltd.: Amsterdam, 1995; p 4. 2. (a) M. D. Lewiset al., J. Am. Chem. Soc.104, 4976,1982. (b) K.Horikaet al.,Synlett,43, 1994. 3. E. C. Chaoet al.,Nat. Rev. Drug Discovery,9, 551, 2010. 4. J. Rohr et al., Nat. Prod. Rep.9, 103, 1992.(b) M. K. Kharel et al., Nat. Prod. Rep. 29, 264, 2012.
P-489: Methodology improvement in synthesis of spiropyrrolidinescaffoldsusing greener aspects AnshuDandia,* PragyaSoni Centre of Advanced Studies, Department of Chemistry, University of Rajasthan, Jaipur-302004 India E-mail: [email protected]
In the present context of vast global energy requirements, there is a growing need for the better advancement of greener and more sustainable technologies. The development of novel methodologies help in the optimal design and operation of industrial production of fine chemicals and pharmaceutics taking into account multiple objectives such as the minimization of the environmental impact, investment and cost of the product.In continuation of our on-going programme for the synthesis of spiropyrrolidine derivatives,we have developed amulticomponent one pot1,3-dipolar cycloaddition reaction for the synthesis ofspiropyrrolidine/thiapyrrolidineoxazine/thiazine derivatives using trifluoroethanol (TFE) as a green solvent. TFEprovides a valuable tool for organic synthesis which promotes faster and cleaner reactions than conventional solvents.The use of alternative reaction media is also one of the aspects that circumvents the problems associated with many of the traditional volatile organic solvent and also provides opportunities for facilitating the recovery and recycling of the catalyst and medium.To achieve these goals, we have contributed to the development of sustainable chemistry by performing synthetic processes in TFEas reaction medium; focusing our mind on recovery and reuse as well as the definition of one-pot protocols.Further characterization was done by spectral analyses. The regio- and stereochemical outcome of the synthesized compound was unambiguously ascertained by single crystal X-ray analysis. The details of our studies will be presented in the conference.
MeOOC H H O MeOOC O N NH N NH X X O N O H
X = O, S
Keywords: 1,3-dipolar cycloaddition, trifluoroethanol. References: A. Dandiaet. al., J. Mol. Catal A: Chem.,394, 244–252,2014. A. Dandiaet. al.,RSC Adv., 4, 6908, 2014. A. Dandiaet. al., Tetrahedron Lett.,54, 3180, 2013. A. Dandiaet. al., Tetrahedron Lett.,54,3929, 2013. A. Dandiaet. al., RSC Adv., 3, 8422, 2013. A. Dandia. et. al. J. Fluorine Chem., 2013.
P-490: Binding of melamine based ligand and its Ce(IV) complex to human telomere sequence–Evaluation by Circular Dichroism, TRAP and MTT assays for telomerase inhibition and antitumor activity
Duraisamy Renuga & Palanisamy Uma Maheswari
Department of Chemistry, National Institute of Technology, Tiruchirappalli – 620 015 email:[email protected]
The melamine based new ligand (ligand 1) is synthesized and characterized using IR, NMR, ESI-MS and CHN analysis. The Ce(IV) metal complex is isolated and characterized using ESI-MS and CHN analysis. The ligands alone and the metal complex are interacted with human telomere DNA sequence and then analyzed for telomerase inhibition assay (TRAP) as substrate [Kim et al] (1). They are as well tested for anticancer activity (MTT assay) in selected cell lines [Maheswari et al] (2). A correlation study between the results of TRAP and MTT assay based on the interaction of the ligand and the metal complex with human telomere DNA sequence towards G-quadruplex
HO
H3CO OCH3 OH NH N HN
NN
NH
OCH3
OH Ligand 1 stabilization was arrived by the modeling studies through the molecular operating environment (MOE) setup. The cancer cell lines invasion and induced apoptosis are observed by confocal imaging studies. All above results will be presented and analysed under the objective of telomerase inhibition and antitumor activity [Renuga et al] (4).
References:
1. Kim, J.H.; Lee, G.E.; Kim, S.W.; Chung. I.K. Biochem. J. 2003, 373, 523. 2. Maheswari, P.U.; Roy, S.; den Dulk, H. ; Barends, S.; van Wezel. G.; Kozlevcar, B.; Gamez, P.; Reedijk. J. J. Am. Chem. Soc. 2006, 128, 710 – 711.
3. Renuga, D.; Nandhakumar, V.; Mugesh, D.; Maheswari, P.U. J. Med. Chem. Communicated.
P-491: CuO-Nanoparticle-Catalysed Oxidative Cycloaddition of Azides with Nitroolefins: Synthesis of 1,4,5-Trisubstitued 1,2,3-Triazoles J. Paul Raj, D. Gangaprasad, R. Sasikala, J. Elangovan* Department of Chemistry, B. S. Abdur Rahman University, Chennai 600048, India Email: [email protected]
The 1,2,3-triazole nucleus represents a significant class of biologically active nitrogen compounds that exhibits a number of important biological properties such as antibacterial, anticancer, antiviral and antituberculosis [1]. Synthesis of 1,2,3-triazoles can be accomplished by copper-catalysed azide-alkyne cycloaddtion (CuAAC) reactions [2] and ruthenium-catalysed azide-alkyne cycloaddtion (RuAAC) reactions [3]. There are few reactions on synthesis of 1,2,3-triazoles via cycloaddtion of azides with nitroolifins in which reaction proceeds through the elimination of nitro group (scheme 1) [4a-c]. Herein, We report that 1,4,5- trisubstituted 1,2,3-triazoles can be obtained by oxidative cycloaddtion of azides with nitroolifins in water without elimination of nitro group (scheme 2). The catalyst is efficient and can be reused several times. The system does not require base, additives and oxygen/nitrogen atmosphere.
Previous Work
TBAF .3H2O N N NO2 NH TMSN3 X X R SFC R R = CN,CO2Et
Scheme 1
This Work
N N 1 CuO nanopaticles NO R + 2 2 NO2 R N3 2 N Water, 90 °C, 12 h R R1 R1 = aryl, heteroaryl 15 examples up to 85% Yield
Scheme 2
Reference 1. K. Jozwiak et al., Chem. Rev., 2013, 113, 4905. 2. L. Micouin et al., Angew. Chem. Int. Ed., 2010, 49, 2607. 3. V. V. Fokin et al., J. Am. Chem. Soc., 2005, 127, 15998. 4. a) Y. Wang et al., J. Org. Chem., 2014, 79, 4463; b) Z. Hou et al. J. Am. Chem.Soc., 2011, 133, 18086; c) L. Vaccaro et al. J. Org. Chem., 2005, 70, 6526.
P-492: Palladium-Schiff base complex catalyzed C-S cross-coupling of thiols with Aryl halides
Pranjit Barman* Prasanta Gogoi
We report an efficient, mild and convenient synthetic protocol for the C -S cross-coupling reaction of various aryl halides and thiols using 2 mol% Palladium-Schiff base catalyst with KOH as the base, in DMF at 90 oC. Using this protocol, we have shown that a variety of aryl sulfi des can be synthesized in excellent yields from readily available aryl halides and thiols.
2 mol% Pd-Schiff-basecomplex ArX + RSH ArSR KOH, DMF, 90 oC X= I, Br
Reference 1. Gogoi,P. et al., Tetrahedron 70, 7484, 2014. 2. Gogoi,P. et. al., Synlett 25, 866, 2014
P-493: CHIRO-OPTIC AND ELECTRONIC STUDIES OF BRIDGED TRIARYLAMINE HETEROHELICENES; A DFT STUDY Nasarul Islam and Swapandeep Singh Chimni
Department of Chemistry, Guru Nank Dev University Amritsar Punjab
Email; [email protected]
Abstract In this work, Density Functional Theory (DFT) calculations have been adopted to analyze the spectral properties, electronic and nonlinear optical (NLO) response of the oxo and thai bridged triarylamine heterohelicenes (TAH). The full geometry optimizations of helical system were performed by employing B3PW91/6-311G (d, p) level of theory using Gaussian 03. We have observed that, the M and P isomeric fors of heterohelicenes of 1, 2, 3 and 4 are enantiomers, while for heterohelicenes 5, 6 and 7 they are atropisomers. The calculated IR and VCD spectra in the mid-IR region 1300-1650 cm-1contains peaks, with characteristic features and provides important information regarding the configuration identifications. Charge transfer and nonlinear optical response were analyzed and correlated with modifications in geometry and energy levels. The calculation indicates that trivial changes of the torsional angle occur in TAH derivatives with electron donating substituents as compared to TAH derivatives with electron withdrawing substituent resulting in less value of
reorganization energies for TAH derivatives 2-6. The TAH derivative with -N(CH3)2 group have highest HOMO level, thus least ionization potential, indicating an significant hole transfer efficiency as compared to unsubstituted TAH. We have observed that the oxo-bridged heterohelicenes show more nonlinear response as compared to thia-bridged hetohelicenes. The hyperpolarizability fallow the trend M-2 > M-4 > M-1 > M-7 > M-6 > M-5 > M-3 while as Bond Length Alternation have reverse trend M-2 < M-4 < M-1 < M-7 < M-6 < M-5 =M- 3. Thus, nonlinear optical response of heterohelicenes is dominated by π-π* charge transfer excitations involving low lying filled orbitals and empty π* virtual orbitals.
P-494: Micellar Effect of Ammonium based Cationic Surfactants on Kinetics of Methylene Blue Assisted Ru (III) and Cu (II) catalyzed Cysteine/Cystine Transformation in Acidic Aqueous Media Roheena Jan, Mohsin Ahmad Bhat, Nasarul Islam, Badruddin Khan Department of Chemistry, University of Kashmir, Srinagar-190006, J&K, India. e-mail; [email protected]
Kinetic investigations of Cysteine-Cystine transformation assisted by model electron acceptor methylene blue (MB) and catalyzed synergistically by Ru (III) and Cu (II) in aqueous media of varying pH, temperature and micellar solutions were carried out. The homogeneous electron transfer between Cysteine and MB was observed to exhibit a pH sensitive kinetics that is affected by the presence of ammonium based cationic surfactants. Among the investigated surfactants while the post micellar concentrations of OAC were found to decrease the rate of the of cysteine oxidation, the presence of OPMAC micelles was observed to accelerate the said reaction. The observed micellar kinetic effects modeled through quantum mechanical calculations are explained in light of the reactant-micelle interactions.
Key Words: Cysteine, Methylene blue, Ruthenium, Octadecylammonium chloride (OAC), Octadecylpyridine-2- yl methyl ammonium chloride (OPMAC), Micellar catalysis.
P-495: Synthesis and physical properties of imidazolium ionic liquid with disiloxane and ether substituents Santosh N. Chavan, 1 D. Mandal *1 1Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar 140001, Punjab, India. *E-mail: [email protected]
Ionic Liquids with low viscosity is of importance in most of its applications. Anions like TFSI and N(CN)2 was already been successful to keep the viscosity low. Recently it was observed that the ether and siloxane functionality has influence on lowering the viscosity of imidazolium and tetraalkyl ammonium ILs. Here we report the synthesis and characterization of imidazolium ILs with both ether and disiloxane substituents in a combination which shows better influence to lower the viscosity (~75 mPa.s at RT) and overcome the increase of high molecular weight. At the same time these ionic liquids show very good thermal properties like very low glass transition (Tg < –75 °C) and high decomposition temperature (Td > 420 °C) which is essential for a good electrolyte and lubricant.
Fig.1: Ionic liquids used in this study.
P-496: A Green Solvent Induced DNA Package Sagar Satpathi, Abhigyan Sengupta, Hridya V. M., Krishna Gavvala, Raj Kumar Koninti,
Bibhisan Roy, Partha Hazra*
Department of Chemistry, Indian Institute of Science Education and Research (IISER)-Pune, Pune (411008), Maharashtra, India Mechanistic details of DNA compaction are essential for its functioning in the process of gene regulation in living systems. Therefore, many in vitro studies have been implemented using several potential compaction agents. However, these compacting agents may have some kinds of cytotoxic effects to the cells. To minimize this aspect, several researches had been performed but people have never focused green solvent, i.e. room temperature ionic liquid (RTIL) as DNA compaction agent. In best of our knowledge, this is the first ever report where we have shown guanidinium tris(pentafluoroethyl)trifluorophosphate (Gua-IL) as a DNA compacting agent. The compaction ability of Gua-IL has been certified by utilizing different spectroscopic techniques like steady state emission, circular dichroism (CD), dynamic light scattering (DLS) and UV melting experiments. Notably, we have extensively probed this compaction process by Gua-IL through field emission scanning electron microscopic (FE-SEM) images. Moreover, herein we also have discussed about the plausible compaction mechanism process of DNA by Gua-IL. Results are suggesting that above a certain concentration ≥1( mM) Gua - IL itself can form a micellar kind of self aggregation, which instigates the DNA compaction process. This study divulges the specific details of DNA compaction mechanism by a new class of compaction agent which has high biodegradability and eco friendly in nature. Keywords: DNA compaction, ionic liquid, dynamic light scattering, FE-SEM, TEM.
*Corresponding author E-mail: [email protected] Tel.: +91-20-2590-8077; Fax: +91-20-2589 9790
P-497: Anion Triggered Structural Variation and Single Crystal to Single Crystal (SCSC) transformation from 1D to 2D Coordination Polymer
Sarita Tripathi, Renganathan Srirambalaji, Samir Patra and Ganapathi Anantharaman* Department of Chemistry, Indian Institute of Technology Kanpur, Uttar Pradesh 208016, India *E-mail: [email protected]
Coordination polymers (CPs) showing flexible and dynamic nature with structural flexibility, unlike rigid CPs, can undergo selective molecular recognition, guest exchange and separation by tuning their cavity according to the guest molecules.1-2 Recently the single-crystal to single-crystal (SCSC) transformation in CPs has received considerable attention as they are found to have applications in gas storage, magnetism, and luminescence. The transformations which are associated with the anion or solvent exchange can be potentially employed as anion exchange materials. SCSC transformations with dimensionality change from lower to higher are very few as it involves the breaking and formation of ligand to metal coordination/covalent bonds which is a difficult phenomena in such extended networks. 3-5 Earlier, we have reported the solvent induced synthesis of chiral and achiral CPs from achiral angular 6 ditopic ligand 2,6-bis(imidazol-1-yl)pyridine (pyim2). In continuation of our previous work, we have synthesized four CPs {[trans-Cd(pyim2)2(H2O)2]∙2NO3)}n (1), {[trans-Cd(pyim2)2(DMF)2]∙(PF6)2(DMF)2}n (2), 7-8 {[trans-Cd(pyim2)2(H2O)2]∙(PF6)(NO3)}n (3) and {[Zn(pyim2)2]·(PF6)2}n (4) with pyim2. The structure and - dimensionality of CPs 1-4 is controlled by the non-coordinating counter anion, since CP 1 with smaller NO3 - forms a 2D double helical architecture, while CPs 2-4 having larger PF6 result into a 1D chain. CPs 2 and 3 via SCSC transformation form CP 1, due to the exchange of the solvent and/or counter anion and resulted into an enhancement in the dimensionality from 1D to 2D. The anion exchange was confirmed by Single crystal X-ray diffraction, PXRD patterns and IR spectroscopy. In addition, the photoluminescence behavior and thermal stability of these complexes were analyzed.
Figure: SCSC transformation of 1D (2 and 3) to 2D (1) CPs.
References 1. S. Kitagawa et al., Chem.Soc. Rev., 34, 109, 2005. 2. S. Kitagawa et al., J. Solid State Chem., 178, 2420, 2005. 3. J. J. Vittal et al., Chem.Soc. Rev., 42, 1755, 2013. 4. P. K. Bharadwaj et al., CrystEngComm, 15, 9239, 2013. 5. X. M. Chen et al., Chem.Soc. Rev., 43, 5789, 2014. 6. G. Anantharaman et al., J. Chem. Sci., 126, 1423, 2014. 7. H. M. Lee et al., Inorg. Chem., 46, 5691, 2007. 8. J. Tejeda et al., J. Organomet. Chem., 617, 395, 2001.
P-498: Synthesis, Characterization, and Density Functional Theory Studies of some Tetra-Coordinated Copper(II) Complexes
R. C. Maurya*, P. S. Jaget, P. K. Vishwakarma and A. K. Sharma Coordination Bioinorganic and Computational Chemistry Laboratory, Department of P. G. Studies and Research in Chemistry and Pharmacy, Rani Durgavati University, Jabalpur-482001 (M.P.), India *Corresponding Author. E-mail: [email protected] / [email protected]
This chapter describes the synthesis of four new mixed-ligands complexes of copper(II) of the general composition [Cu(L)(ka)(H2O)]⋅H2O, where ka = kojic acid, LH= β- ketonolates viz., methylacetoacetate (macacH), ethylacetoacetate (eacacH), dibenzoylmethane (dbmH) or benzoylacetone (baH). The resulting obtained have been characterized by physiochemical and spectral studies the basis of elemental analysis, copper determination, molar conductance, magnetic measurements, thermogravimetric analysis, infrared, electron paramagnetic resonance and electronic spectral studies. DFT studies have been carried out for one of the representative complex, [Cu(ka)(bac)].2H2O. The molecular structure, vibrational wave numbers, infrared intensities, were obtained for molecule using the B3LYP density functional theory (DFT) with the standard B3LYP/6-31+G(d, p)/LANL2DZ basis set. The activation parameters were calculated using non-isothermal methods. Theoretical calculations invoking geometry optimization, charge distribution and molecular orbital descriptions- HOMO and LUMO were done using density functional theory. The absolute electronegativity (χabs) and absolute hardness (η) were obtained for molecule. The experimental results and the calculated molecular parameters such as, bond distances and angles revealed square planner geometry of the compound.
Fig. Molecular structure of complex, [Cu(ka)(bac)]⋅2H2O
P-499: Probing the Strength of S…X non-covalent interactions and their role in controlling the conformations of organic systems: A Computational Study Mrinal Kanti Si, Rabindranath Lo and Bishwajit Ganguly Computation and Simulation Unit (Analytical Discipline and Centralized Instrument Facility), CSIR-Central Salt & Marine Chemicals Research Institute, Bhavnagar, Gujarat, India-364 002
E-mail: [email protected]
Noncovalent interaction plays an important role for determining the 3D structure of biological molecules,organic crystals and reactivities in organic/inorganic reactions [1-3]. The strength of the 1,5 intramolecular hypervalent→X Y (Y= O,S and X=S-H) bonds in cyclic conjugated five membered systems have been examined with DFT and complete basis set (CBS-QB3) methods. AIM and GIAO and NBO analyses have been performed to gauge the factors responsible for the strength of such non-bonded interactions. The role of solvent has also been studied and compared with the corresponding five-membered intramolecular hydrogen bonds.
Figure 1: Optimized geometries of cyclic conjugated five membered system and it’s isomer at CBS-QB3 method. (ΔE is the strength of S…O and S…S interaction).
References:
[1] Fang, L.; Liu, P.; Sveinbjornsson, B. R.; Atahan-Evrenk, S.; Vandewal, K.; Osuna, S.; Jimenez-Oses, G.; Shrestha, S.; Giri, G.; Wei, P.; Salleo, A.; Aspuru-Guzik, A.; Grubbs, R. H.; Houkb, K. N.; Baoa, Z. Confined Organization of Fullerene units along High Polymer Chains. J. Mater. Chem. C 2013, 1, 5747–5755.
[2] (a)Moon, H.; Zeis, R.; Borkent, E. J.; Besnard, C.; Lovinger, A. J.; Siegrist, T.; Kloc, C.; Bao, Z. Synthesis, Crystal Structure, and Transistor Performance of Tetracene Derivatives. J. Am. Chem. Soc. 2004, 126,15322–15323.
(b) Gsanger, M.; Oh, J. H.; Konemann, M.; Höffken, H. W.; Krause, A. M.; Bao, Z. N.; Wurthner, F. A Crystal-Engineered Hydrogen-Bonded Octachloroperylene Diimide with a Twisted Core: An n-Channel Organic Semiconductor. Angew. Chem. 2010, 49, 740–743.
(3) Dixit, A. N.;Reddy, K. V.;Rakeeb, A.; Deshmukh, A.S.; Rajappa, S.;Ganguly, B.;Chandrasekhar, J. Conformational preferences of α-Functionalised Keten-S,N-acetals: Potential role of S..O and S..S Interactions in Solution. Tetrahedron. 1995, 51, 1437.
P-500: Quantum Chemical and Steered Molecular Dynamics Studies for One Pot solution to Reactivate Aged Acetylcholinesterase with alkylatoroxime
Nellore Bhanu Chandar, Rabindranath Lo and BishwajitGanguly
Computation and Simulation Unit (Analytical Discipline and Centralized Instrument Facility), CSIR-Central Salt & Marine Chemicals Research Institute, Bhavnagar, Gujarat, India-364 002.
E-mail: [email protected]
Acetylcholinesterase (AChE, EC 3.1.1.7) is one of the most important hydrolytic enzymes in many living organisms such as humans and vertebrates[1].AChE is prone to irreversible inhibition by certain organophosphorus compounds (OPs) such as nerve agents and a group of insecticides[2]. Thephosphenyl enzyme may undergo a spontaneous, time-dependent intramolecular reaction yielding an ‘aged’ form of the conjugate[3].The aged conjugate restricts negatively charged nucleophilesfor approaching the phosphorus atom to reactivate the inhibited AChE. We have reporteda computational study to reverse the aging process of organophosphorus inhibited AChE and reactivate the aged-AChE adduct by single attempt (reactivator). To revert the inhibited AChE,we have designed Dimethyl(pyridin-2- yl)sulfonium based oximeforthe alkylation of the aged adduct and subsequently, can reactivate the inhibited AChE to free enzyme,which excludes the use of any external oximereactivators for this purpose [4].
Fig 1.Schemetic representation of reactivation of aged soman inhibited human AChE with reactivator.
Fig 2..Docked conformation of soman-aged AChE with oxime3. Distance is in Å (cyan= carbon, blue = nitrogen, white = hydrogen, yellow = sulphur, brown = phosphorus and red = oxygen) (Interacting residue is shown in tube format)
References:
[1] J.L. Sussman, M. Harel, F. Frolow, C. Oefner, A. Goldman, L. Toker, I. Silman, Science253(1991)872-879.
[2] J. Wang, S. Roszak, J. Gu, J. Leszczynski, J. Phys. Chem. B.109 (2005) 1006-1014.
[3] F. Berends, C.H. Posthumus, I.V.D. Sluys, F.A. Deierkauf, Biochim. Biophys.Acta34 (1959) 576-578.
[4] N. B.Chandar, R. Lo, B.Ganguly, Chemico-Biological Interactions 223 (2014) 58-68.
P-501: Can membrane mimetics screen the efficacy of antimicrobial compounds? A case study with gallic acid and its esters
M. Raju and Pabitra B. Chatterjee*
Analytical Discipline and Centralized Instrument Facility (AD&CIF) CSIR-Central Salt & Marine Chemicals Research Institute (CSIR-CSMCRI) G. B. Marg, Bhavnagar-364002, Gujarat, India. [email protected]
Abstract: Interaction of antibacterial compounds with bacterial extracytoplasmic cell membrane is an important step in the course of action of any bactericidal compound since these molecules do not require entering bacterial cell. By simplifying the complex extracytoplasmic cell membrane, large varieties of model membrane systems have appeared in the literature1 such as micelles and reverse micelles, bicelles, monolayers and bilayers, nanodiscs, amphipols, etc. Whether the interactions of bactericidal molecules with membrane mimetic systems correlate with the antibacterial activity in vivo herein in this study we have explored two model membrane systems, viz. Langmuir monolayers and microemulsion interfaces (micelles and reverse micelles). We explored the location and interaction of five natural polyphenolic antimicrobial phytochemicals gallic acid and its esters (methyl-, propyl-, octyl- and lauryl gallates) in SDS and Triton X-100 micelles, CTAB micelles and reverse micelles and phospholipid 1,2-Distearoyl-sn-glycero-3-phoshocholine (DSPC) mololayers. Results from phospholipid based Langmuir monolayer systems (LB films) show decrease in molecular area with the addition of gallic acid and its esters indicating ordering in the phospholipid molecules and is happening due to the condensing effect of these natural antibiotics. However, the extent of surface area contraction varies within the group e.g. octyl gallate interacts most significantly whereas lauryl gallate interacts moderately followed by propyl- and methyl gallates. Microemulsion based interfaces are best suited for detailed spectroscopic characterization for these types of interactions. Results from proton NMR (1D & 2D) studies corroborate with our earlier findings from LB. Our investigations have nicely addressed why the MIC/MBC values for gallic acid and methyl- and propyl gallates are higher than the corresponding values for lauryl- and octyl gallates.
Reference 1. D. E. Warschawski, et al., Biochimica et Biophysica Acta 1808, 1957, 2011.
P-502: Atomically precise clusters of iridium
Shridevi Bhat, Indranath Chakraborty and Thalappil Pradeep* DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry Indian Institute of Technology Madras. * E-mail: [email protected]
Abstract:
Noble metal quantum clusters are being studied with a large interest today due to their attractive physical and chemical properties and promising applications.1 Though monolayer protected Au2 and Ag3 clusters in solutions are understood to a larger extent, other metal cluster systems are yet to be explored. Iridium is an interesting metal due to its reactivity, stability and selectivity under different conditions and possesses good catalytic and electrocatalytic activity for various reactions. Its complexes are also well known for their catalytic properties. Ir clusters in gas phase and on inert supports like zeolites are known and studied to some extent.4-6 But no attempt has been reported for the synthesis of thiol-protected Ir clusters in solution. Herein, we discuss an attempt to synthesize Ir clusters protected by 2-phenylethane thiol and characterize the product using UV/vis spectroscopy, MALDI MS (Matrix Assisted Laser Desorption Ionization Mass Spectrometry), TEM (Transmission Electron Microscopy), XPS (X-ray Photoelectron Spectroscopy), SAXS (Small Angle X-ray Scattering) analysis, IR (Infra-Red) spectroscopy and XRD (X-Ray Diffraction) analysis, etc. As Ir is well known for its catalytic activity, these clusters are expected to be of a greater application in catalysis.
References:
(1) Mathew, A.; Pradeep, T. Particle & Particle Systems Characterization 2014, 31, 1017. (2) Daniel, M.-C.; Astruc, D. Chemical Reviews 2003, 104, 293. (3) Udayabhaskararao, T.; Pradeep, T. The Journal of Physical Chemistry Letters 2013, 4, 1553. (4) Aydin, C.; Lu, J.; Shirai, M.; Browning, N. D.; Gates, B. C. ACS Catalysis 2011, 1, 1613. (5) Aydin, C.; Lu, J.; Liang, A. J.; Chen, C.-Y.; Browning, N. D.; Gates, B. C. Nano Letters 2011, 11, 5537. (6) Rueping, M.; Koenigs, R. M.; Borrmann, R.; Zoller, J.; Weirich, T. E.; Mayer, J. Chemistry of Materials 2011, 23, 2008.
P-503: Bacterial mediated synthesis of silver nanoparticles and their biological activity Shital V. Sable1, Suvidya Ranade*1 Chemistry Department, Savitribai Phule Pune University, Pune 411007, India. *Email: [email protected] Abstract: The properties of nanomaterials have offered many profitable products and applications. The present study involves bacterial mediated synthesis of silver nanoparticles, their characterization, biological activity and mechanism of reduction. Bioreduction of silver was obtained by adding bacterial supernatant (Bacillus subtilis spizizenni 2063) to the silver nitrate solution. The stability of silver nanoparticles was checked after three months. The characterization was done by SEM, TEM, XRD and IR. The reduction mechanism was studied by gel filtration chromatography followed by LC/MS. Bioreduction of silver using bacterial supernatant was obtained in 24hr as seen from dark brown colour. Nanoparticles shows lambda max at 430nm they are of spherical shape and crystalline nature in the size range 20-50nm. XRD revealed 111, 311, 211, 222 planes and LC/MS indicated involvement of tyrosine and tryptophan amino acids, simvastatin-6-carboxylic acids, vitamins.
a b
c
Fig. 1: Bioreduction for synthesis of silver nanoparticles a) initial colour, b) final colour; c) TEM image.
References 1. Vidhya Lakshmi Das et al., 2013. DOI 10.1007/s13205-013-0130-8. 2. N. Kannan et al., 2011. Colloids and Surfaces B: Biointerfaces, 86 378–383.
P-504: Electrochemical sensing of nitrite by silver nanoparticles incorporated amine functionalized silica Piyush Kumar Sonkar and Vellaichamy Ganesan* Department of Chemistry, Faculty of Science Banaras Hindu University, Varanasi-221 005, UP, India E-mail: PKS: [email protected], VG: [email protected]
Recently, metal nanoparticles (Nps) and their composites are subjected to intensive research due to their wide range of applications in several fields like material science, microelectronics, energy storage, medicine, catalysis - and electrochemical sensors [1, 2]. On the other hand electrochemical determination of NO2 is significant due to environmental and biological related issues [1-5]. Therefore in the present work, Ag Nps are incorporated into the amine functionalized mesoporous silica without any external reducing agents. Uniform sized Ag Nps with even distribution throughout the silica is obtained by this technique. Using this new silica material efficient - - electrocatalytic oxidation of NO2 is realized and an amperometric sensor for the sensitive determination of NO2 in real samples is constructed.
3 400
300
A µ 200 / 2 I A 100 µ
/ I 1 0 0 4000 8000 12000 16000 [NO - ] / µM 2
0
-0.5 0.0 0.5 1.0
E / V - Fig. 1: Electrocatalytic oxidation of NO2 by Ag Nps incorporated amine functionalized silica in 0.1 M PBS pH - 7.0 buffer. Inset shows the calibration plot for NO2 determination.
Acknowledgements: CSIR and UGC, New Delhi for financial support: PKS acknowledges UGC for RGNF.
References 1. Y. Zhang, Y. Zhao, S. Yuan, H. Wang, C. He, Sens. Actuators B, 185, 602, 2013. 2. Y. Li, Y. Zhou, H. Xian, L. Wang, J. Huo, Anal. Sci. 27, 1223, 2011. 3. M. Pal, V. Ganesan, Analyst, 135, 2711, 2010. 4. M. Pal, V. Ganesan, Electrochim. Acta, 55, 4071, 2010. 5. P. K. Rastogi, V. Ganesan, S. Krishnamoorthi, J. Mater. Chem. A, 2, 933, 2014.
P-505: Metal Nanoparticles Stabilized by Metal-Carbon Covalent Bonds: An Efficient and Reusable Nanocatalyst
Dr. G. Sekar
Department of Chemistry, IIT Madras, Tamil Nadu-600 036, INDIA
Email: [email protected]
Metal nanoparticles (NPs) have attracted a remarkable interest in academic as well in industrial research[1]. NPs show enhanced catalytic reactivity due to their larger surface-to-volume ratio[2]. Generally, phosphines, amines, thiols and dendrimers are used as stabilizers for NPs [3] where the stablization is through coordination of heteroatom to the metal NPs. During the catalytic reactions, these NPs often result in 2 agglomeration to yield an inactive catalyst [4]. A stable Pd and Pt NPs stabilized by M-C(sp ) covalent bonds have been designed, synthesized, characterized and successfully utilized as catalysts for organic reactions (Scheme 1)[5]. The new metal nanocatalysts were quantitatively recovered and reused without any loss in the 2 catalytic activity and particle size, due to the stable M-C(sp ) covalent bonds stabilization.
Scheme 1
Reference 1. D. Astruc et al., Angew. Chem. Int. Ed., 44, 7852, 2005. 2. V. Polshettiwar et al., Green Chem., 12, 743, 2010. 3. G. C. Bond, Chem. Soc. Rev. 20, 441, 1991. 4. N. R. Jana and X. Peng, J. Am. Chem. Soc. 2003, 125, 14280. 5. (a) G. Sekar et al., Cat. Commun., 39, 50, 2013; (b) G. Sekar et al., Org. Lett., 16, 3856, 2014; (c) G. Sekar et al., Tet. Lett., In Press, 2014.
P-506: Highly selective liquid-phase aerobic oxidation of vanillyl alcohol to vanillin on cobalt oxide (Co3O4) nanoparticles S. H. Shinde, 1 A. Jha, 1 C. V. Rode *1 1Chemical Engineering and Process Development Division, National Chemical Laboratory, Pune 411008, India
Spinel Co3O4 nanoparticles prepared by solution phase method having particle size in the range of 12–20 nm exhibited excellent activity for the liquid-phase aerobic oxidation of vanillyl alcohol with 80% conversion and 98% selectivity to vanillin. Our catalyst could be reused three times without appreciable loss in activity. The catalytic activity of the Co3O4 nanoparticles was found to be similar to its homogenous precursor (cobalt acetate) and greater than the commercial Co3O4 oxide. The detailed characterization results of morphology, size and structure of the prepared Co3O4 nanoparticles obtained by XRD, FT-IR, H2-TPR, HR-TEM and cyclic voltammetry technique were used to understand the roles of various Co species in directing the selectivity towards vanillin.
Reaction Scheme:
Fig. 1 Fig. 2
Fig.1: XRD patterns of (a) the as-synthesized cobalt hydroxy carbonate, (b) Co3O4 nanoparticles, and (c) commercial Co3O4 Fig. 2 H2-TPR profile of Co3O4 nanoparticles
Reference 1. A. Jha et al., New J. Chem. 37, 2669, 2013.
P-507: Green synthesis and stabilization of biocompatible gold Nanoparticles and their potential applications in Diabetes. Aishwarya Yadav1, Suvidya Ranade1* 1Department of Chemistry, Savitribai Phule Pune University, Pune 411007 Email: [email protected]
The green approach to synthesis of AuNPs is to develop eco-friendly method alternative to chemical methods. AuNPs were synthesized by adding a water extract of Cassia fistula leaves to aurochloric acid at room temperature. The AuNPs are formed within 7 min. The bioreduced AuNPs were characterized by TEM, FTIR, XRD, and DLS. Studies on effect of pH, Temperature and NaCl concentration on stability of gold nanoparticles were studied. A plausible mechanism for the synthesis of AuNPs by Cassia fistula extract has been discussed. Finally, we have developed AuNPs-based drug delivery system (Au- ROZ) containing Roziglitazone (ROZ), an antidiabetic drug. A UV vis spectrum shows λmax at 535 nm. The TEM images of AuNPs showed that the particles are poly-dispersed with triangular and hexagonal shapes. The FTIR studies showed presence of functional groups corresponding to leaf extract on AuNP surface. Binding of Folic acid drug and PEG was confirmed by UV spectroscopy.
1 Hour 12 min 1.6 15 min 1.4 18 min 21 min 1.2 24 Hour 1.0 24 min 0.8 27 min 0.6 03 min 0.4 30 min 33 min 0.2 39 min 0.0 Absorbance 45 min -0.2 51 min -0.4 06 min -0.6 09 min 0 min -0.8 -1.0 400 450 500 550 600 650 700 Wavelength (nm)
(a) (b) (c)
Fig. 1: (a) TEM images of AuNPs, (b) Development of UV spectra of AuNPs, (c) FTIR analysis of AuNPs.
References:
1. S. Mukherjee et al., Nanotechnology, 23, 2012. 2. P. Daisy et al., International Journal of Nanomedicine, 2012.
P-508: Self-Sorted Donor-Acceptor Coaxial Assemblies with High Photoconductivity Seelam Prasanthkumar,1 Samrat Ghosh,1 Vijayakumar C. Nair,1 Akinori Saeki,2 Shu Seki,2 Ayyappanpillai Ajayaghosh*1 1Photosciences and Photonics Group, Chemical Sciences and Technology Division, CSIR- National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Trivandrum- 695019 (India). 2Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan). *E-mail: [email protected]
Unidirectional charge transport properties of self–assembled, one−dimensional (1-D) donor−acceptor nanostructures, have made them an ideal candidate for organic bulk heterojunction (BHJ) solar cells. [1] In this context, self–sorted assemblies of electron rich (D) and electron deficient (A) molecules provide ample scope for facilitating photocurrent generation whereas formation of charge transfer (CT) complexes inhibit photocurrent through recombination. Localized heterojunctions are much trivial and less efficient for photocurrent generation. [2] Herein, we have developed coaxial p-n heterojunctions by mesoscale alignment of self–sorted donors and acceptors for achieving high photocurrent generation. [3] Mixing of a p−type π -gelator (TTV) having high charge carrier mobility [4] with an n–type semiconductor (PBI) leads to self−sorted fibers which are coaxially aligned to form interfacial p−n heterojunctions. Contrasting structural and aggregation features of TTV and PBI discourage a direct CT interaction. Detailed UV–Vis spectral studies along with powder X−ray diffraction patterns, atomic force microscopy and Kelvin probe force microscopy revealed an initial molecular level self–sorting and a subsequent mesoscale self-assembly. A 12–fold enhancement in the anisotropic photoconductivity was obtained for TTV/PBI (1:1 molar ratio) coaxial fibers when compared to the individual assemblies of the donor or acceptor molecules measured by flash photolysis time resolved microwave conductivity (FP−TRMC) experiments. Details of these studies will be presented.
Fig.1: (a) Molecular structure of TTV and PBI with corresponding TEM image. (b) FP−TRMC photoconductivity transients of a) TTV (blue), PBI (red) and TTV/PBI (1:1) (black) films upon 355 nm laser excitation at 9.1 × 1015 photon/cm2.
Reference 1. (a) T. Aida et al., Science, 335, 813, 2012; (b) A. Ajayaghosh et al., Angew. Chem. Int. Ed. 51, 1766, 2012. 2. S. Shinkai et al., Chem. Mater., 20, 2863, 2008. 3. A. Ajayaghosh et al., Angew. Chem. Int. Ed., doi: 10.1002/anie.201408831. 4. (a) A. Ajayaghosh et al., J. Am. Chem. Soc., 132, 8866, 2010; b) A. Ajayaghosh et al., J. Am. Chem. Soc., 132, 13206, 2010.
P-509: Silica Supported One Pot Synthesis of Ferrocenyl Quinolines
Rahul Borse, Amruta Kanchagar, Amol Kale and Vidya Avasare* Department of Chemistry, Sir Parashurambhau College, Pune 411030, India [email protected]
Quinoline, ferrocene and its derivatives have wide applications in medicines as antimalarials, antibacterials, anticancer agents etc It has also been used in catalysis, pigments dye. Skraup has reported the first synthesis of quinoline[1] and after that large numbers of attempts have been made to synthesise quinoline from different precursors and under various reaction conditions[2-4]. In many reported synthesis either very expensive catalyst or complicated reaction conditions have been employed. Most importantly, many of these methods cannot be utilized for the synthesis of ferrocenylquinolines in single step. Here, we have attempted facile synthesis of ferrocenyl quinolines from aromatic amines and 3-chloro-3- ferrocenylacrylaldehyde in almost good purity and high yields (Scheme 1).
Fe NH 2 Cl O SiO2 + Fe H RT, 3-12 hrs N R R Scheme 1
References
1. Skraup, H. Chem. Ber. 13, 2086, 1880.
2. R. Yan, X. Liu, C. Pan, X. Zhou, X. Li, X. Kang, G. Huang, Org. Lett., 15, 4876, 2013.
3. T. M. Gøgsig, A. T. Lindhardt, T. Skrydstrup, Org. Lett., 11, 4886, 2009.
4. S. Khong, O. Kwon, J. Org. Chem.,77, 8257-8267, 2012,.
P-510: Ferrocene-Maltose Conjugate: A Selective Fluorescent Probe for Detection of Magnesium (II) Ion in the Living Cell Amol B. Kale, Rahul A. Borse and Dr. Vidya Avasare* Department of Chemistry, Sir Parashurambhau College, Pune-411030, India [email protected]
Magnesium(II) is the second most abundant metal ion (intracellular labile Mg(II) concentration ranges between 0.5-0.7 mM) after potassium. It plays crucial role in many metabolic pathways such as RNA & DNA synthesis, protein phosphorylation, ATP synthesis of mitochondria [2] and many enzymes metabolites..In the recent report, Feng –Yen Li and his group has unveiled the role of Mg(II) ion in the intracellular signaling like Ca2+ .An abnormality in the concentration of intracellular Mg(II) ion can lead to various disorders like Migraines , Diabetes , Hypertension and Parkinson’s disease[2-5]. In our group, we have synthesized a selective fluorescent probe, ferrocene-maltose conjugate to understand the presence of labile pool of Mg(II) ions in the cell in the presence of other biologically significant metal ions.
References
1. L. Feng-Yen et al, Nature 475, 471, 2011. 2. J.S. Rodriguez-zavala & et al J. Biol. Chem. 273,7850 , 1998. 3. M.D. Boska , Neurology 58,1227,2002 4. M. Yasui Neurotoxicology 13, 593, 1992 5. D. Keenan FEBS Lett 395,241, 1996
P-511: Extending Copper Redoximetry Via Anion Solvent Cooperativity. Showket Ahmad Akhoon, G. M. Peerzada and M. A. Rizvi Department of Chemistry, University of Kashmir, Hazratbal, Srinagar, 190006, J&K, India
Abstract We investigated the impact of perchlorate ions and acetonitrile medium on copper redox couple. The acetonitrile solvent and perchlorate ions were found to synergistically increase the redox potential of Cu(II)-Cu(I) couple, thereby increasing its ability to oxidize more systems and expand the copper redoximetric analysis window. The difference in the behavior of thiourea towards copper(II) salts in aqueous and non-aqueous media was also explored. Based on the synergistic effect, an electroanalytical method for composition analysis of copper(I) thiourea complexes is proposed. Kinetic and quantum chemical studies have been used for mechanistic insight of synergistic effect of acetonitrile and perchlorate ions on copper redox couple. Keywords: Synergistic effect, copper redoximetry, non aqueous electrochemistry, acetonitrile, copper thiourea complexes, composition analysis.
P-512: Highly Luminescent Europium (III) and Terbium (III) Complexes for Biosensing Applications Srikanth Dasari, Ashis K. Patra* Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India E-mail: [email protected]
The unusual and fascinating luminescence properties of lanthanides (Ln) have diverse applications in biology and medicine.[1,2]Lanthanide complexes have been widely used as luminescent sensors due to their longer excited state life times, suitable excitation and emission wavelengths in biological media, and sharp emission bands distinct from organic flurophores. Lanthanide based bioprobes could be elegantly designed and used for biological sensing and imaging applications in a wide spectral window which are not accessible to organic molecular probes.[3-5] In this presentation, we will describe synthesis, structures, photophysical properties, binding interactions with biomolecules and bioanalytes of a series of Eu(III) and Tb(III) complexes containing planar N,N-donor heterocyclic bases, viz. dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), dipyrido[3,2-a:2′,3′-c]phenazine (dppz)and 4,4,4-trifluro-1-(2-napthyl)-1,3-butanedionate (tfnb) as photosensitizer to induce desirable optical properties. We will also emphasize the applications of these complexes as phototherapeutic and diagnostic agents.
References 1. Bünzli, J.-C. G. et al.,Chem. Soc. Rev.34, 1048, 2005. 2. Bünzli, J.-C. G. et al.,Chem. Sci.4, 1939,2013. 3. Hefferin, M. C. et al.,Chem. Rev. 114, 4496, 2014. 4. Leonard, J. P. et al.,Chem. Commun.129, 129, 2007. 5. Wang, X. et al.,Chem. Sci. 4, 3748, 2013.
P-513: In vitro cytotoxicity and in vivo systemic toxicity studies of heteronuclear Cu(II)–Sn(IV) chemotherapeutic anticancer drug entity Farukh Arjmand *1, Yusra Zaidi 2 1Department of Chemistry, Aligarh Muslim University, Aligarh–202002, India. 2Department of Zoology, Aligarh Muslim University, Aligarh 202002, U.P., India. *Corresponding author. Tel.: +91 5712703893. E–mail: [email protected] (F. Arjmand).
Chiral L–tryptophan derived [bis(1,2–diaminobenzene) copper(II)] chloride complex [CuSn2(Trp)] was synthesized previously as an active chemotherapeutic agent. We have investigated CuSn2(Trp) induced in vitro cytotoxicity on a panel of human cancer cell lines and in vivo acute and systemic toxicities in healthy female Wistar rats. MTT assay showed that CuSn2(Trp) exhibits strong anticancer potency against ovarian (PA–1) and prostate carcinomas (PC‒3) but lower potency towards liver (HepG2) and breast carcinomas (MCF–7). Further, flow cytometric analysis demonstrated that CuSn2(Trp) kills PA–1 cells dose‒dependently after 48 h treatment. Fluorescence microscopy and western blotting studies revealed that the plausible mechanism behind CuSn2(Trp) cytotoxicity was apoptosis, which was further substantiated by cleavage of caspase–3 and poly–(ADP–ribose) polymerase (PARP). Furthermore, complex demonstrated lower toxicity than CDDP in rats as evident from its eight fold (98.11 mg kg−1) more medial lethal dose (LD50) than CDDP (12 mg kg−1). Besides, the safety profile of CuSn2(Trp) was also established and no measurable DNA damage, nephrotoxicity, hepatotoxicity and neurotoxicity were observed when assessed as a function of oxidative stress markers in contrast to CDDP at equivalent lower doses [1,2].
References 1. Y. Zaidi, F. Arjmand, N. Zaidi, J. A. Usmani, H. Zubair, K. Akhtar, M. Hossain and G.G.H.A. Shadab, Metallomics, 6, 1469, 2014. 2. M. Chauhan, K.Banerjee, and F. Arjmand, Inorganic Chemistry, 46, 3072, 2007.
P-514: Azo-phenol Zn(II)/ Cu (II) Complex: Selective Receptor for Copper(II) ion.
Niraj Kumari, Pramod Kumar Yadav, Abhishek Rai, and Lallan Mishra*
Department of Chemisty, Faculty of Science
Banaras Hindu University, Varanasi- 221 005, India
The design and synthesis of simple and efficient chemo sensors of high selectivity and sensitivity for the recognition of biologically important and environmentally relevant metal ions have attracted a great deal of attention in recent years. Copper is the third most abundant transition-metal ion in the human body (after FeIII and ZnII) and is essential for many biochemical and physiological functions. Zn(II) and Cd(II) complexes of type
[M(LH)2(bpy)2] where, {M= Zn(II), Cd(II), LH2= 4-(2-hydroxy-naphthalen-1-ylazo)-benzoic acid, bpy= 2,2'-bpy) showed strong affinity for Cu(II) ion. The receptors sense Cu2+ in solution by changing its color from light yellow to deep pink. The sensors have visual detection limits of 15-35μM and have been used as staining agents for Cu2+ in microorganisms. A detailed account of the study will be presented.
Fig. A Representative Ortep diagram of Zn(II) complex
P-515: Synthesis, spectral and X-ray characterization of Cu(II), Zn(II) and Mn(II) complexes of NNS tridentate and Pd(II) complex of NN(µ-S) tetradentate thiobenzyl esters M.K. Bharty* & Pooja Bharati Department of Chemistry, Banaras Hindu University, Varanasi- 221005, India. E-mail: [email protected], [email protected] Abstract New type of NNS tridentate ligands N'-[bis(benzylsulfanyl)methylene]-picolinoyl hydrazide (Hbsmph) (1) and N'-(pyridine 2-carbonyl) hydrazine carbodithioic acid benzyl ester (H2pchcbe) and their Cu(II), Zn(II)/Mn(II) and tetranuclear Pd(II) complexes have been synthesized and well characterized by elemental analyses, IR, NMR and single crystal X-ray diffraction techniques. The reactions of N'-[bis(benzylsulfanyl)methylene]-picolinoyl hydrazide (Hbsmph) (1) with CuCl2·2H2O, CuBr2 and CuCl gave [Cu(bsmph)X·CH3OH] {X = Cl(2), Br(3)} and [Cu(bsmph)(µ-Cl)]2·2H2O (4) respectively which are mononuclear/ dinuclear five coordinate possessing square pyramidal geometry. The reactions of N'- (pyridine 2-carbonyl) hydrazine carbodithioic acid benzyl ester (Hpchcbe) with ZnCl2·2H2O, MnCl2·4H2O and ZnBr2 yielded [M(Hpchcbe)2]·CHCl3 {M = Zn(5), Mn(7)} and [Zn(Hpchcbe)2] (6) which possess distorted octahedral geometry. A tetranuclear [Pd4(µ- pchcbe)4]·4H2O (8) complex has also been prepared by the reaction of Hpchcbe with PdCl2 which has square planar geometry around each Pd(II) centre. In the [Pd4(µ-pchcbe)4]·4H2O, the ligand behaves as a NN(µ-S) dinegative tetradentate whereas in Zn(II) and Mn(II) complexes it acts as mononegative NNS tridentate.
Molecular structure of [Cu(bsmph)(µ-Cl)]2·H2O (4) Molecular structure of [Pd4(µ-pchcbe)4]·4H2O (8) References: [1] H. H. Nguyen et al., Inorg. Chem. 48, 25, 2009.
[2] P. I. da S. Maia, et al., Inorg. Chem. 51, 1604, 2012.
[3] N.K. Singh et al., J. Mol. Struct. 936, 257, 2009.
P-516: Synthesis,Characterization and Biological Activity of (O, N) type Schiff’s bases and their Pd(II) and Ni(II) complexes Satheesh C E1, Pankaj Sharma, P2, Marulasiddeshwara M B1, Rajegowda H R1, and Raghavendra Kumar P1* Department of Studies and Research in Chemistry, Tumkur University, Tumkur-572103, Karnataka, India. *E-mail address: [email protected] and contact no. 9901511112
Abstract: New (O,N) type of bidentate Schiff’s base ligands, L1H and L2H and their Pd(II) and Ni(II) complexes [1],[M(L1-2)2] (1-4), were synthesized and characterized. L1H and L2H were synthesized by reaction of 2-(3,4- dimethoxyphenyl) ethanamine with 2-hydroxy benzaldehyde and 2-hydroxyacetophenone respectively. The 1 2 Pd(II) and Ni(II) complexes were prepared by reaction of L H and L H with precursors Na2PdCl4 and 1 13 1 NiCl4.6H2O in 1:2 ratio. The ligands and metal complexes were characterized by H, C{ H} NMR, elemental analysis, FT-IR, UV, Vis. Spectroscopy. The single crystal structure of 3 and 4 were characterized by single crystal X-ray diffraction. The Ni-O, Ni-N, C=N and C-O bond lengths are 1.825, 1.927, 1.290(2) and 1.311 Å while Pd-O, Pd-N C=N and C-O bond lengths are 1.99, 2.02, 1.32(2) Å respectively. The bond angles represent square planner geometry around palladium and nickel atoms. The ligands L1H and L2H and complex compounds 1-4 were screened for their antibacterial activities and antifungal activities [2]. Key words: Schiff’s base, Palladium, Nickel, (O, N) ligands, Complex
1) Molecular structure. 2) Crystal packing . 3) Antibacterial activities of 1-4.
M= Pd(II)(3) M=Ni(II)(4) M= Pd(II)(3) M=Ni(II)(4)
Reference a ,* 1. Mojtaba Bagherzadeh , Mojtaba Amini a, Arkady Ellern b, L. Keith Woob. M. Bagherzadeh et al. / Inorganica Chimica Acta 383 (2012) 46–51.
2. C.Perez,M. Paul,and P. Bazerque, “An antibiotic assay by the agar well diffusion method”, Actabiologiaeet Medicine Experimentalis,15,113-115,1990.
P-517: Preliminary investigations of homobimetallic ruthenium complexes bearing N-heterocyclic carbene ligand Deep Mala,Balaji R. Jagirdar* Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India Email:[email protected] Corresponding Author: Balaji R. Jagirdar, Fax No: 91-80-2360-1552, Email: [email protected]
Abstract Keywords: N-heterocyclic carbene, homobimetallic complexes The chemistry of N-heterocyclic carbenes(NHCs) has been explored extensively in different catalytic applications due to their strong sigma donor ability and steric tunable capability. There are many bimetallic transition metal complexes reported in literature [1-3]. However, the chemistry of NHC bearing homobimetallic complexes has been studied to a very small extent.4,4’-bipyridine (4,4’-bpy) is a useful bridging ligand for the synthesis of bimetallic complex.
A homobimetallic ruthenium complex [RuHCl(CO)(IMes)(PPh3)]2(4,4’-bpy) (IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazole-2-ylidene) (1a) was synthesized in a quantitative yield and the complete characterization of the complex was carried out by 1H NMR, 31P{1H} NMR, 13C{1H} NMR spectroscopy, elemental analysis, IR and X-ray crystallography. Synthesis of some similar bimetallic complexes have been done by taking other bridging ligands such as 1,2-bis(4-pyridyl)ethylene, and 1,2-bis(4-pyridyl)ethane. The protonation reaction of 1afor the synthesis of corresponding dihydrogen complexes will be presented.
References
1. Tian, L. Y. et al.Dalton Trans2014,43, 4093-4101 2. Lui, S. H. et al.Organometallics 2003,22, 737-743 3. Wu, X. H. et al.Organometallics 2010,29, 1150-1156
P-518: Construction of Solvent Mediated Supramolecular Isomers of Metal Organophosphonate via Crystal-Amorphous-Crystal Transformation Shikha Narang, Udai P. Singh* Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee - 247 667, India E-mail: [email protected]
ABSTRACT It is well established that the metal organophosphonate has the strong feasibility to exhibit voluminous coordination chemistry including mononuclear, layered complex and 3D structures [1-3]. However, the propensity of organophosphonate to show multidenticity is often confronted obstacle for crystallizing the phosphonate. Three Cu(II) based organophosphonate i.e. two molecular cationic zero dimensional complexes 1, 3 and one neutral complex, 2 involving phosphonomonoester, (ethylhydrogen(anthracen-9- ylmethyl)phosphonate) and auxillary ligand, bidendate pyridyl (2,2'BPy) have been synthesized. Structurally characterized, complex 1 led to the formation of supramolecular porous network with 1D channel. Remarkably, it resulted in the formation of complex 2 via solid state transformation (crystal-amorphous-crystal transformation), involving the formation of neutral coordination complex from cationic coordination complex on external stimuli. The structural change from porous to non-porous has been evidenced by single-crystal XRD. On the other hand, the cationic complexes 1 and 3 showed supramolecular isomerism with the change in solvent. It is hypothesized that the compound showed the mobility of uncoordinated nitrate ion from the lattice to the metal, hence, resulting in the transformation of cationic metal complex to neutral metal complex and thereby, it may show tunable luminescent behavior.
Fig. 1. Schematic representation of metal organophosphonate Keywords: Supramolecular isomers, phosphonate, solid state transformation, cationic metal complex Corresponding Author: contact number: +91-1332-285329 and E-mail ID: [email protected] REFERENCES
[1] Yang, X.-J., Bao, S.-S., Ren, M., Hoshino, N., Akutagawa, T. and Zheng, L.-M., Chem. Commun., 50, 3979, 2014.
[2] Mateescu, A., Raptopoulou, C. P., Terzis, A., Tangoulis, V. and Salifoglou, A., Eur. J. Inorg. Chem., 1945, 2006. [3] Cao, G., Hong, H.-G. and Mallou, T. E., Acc. Chem. Res., 25, 427, 1992.
P-519: Asymmetric Synthesis of Antiepileptic Drug (R)-Lacosamide (Vimpat) Yuvraj Garg and Satyendra Kumar Pandey* School of Chemistry and Biochemistry, Thapar university, Patiala-147005, India [email protected] Epilepsy is the neurological disorder that disturbs the normal activity of the brain cells. It is estimated that this disease affects over 50 million people all over the world, and an additional hundreds of thousands are diagnosed with epilepsy every year.1 Although it was introduced to medical treatment in the U.S. and Europe just in 2008, the worldwide net sales of Vimpat strongly increases from year to year, from €211 million in 2011 to over €411 million in 2013.2 The mechanism of action of Lacosamide has not been completely known, but it is believed that Lacosamide operates on the sodium channels of the neurons, reducing their activity. In addition, Lacosamide was also under clinical trials for treatment of a neuropathic pain.3
O H H C N 3 N H O O
CH3 (R)- Lacosamide (Vimpat ®)
Because of novel class of anticonvulsant agent, various methods for the synthesis of Lacosamide have been known in the literature, but most of the synthesis described from chiral pool approach starting from unnatural amino acid D-serine and derivatives.4-5 The details of these results obtained during the course of my Ph. D. work will be presented.
References:
1. World Health Organisation Reports; 2012. www.who.int. 2. UCB S.A.; Brussels, Belgium. www.ucb.com/investors/UCBtoday/Vimpat. 3. (a) Biton, V. Expert Rev. Neurother. 2008, 8, 1649-60. (b) McCleane, G. Expert Opin. Invest. Drugs 2010, 19, 1129-1134. (c) Hearn, L.; Derry, S.; Moore, R. A. Cochrane Database Syst. Rev. 2012, 2, CD009318. 4. (a) Choi, D.; Stables, J. P.; Kohn, H. J. Med. Chem. 1996, 39, 1907−1916. (b) Andurkar, S. V.; Stables, J. P.; Kohn, H. Tetrahedron:Asymmetry 1998, 9, 3841−3854. 5. Stecko, S. J. Org. Chem. 2014, 79, 6342-6346.
P-520: Phytochemical screening and antibacterial activity of Dodonaea viscosa powdered leaf extracts M. Anandan1 and H. Gurumallesh Prabu*1 1Department of Industrial Chemistry, School of Chemical Sciences, Alagappa University, Karaikudi -630 003, India E-mail address: [email protected] *Corresponding author. Tel.: +919443882946; Fax: +91 4565225202
Abstract
Phytochemical screening is important in the enumeration of bioactive compounds in medicinal plants. Dodonaea viscosa was known for its traditional medicinal activity. Room temperature stirring method was used for the extraction of active compounds from the air dried, powdered leaves. Petroleum ether and Acetonitrile were used as a solvent for the extraction process. The phytochemical results revealed that cellulosic materials, alkaloids and flavonoids were present in petroleum ether extract but terpenoids, phenols, flavonoids and quinones were present in Acetonitrile extract. The absence of carbohydrates, glycosides, tannins, saponins and steroids were observed in both the extracts. The antibacterial results showed that the petroleum ether extract has a better zone of inhibition than the Acetonitrile extract. The increasing concentration of the extract increases the zone of inhibition against the bacterium Streptococcus thermophilus.
Key words: Phytochemistry, Dodonaea viscosa, Antibacterial activity
Fig.1: Antibacterial activity of A. Acetonitrile and B. petroleum ether
P-521: Novel Protocol for Synthesis of Organic Ammonium Tribromides and Investigation of 1,2-Dipiperidinium Bistribromide-ethane in the Silylation of Alcohols and Thiols Siddhartha S Dhar*, Rupa R Dey, Bappi Paul National Institute of Technology, Silchar, Silchar 788010, Assam, India *E-mail: [email protected]
Keywords: Ditribromide; silylation, alocohols, thiols, catalyst
Tribromide based reagents especially organic ammonium tribromides (OATBs) have garnered significant attention due to their wide ranging applications in synthetic organic chemistry[1] Tribromides, often known as solid bromine have already been established to be superior to liquid bromine, NBS, Br2/HBr and many other traditional brominating reagents because of their easy-handling, non-hazardous nature, mildness, efficiency and selectivity. Recent past has also witnessed remarkable growth of chemistry of di-tribromide - reagents particularly owing to their ability to hold two equivalents of Br3 moieties in a single molecule[2,3] The work reported herein emphasizes on a novel and efficient protocol for the synthesis of organic ammonium tribromides, OATBs is developed by using inexpensive and eco-friendly periodic acid as oxidant for the - - conversion of Br to Br3 . The method does not use any mineral acid and metal oxidants. The protocol is utilized to synthesize a new bistribromide viz., 1, 1´-(ethane-1, 2-diyl)dipiperidinium bistribromide, EDPBT. EDPBT is investigated as catalyst in the silylation of alcohols and thiols by HMDS (hexamethyldisilazane) under solvent- free condition. The encouraging results obtained on silylation suggest that the procedure may serve as an efficient alternative route for protection of alcohols and thiols.
2 N EDPBT H ROH ROSiMe3 (2.5 mol %) Br + HMDS + NH3 Br 5-17 min, RSH 80-95 % RSSiMe3 (1 equiv) Magnetic Stirring o (5-10 C)
Br 4 equiv KBr Br3 NH NH NH NH 4 equiv H5IO6 Br Br3 Ground, r.t.
(Yield 95 %) EDPBT (Yield 92 %)
Fig.1: Synthesis of EDPBT from piperidine; (Inset): Silylation alcohols and thiols by HMDS catalyzed by EDPBT
References 1. U. Bora, M. K. Chaudhuri, D. Dey, S. S. Dhar, Pure Appl. Chem. 2001, 73, 93. 2. M. M. Hevari, F. Derikvand, M. Ghassemzadeh, B. Meumuller, Tetrahedron Lett. 2005, 46, 6243. 3. V. Kavala, S. Naik, B. K. Patel, J. Org. Chem. 2005, 70, 4267.
P-522: Ru(II)-catalyzed, β-carboline directed C-H functionalization: Selective arylation of C1-(hetero)aryl/PAHs-β-carboline derivatives and isolation of its cycloruthenated intermediates
Subramani Rajkumar, Shanmugam Karthik and Thirumanavelan Gandhi* Materials Chemistry Division, School of Advanced Sciences, VIT University, Vellore – 632 014, Tamil Nadu INDIA E-mail: [email protected]
A Ru(II)-catalyzed C-H arylation approach has been developed by utilizing β-carboline alkaloids as the directing group. Selective formations of diarylated products from moderate to excellent yields were accomplished. Broad substrate scope with excellent functional group tolerance for C1-phenyl/thienyl/PAHs-β- carbolines was demonstrated. A series of cycloruthenated β-carboline intermediates, and a library of new functionalized C1-phenyl/thienyl/PAHs-β-carbolines have been synthesized which is expected to possess photophysical properties and biological values. Furthermore, the stability studies of these cycloruthenated complexes will be presented.
Fig 1: ORTEP diagram of Ru(II) complex 2cr (50 % probability ellipsoids). Hydrogen atoms and solvent molecules are omitted for clarity.
P-523: Non-catalytic synthesis of methyl carbamate in high yield from urea and methanol using semi continuous stirred tank reactor
M. H.Ghom, H. Bandal, H. Reddy, L.S. Roy, S.K. Shingote, A. K. Kinage, V.H. Rane, A.A. Kelkar, V. V. Ranade*. CEPD Division, National Chemical Laboratory, Pune 411008, India [email protected]
Alkyl carbamates are important intermediates in the synthesis of number of microbicides, herbicides, pesticides, pharmaceutical agents etc [1]. They are important in organic synthesis as novel protecting group [2]. Synthesis of carbamates from urea is a cheaper route due to the low cost of urea and also ammonia generated in the process can be reused for urea synthesis. Synthesis of carbamate from urea and methanol is an equilibrium controlled reaction and efficient removal of ammonia from the reaction mixture by stripping with nitrogen and methanol is necessary to improve the carbamate yield. Herein we present our results on the selective synthesis of methyl carbamate in a continuous stirred tank reactor. Continuous stripping of the reaction mixture with methanol/nitrogen helped in removal of ammonia and shift equilibrium towards the product side. Fig 1 shows effect of different stripping agents on methyl carbamte yield. Yield of methyl carbamate was increased from 73% in batch to 97% when reaction was conducted at 170°C for 5 hrs using MeOH and N2 as stripping agent.
100 98 100 80.48
80 95.80 97.31
60 72.81 MC yield (%) 40 urea conv. (%) Conv./Selec% 20 urea conv. (%) 0 MC yield (%) None MeOH N2+MeOH
Stripping agent
Figure 3: Effect of Various stripping agents on Urea conversion and MC selectivity
Keywords- : Urea, carbamate, methanol, methanol stripping. Reference 1. Sun et al., chem. Eng Tecnol 27, 4. 2004 2. Salvator et al J. Org. Chem. 66, 1035-1037 2001
P-524: Synthesis of dimethyl carbonate from methyl carbamate and methanol by non-phosgene route: Influence of various catalysts on DMC yield. T.S. Jadhav, P. Biradar, G. Pande, L.S. Roy, S.K. Shingote, A. K. Kinage, V.H. Rane, A.A. Kelkar, V. V. Ranade*. CEPD Division, National Chemical Laboratory, Pune 411008, India [email protected]
Dimethyl carbonate (DMC) is gaining importance as green chemical product due to its low toxicity, low bio- accumulation, high oxygen content, and good bio-degradability [1]. Nowadays it is considered as an important intermediate in chemical industry and finds wide applications as methylating agent, green solvent, ideal additive for gasoline, and electrolyte for lithium battery [2]. Current research activities world over are focused on the development of environmentally safer routes for DMC and avoid use of hazardous phosgene [3]. In the present work we have attempted synthesis of DMC from methyl carbamate and methanol (scheme 1) using various catalysts under mild reaction conditions. Various catalysts like cenosphere, mixed metal oxide, double metal cyanides and ionic liquids were investigated for the synthesis of DMC in a batch reactor and continuous reactor with the aim of improving MC conversion and selectivity to DMC. The best results under batch conditions were obtained with 10%KNO3 impregnated on cenosphere which gave 29% DMC selectivity and 21% MC conversion. Some of the promising catalysts were tested in CSTR reactor using nitrogen and methanol as stripping agents for continuous removal of ammonia and DMC from the reaction mixture.
Scheme 1 Synthesis of DMC from urea and methanol
Keywords: non-phosgene, dimethyl carbonate, hydrotalcites, ionic liquids, cenosphere, double metal cyanide.
Reference
1. Pacheco et al., Energy & Fuels, 11, 1, 1997 2. D. Wang, Journal of Physics and Chemistry of Solids, 71, 427, 2010 3. Wangrae Joe et al., Journal of Industrial and Engineering Chemistry, 18, 1018 2012.
P-525: A Tandem Synthesis of Indolizine Derivatives and Docking Studies with Biological Receptors
Lokesh Kr. Agarwal & Neelima Gupta*
Department of Chemistry, University of Rajasthan, Jaipur 302 004, India Email: [email protected]; [email protected]
Keywords: Indolizine, [3+2]cycloaddition, Drug-DNA interactions
A number of naturally occurring alkaloids possess indolizine or hydrogenated indolizine nuclei as constituting moiety. [5,6]- and [7,8]-benzo fused indolizines show valuable biological activities and have been widely studied for their psychotropic, anti-inflammatory, analgesic, antimicrobial, antiexudative, antitumor and hypoglycemia activities. Consequently during recent years, plenty of attention has been paid to the synthesis of systems incorporating indolizine nucleus. We have synthesized a library of benzofused indolizine derivatives via a tandem [3+2] cycloaddition reaction of N-ylide with electron deficient dienophiles.
EE N COR N Et CH2COR Br E E O
E = COOMe, COOEt, CN
We also investigated the binding affinity of these molecules with a variety of biological receptors using computational tools such as Docking and Molecular Modeling programmes. These results show preference of strong intercalation by planar aromatic ring between adjacent DNA base pairs than groove binding.
P-526: Discovery of novel Anti-Cancer Ruthenium-Arene Pyridinylmethylene & Ruthenium–Arene Arylidineamino benzenethiol Scaffolds via Combinatorial Three Component Assembly
Aastha Sharma, Priyankar Paira* Pharmaceutical Chemistry Division; School of Advanced Sciences; VIT University Vellore, 632014 Tamil Nadu; India Email:
Abstract
Diversity oriented metal based scaffolds craft them a viable alternative to traditional organic scaffolds for drug design. Currently multi component combinatorial looms has been discovered and coupled with high-throughput screening in drug discovery, but they are not often used in metal-based drug design. Here we have developed a new combinatorial, metal-based, three components assembly green reaction for the synthesis of a library of Ru−arene (pyridinyl methylene) & Ruthenium–Arene (arylidine amino) benzenethiol complexes. These newly developed complexes were synthesized in a one-pot sequence using commercially available starting materials under green conditions. These libraries preserve a breakthrough in cancer drug discovery. IC50 Values for all these scaffolds against Various Cancer Cell Lines Determined Using the MTT Assay after 72 h and it was established that these Ru-arene scaffolds are more potent than Cisplatin.
References:
[1] Dobson et. al., Nature, 432, 824, 2004. [2] Paira et. al., Chem. Eur. J., 19, 8321, 2013.
P-527: Synthesis of Fused Pyrans and Thiopyranoindoles from Morita-Baylis-Hillman Acetate of Dicyclopentadienone
Alati Suresh and Irishi N. N. Namboothiri* Department of Chemistry, Indian Institute of Technology Bombay, Mumbai-400076 [email protected] Functionalized pyrans and thiopyranoindoles are important compounds in medicinal chemistry due to their wide range of biological activities.1 They display spasmolytic, diuretic, clotting, anti-viral, anti-tumoral and anti-anaphylatic activities and can be used as pigments of numerous natural products.2 Fused pyrans 5 and thiopyranoindoles 3 were synthesized by the reaction of MBH acetate 1 derived from dicyclopentadienone and various binucleophiles such as 1,3-dicarbonyls 4 and thioindoles 2. The reaction involves a cascade double Michael addition of β-dicarbonyls 4 and thioindoles 2 to the MBH acetate 1 in presence of amine bases such as DABCO and DBU, respectively. The obtained fused pyrans 5 were also subjected to retro-Diels-Alder reaction to give chromenes 6 and cyclopentadiene 7.
Reference 1. a) Humphrey, G. R.; Kuethe, J. T. Chem. Rev. 2006, 106, 2875. b) SandroCacchi, S.; Fabrizi, G. Chem. Rev. 2005, 105, 2873. 2. Rueping, M.; Sugiono, E.; Merino, E. Chem. Eur. J. 2008, 14, 6329.
P-528: Fructose derived δ-sugar aminoacid oligomers as a
new class of glycofoldamers
Madhuri Vangala
Chemistry Department,
Indian Institute of Science Education and Research, Pune 411008, India
*E-mail: [email protected]
Among the major classes of biomolecules, carbohydrates with their molecular diversity find applications in molecular recognition, drug design and material sciences [1]. Exploitation of the rigidity and diversity of the sugar from a structurally defined backbone leads to rational design of oligomeric derivatives with tendency to adopt specific compact conformations [2]. Carbopeptides are oligosaccharides having carbohydrate subunits linked to one another by amide bonds. This poster describes the synthesis of new sugar aminoacid derived from D-psicofuranose. The key step involves stereoselective opening of spiroketal ring with
TMSOTf and TMSN3 as nucleophile. The synthesis of these conformationally constrained sugar aminoacid with their unique combination of α & δ-aminoacid and their subsequent oligomer synthesis using solid phase peptide synthesis will be presented. These carbopeptides are expected to be soluble in water and with diverse substitution patterns will show unprecedented molecular architectures.
Fig. 1: Fructose derived Carbopeptides
Reference
1. Jose L.Jimenez Blanco et al., Beilstein Journal of Organic Chemistry. 2010, 6, No. 20. 2. A. Siriwardena et al., Angew. Chem. Int. Ed. 2013, 52, 10221.P-529: Reversible Turn On/OffFluorescent Chemosensor for Cu(II) with High Selectivity and Sensitivity
Ratish R. Nairand Pabitra B. Chatterjee* Analytical Discipline and Centralized Instrument Facility (AD&CIF), CSIR-CSMCRI, G. B. Marg, Bhavnagar-364002, Gujarat, India.
Abstract: The demand of artificial receptors that are selective for sensing and recognition of specific target ions(which are biologically and environmentally important)is continuously increasing.1 Colorimetric sensing of these ions has been shown to be a less labour-intensive alternative techniques based on fluorescence response. Utilizing the well-known spirolactam (non-fluorescent) to ring opened amide (fluorescent) equilibrium of rhodamine derivatives we have designed and synthesized a novel series of multidentatechemosensorsfrom Rhodamine 6G for selective detection of important analytes in aqueous solutions.These compounds are found to be very selective for sensing Cu2+ ionsin aqueous solutions. Colourless solution of the dye changes to pink colour in the presence of Cu(II) (Fig. 1). Other metal ions have almost no effect on Cu(II) sensing. Control studies have also proved that this fluoroionophore is very selective for Cu(II) over Cu(I) or Cu(0)(Fig. 2) and with perchlorateas counter anion it functionsmost efficiently. At physiological conditions onechemosensor has visual detection limit of 1 ppm (Fig. 3)andthe LDL value is 0.1 ppm using spectrofluorimeter.
References 1. V. Amendola et al., Coord. Chem. Rev. 37, 273, 2006.
P-530: Methyl Rotation during Thiolization – A Qualitative and Quantitative study
E. G. Jayasree* , S. Soorya Department of Chemistry, School of Physical and Mathematical Sciences, University of Kerala, Trivandrum, Kerala, India. 695581
Key words: Thiolization, methyl rotation and density functional theory Ph No. *9746790202, Email ID: *[email protected], [email protected]
Abstract Thiolization is one of the significant biochemical processes including that in enzyme catalysis. Comparison of mechanism of tautomerisation of thione and its oxygen analogue reveals that a methyl rotation takes place during the product formation. This study analyzes this C-C bond rotation both qualitatively and quantitatively.
Thione TSenethiol Enethiol
The calculated conformational change can be explained by fragment orbital analysis using Extended Hückel (EH) and ab initio methods. The two electron stabilization of HOMO of staggered conformer computed by the EH and the ab initio methods explains the C-C rotation. Calibration study was also performed to obtain the best level of theory for these reactions and M06-2X/6-31+G* has been found to be the best method among many density functionals studied.
P-531: Theoretical Analysis of Corrosion Inhibitors Invoking DFT Based Descriptors
B.Malik, 1 T.Chakraborty*1
1Department of Chemistry, Manipal University Jaipur, Jaipur 303007, India
*E-mail: [email protected] ; [email protected]
Corrosion inhibition is such a process through which the metal and alloy surfaces can be successfully protected in proper environment. Heterocyclic organic compounds containing sulfur atoms have been identified as good corrosion inhibitors. A number of researchers have already pointed out Sulfonamides for their remarkable corrosion inhibition efficiency. Now a days, theoretical study of molecular properties invoking Density Functional Theory (DFT) based descriptors has gained immense importance. Recently, Ebenso et al [1] have extensively studied the corrosion inhibition activity of a group of sulfonamides. In this venture, we have used semi empirical PM3 method to study corrosion inhibition efficiency of same sulfonamide derivatives. A nice correlation has been made between experimental inhibition efficiency of sulfonamide derivatives with their calculated DFT based descriptors. Our computed result is in same line with Ebenso et al [1]. Mchanistic activity of inhibition efficiency of sulfonamides has been further analyzed invoking local DFT based descriptors.
Reference
1. E. E. Ebenso et al., Int. J. Quant. Chem., 110, 2615, 2009.
P-532: Transformation of Macroscopic Diamond State into Medicinally
Important Nanographite State using Ayurvedic Technique of Bhasmikarana
Shivaji Takale1, R.W. Jawale2, B.A. Kulkarni3, M.P. Wadekar3, Yogesh Bendale4 and V.V. Dhapte*3
1. Bharati Vidyapeeth's College of Engineering Lavale Pune412115 2. BVDU College of Engineering, Katraj-Dhankawadi, Pune-411 043 3. BVDU Y. M. College, Paud Road, Pune-411 038 4. Ayurved Rasayani, Amrutkumbh, Navi Peth, Pune-411 030
E-mail : [email protected]
ABSTRACT
Although the concept of nanoscience and nanotechnology are recently established and rapidly developed their knowledge and existence may be found in Indian system of Medicine known as Ayurveda. In this system, there is an extremely important class of drugs of mineral origin called as ayurvedic bhasmas, which are derived from metals, non-metals, alloyes as well as naturally occurring complex materials like ores, gemstones, calcium-based marine products. The technique through which these bhasmas are synthesized is known as ayurvedic bhasmikarana whose art and Science was well established and systematically developed in ancient ayurvedic pharmacy. Through this technique of bhasmikarana, it is possible to transform macroscopic elemental state into medicinally important nanometric bhasma state where by miraculous medicinal properties are induced in the resultant bhasma state. Our research group is working in this challenging but promissing research area of vital importance since past several years and we have obtained some exciting results. Recently, we have carried out an interesting research project on the elucidation of the chemical and structural aspects of a famous carbon-based ayurvedic drug derived from natural diamond which is popularly known as ‘hiraka bhasma’ in India. This traditional drug is claimed to possess some extraordinary medicinal properties. It is used all over India since antiquity but till today its exact chemical and structural aspects are not explored. We have made some successful attempts to explore there aspects using modern analytical techniques. Our significant findings, results and conclusions will be presented through this communication. P-533: An Unconventional Approach to Study Kinetics and Thermodynamics Using Density Functional Reactivity Theory
Roy, R. K.
Department of Chemistry, Birla Institute of Technology and Science, Pilani-333031, Rajasthan, India E-mail: [email protected]
ABSTRACT: Density Functional Reactivity Theory (DFRT) based CDASE (Comprehensive Decomposition Analysis of Stabilization Energy, Bagaria et al. Phys. Chem. Chem. Phys. 2009, 11, 8306) scheme [1] is used to study kinetic and thermodynamic aspects of different types of chemical interactions. The interactions between different nucleobases and base pairs with Single Walled Carbon Nano Tubes (SWCNTs) as well as gold clusters are investigated and that is also without performing computationally intensive transition state optimization or thermochemistry calculation [2]. Binding interaction of cisplatin (hydrated) and cisplatin analogues with nucleobases guanine and adenine as well as with various protecting agents is also investigated using this scheme [3]. The study thus helps to predict the suitable combination of cisplatin drugs and protecting agents to be used in cancer treatment [4].
1. P. Bagaria, S. Saha, S. Murru, V. Kavala, B. K. Patel and R. K. Roy, Phys. Chem. Chem. Phys., 2009, 11, 8306 2. A. Sarmah and R. K. Roy, J.Phys.Chem. C 2013, 117, 21539. 3. A. Sarmah and R. K. Roy, RSC Adv. 2013, 3, 2822. 4. A. Sarmah and R. K. Roy, J Comput Aided Mol Des 2014 Sep 3.
P-534: Sulfonic acid functionalized mesoporous silica gel: An efficient adsorbent for the adsorption of reactive Dye- Rhodamine B Adarsh S. Bhatt, Kalpeshgiri A. Gosai, Haresh M. Mody* and Hari C. Bajaj* 1Discipline of Inorganic Materials and Catalysis, Academy of Scientific and Innovative Research, Central Salt and Marine Chemicals Research Institute (Council of Scientific and Industrial Research), G.B. Marg, Bhavnagar-364002, Gujarat, India. 2Electro-Membrane Processes, Academy of Scientific and Innovative Research, Central Salt and Marine Chemicals Research Institute (Council of Scientific and Industrial Research), G.B. Marg, Bhavnagar-364002, Gujarat, India. *E-mail: [email protected]:;[email protected]
Abstract
Mesoporous silica gel, sulfonated silica gel has been prepared and characterized by surface area analysis. The dye adsorption investigation has been conducted in batch reactor system to study the adsorption behavior of reactive dye (Rhodamine B, RHB) on silica gel (G) and sulfonic acid functionalized silica gel (SG). The maximum adsorption capacity was found to be 128 and 232 mg/dm3 for G and SG respectively. The kinetic study was done at 500 mg/dm3 and pseudo second order kinetic model was used to describe the kinetic data.
250 7 y = 0.008x + 0.829 6 R² = 0.992 200 5
150 4 G SG
3
Qe (mg/g) Qe 100 Qe (mg/g) Qe 2 50 G 1 y = 0.004x + 0.161 SG R² = 0.990 0 0 0 500 1000 1500 0 500 1000 Ce (mg/L) Ce (mg/L)
Fig. Adsorption isotherms of RHB dye on G and SG
References
1. J.B. Haredia et al. Color. Techn. 124, 310, 2008. 2. C.K Lee et al., J. Hazard. Mater 147, 997, 2007. 3. A.R. Cestari et al., J.Hazard. Mater.B 138, 133, 2006.
P-535: Insights into the interactions between enzyme and co- solvents: Stability and activity of stem bromelain
Anjeeta Rani and Pannuru Venkatesu* Department of Chemistry, University of Delhi, Delhi-110 007, India
ABSTRACT: Understanding the structural and functional property of stem bromelain (BM) provides insight into the mechanism underlying its clinical utility and also fulfills the purpose of storage, transport and shelve-life during industrial applications. In present study, an attempt is made to elucidate the effects of various naturally occurring osmolytes and
denaturants on BM at pH 7.0. The effects of the varying concentrations of glycerol, sorbitol,
sucrose, trehalose, urea and guanidinium chloride (GdnHCl) on structure, stability and
activity of BM are explored by fluorescence spectroscopy, circular dichroism (CD), UV-vis
spectroscopy and sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE).
Our experimental observations reveal that glycerol and sorbitol are acting as stabilizers at all concentrations while sucrose and trehalose are found to be destabilizers at lower concentrations, however, acted as stabilizers at higher concentrations. On the other hand, urea and GdnHCl are denaturants except at lower concentrations. The catalytic activity measurements of BM give direct signature to the function and conformation relationship as activity data are in accordance to the conformational stability parameters and BM profile on
SDS-PAGE.
P-536: An amphiphilic and thermoresponsive conjugated block copolymer with its solvent dependent optical and photoluminescence properties: towards sensing applications Pallavi Kumari1, Manas Kumar Bera2, Sudip Malik2 and Biplab K. Kuila1* 1Centre for Applied Chemistry, Central University of Jharkhand, Brambe, Ranchi, India, Pin- 835205, Email: [email protected] 2Polymer Science Unit, Indian Association for the Cultivation of Science, 2A&2B Raja S. C. Mullick Road, Kolkata-700 032, India
Design and synthesis of conjugated polymeric materials with new functionality and wide processibility has attracted a great deal of research attention because of their potential applications in many fields like sensors, energy storages and optoelectronic devices etc.[1,2]. Block copolymers where the functionality of the blocks can be varied independently, self- assemble into fascinating set of periodic nanostructures and are very attractive targets to device new materials where precise control over nanoscale organization is crucial[3]. Her we have reported a novel class of amphiphilic, thermoresponsive rod-coil conjugated block copolymer consist of regioregular poly(3-hexyl thiophene) and Poly(N-isopropyl acrylamide). The block copolymer is synthesized by facile click reaction (scheme-1). The successful synthesis of the block copolymer was confirmed by NMR, FTIR and MALDI-ToF MS. Optical and luminescence properties of theses polymers significantly depend on the self- assembled nanostructures formed in different solvent and are easily controlled by altering the solvent composition or external stimuli like heat.
Scheme 1 Total Reaction Scheme for the synthesis of P3HT-b-PNIPAM
References 1. H.Sirringhaus, N. Tessler, R. H. Friend, Science 280,174, 1998. 2. A. J. Heeger, Angew. Chem. Int. Ed., 40,2591, 2001. 3. B. K. Kuila, C. Chakraborty, S. Malik, Macromolecules 46, 484, 2013.
P-537: Adsorption and Enantiomeric separation of amino acids on polycrystalline metal surfaces: A spectroelectrochemical approach Deepak Kumar,1 Meenu Chhabra,1S. Harinipriya,2 Samanwita Pal,*1 1Center for Biologically Inspired System Science, Indian Institute of Technology Jodhpur 342011, India 2Non Ferrous Materials Technology Development Center, Hyderabad 500058, India E-mail: [email protected] Key words: enantiomers, amino acids, alanine, Circular Dichroism, UV-Vis, FTIR, Cyclic Voltammetry *E-mail: [email protected] Mobile: +918561881456
Abstract:
In recent years enantiomeric separation of biologically relevant molecules e.g., amino acids, peptides etc. has gained immense importance since optically pure materials are vital in pharmaceuticals, fine chemicals and electronic industries. Over the past various physicochemical techniques have been developed in order to investigate adsorption and consequent chiral discrimination of amino acids in solution at metal surfaces [1-3]. In this study we report the adsorption behavior of racemic alanine in LiClO4 medium on different polycrystalline metal surfaces viz., Ag, Au, Cd, Ni, Cu and Zn using Cyclic Volatammetry (CV). Spectroscopic analysis of the resulting amino acid solutions after CV scan by FTIR indicated dissociative adsorption with the formation of - C≡N and terminal alkynes. Dextro rotation of the resulting solution as measured by Circular Dichroism (CD) implied preferential adsorption of L-alanine over D enantiomer on the above mentioned metal surfaces. This could be attributed to the umbrella inversion of the molecule after adsorption on the metal surface in presence of the applied electric field in the LiClO4 environment [4]. The enantiomeric excess of the resulting solution has also been quantified using CD.
References
1. Andrea P. Sandoval et al, Electrochimica Acta, 89, 72, 2013
2. Tatiana Popa et al, Surface Science , in press, 2014
3. Maria Jurkiewicz-Herbich et al., Colloids and Surfaces A: Physicochemical and Engineering Aspects, 178 , 325, 2001 4. S. Harinipriya et al., J. Electrochem.Soc., 160, G102, 2013
P-538: Chemoselective Surface Immobilization of Quantum Dot Conjugates via Bioorthogonal Strain-Promoted Click Chemistry: An Efficient Technique for Direct Gene Detection
Kamal Peshwani, Priyankar Paira* Pharmaceutical Chemistry Division; School of Advanced Sciences; VIT University Vellore, 632014 Tamil Nadu; India Email: [email protected]
Abstract Health risks caused by microbiological organisms are of an increasing concern. Nowadays, Polymerase chain reaction (PCR) based diagnostics are promising approaches for the detection and identification of microorganisms from clinical and environmental samples because of its high level of accuracy, sensitivity and reproducibility.[1] The advent of real-time PCR has facilitated the development of a portable instrument for genetic testing of infectious organisms. However, RT-PCR also has some drawbacks such as its complicated procedures, high costs, and high false positive rates arising from cross contaminations between samples. As a result, the development of a simple, rapid and sensitive detection technique is still required. Semiconductor QDs as fluorescent labels are particularly fascinating for in vitro diagnostics due to their relatively high quantum yield (> 90%), very high levels of brightness and photo stability, narrow emission bands (>30 nm), tunable and size-dependent emission wavelengths, which are not available from conventional fluorescent dyes and proteins.[2] Here, we have demonstrated a simple, efficient and chemoselective technique for gene detection by QD-immobilization through the biocompatible SPAAC Click Chemistry. The proposed QD-based PCR-coupled detection scheme exploits high specificity of PCR to amplify and label a target gene sequence. QD conjugates selectively immobilized on the DBCO modified bead surface via SPAAC provide direct and strong fluorescence in Fluorescence Microscopy. Therefore, this detection scheme leverages PCR for the selective amplification and the subsequent orthogonal binding between the amplicons and the beads surface validates the high specificity, sensitivity, as well as its feasibility for target gene detection.
Fluorescence imaging
Figure 1: Immobilization of Quantum dot-Streptavidin modified DNA conjugate on polystyrene beads via SPAAC
Keywords: Quantum Dots, SPAAC, Fluorescence, PCR, Gene Detection Corresponding Author: Dr. Priyankar Paira;Contact: 8110020748 [email protected] References: [1] K. Mullis et.al. Science, 252, 1643, 1991 [2] Alivisatos et.al., Annu. Rev. Biomed. Eng., 7, 55, 2005; A. M. Smith et. al., Acc. Chem. Res., 43, 190, 2010. P-539: Oriented Single Crystalline 1D Rutile TiO2-MWCNT Composite for Enhanced
Photoelectrochemical Activity
Subha Sadhu, Pankaj Poddar*
Physical & Material Chemistry Division, CSIR-National Chemical Laboratory, Pune 411008, India, [email protected]
Template free synthesis of phase pure one-dimensional (1D), single crystalline rutile titania nanorods or wires in low temperature still remains a challenging task due to its complex nature of surface chemistry. To further modify the electrical conductivity and optoelectronic properties of these 1D structures various methods such as doping of TiO2 with metal and non metal, synthesis of branched and hybrid structures are developed. In this effort, for the first time we have simultaneously synthesized 1D-rutile TiO2-multiwalled carbon nanotube (MWCNT) composite film directly grown on fluorine dope conducting oxide (FTO) substrate along with 1D rutile TiO2-MWCNT composite powder. The as-grown nanorods film were single crystalline and oriented vertically with respect to the substrate, having average length of 2 µm. The composite film shows positive movement of the flat-band edge and increase in charge carrier density. The TiO2-MWCNT composite was successfully used as photoanode in a dye sensitized solar cell (DSSC) and exhibits a 60 % increase in energy-conversion efficiency compared with only TiO2 nanorods. )
2 TiO -MWCNT 8 2 TiO2
mA/cm 6
4 CNT e- TiO2 2 e e e e -e e - - - - - Dye Current Density ( Density Current 0 0.0 0.2 0.4 0.6 0.8 Potential (V)
References 1. J. Bang and P. Kamat, Adv. Funct. Mater, 2010, 20, 1970–1976. 2. S. Sadhu and P. Poddar, J. Phys. Chem. C, 2014, 118, 19363-19373.
P-540: Nitrogen-doped graphene interpenetrated 3D Ni-nanocages: efficient and stable water-to-dioxygen electrocatalysts
Vishal M. Dhavale, Sachin S. Gaikwad, Leena George, R. Nandini Devi, Sreekumar Kurungot*
We report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni- nanocage (Ni–NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water-to-dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni–NGr nanocage displays a substantially low overpotential of 290 mV at a practical current density of 20 mA cm−2 in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of 570 and 370 mV under similar conditions. Moreover, the long term stability of Ni–NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm−2 was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm−2, which highlights the better sustainability of Ni–NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h−1 g−1 of oxygen, which is constant in the second cycle as well.
Scheme . Schematic illustration for the synthesis of Ni-NGr nanocage particles.
P-541: Facile and rapid synthesis of tryptophan based carbon dot and its application for sensing of CN- in aqueous media
Shreya Bhatt1, Madhuri Bhatt,1,2 Anshu Kumar,1,2 Parimal Paul1,2*
1 Analytical Discipline and Centralized Instrument Facility, Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, India 2 Academy of Scientific and Innovative Research, Central Salt and Marine Chemicals Research Institute, Bhavnagar-364002, India. *E-mail: [email protected]
Among optical materials, those that are strongly fluorescent have attracted much attention for their variety of applications in field of display technologies, biology, medicine and sensing. As fluorescent probe many dyes and fluorogenic entities1, high-performance Quatum Dots (QDs)2 are used. Recently, carbon nanoparticles/carbon dots (C-dots) have emerged as a promising fluorophore because of their photo luminescent property, chemical inertness and biocompatibility3. The sensing and recognition of CN- have received considerable attention for their toxic effect in mammalians. Humans and animals cardiovascular, respiratory and central nervous systems are highly affected by cyanide poisoning. Therefore the need for the development of probes in detection of CN- in aqueous medium has become a prime necessity4. A facile route has been developed to synthesize and isolate fluorescent carbon dots from tryptophan (Try-CD) without any additional surface passivation. Try-CD is characterized by different analytical (TEM, AFM, FT-IR, C,H,N,S) tools. Small sized Try-CD (< 5 nm) is highly fluorescent and gives white light in longer wavelength. In presence of ethanol it gives high fluorescence which changes with change in water ratio. This Try-CD was further used for CN sensing in aqueous medium.
Fig.1: Synthesis route for TRP-CD and its interaction with cyanide.
Reference 1. S. Kay et al., J. Comb. Chem., 12, 595, 2010
2. Z. Jun-Jie et al., J. Mater. Chem. C, 2, 595, 2014
3. L. Shuit-Tong et al., J. Mater. Chem., 22, 24230, 2012
4. Y. Juyoung et al., Chem. Soc. Rev., 43, 4312, 2014
P-542: A Distinctive PdCl2 Mediated Transformation of Fe-based Metallogels into Metal Organic Frameworks
Harshitha Barike Aiyappa, Sreekumar Kurungot* and Rahul Banerjee*
Physical Chemistry Division, National Chemical Laboratory, Pune 411008, India
*E-mail: [email protected]
3+ Simple, efficient conversion of viable Fe -based metallogels into Fe-MOFs has been achieved by PdCl2 mediated gel degradation. The metallogels and the resulting MOFs have been characterized and a probable mechanism for the event has been elucidated. The formation of large mountable Fe-MOF crystals is found to be mediated via formic acid/DMF oxidation [1]. This route paves way for an efficient synthesis and single crystal structure determination of most of the MOFs, in particular, Fe-based MOFs which are otherwise difficult to synthesize and demand high-resolution powder X-ray diffraction data for their structure determination through Rietveld refinement techniques.
3+ Fig.1: Simple, efficient transformation of viable Fe -metallogels into Fe-MOFs has been achieved via PdCl2 mediated metallogel degradation.
Reference
1. H. B. Aiyappa, S. Saha, B. Garai, J. Thote, S. Kurungot, R. Banerjee, Cryst. Growth Des. 2014, 14, 3434.
2. H. B. Aiyappa, S. Saha, P.Wadge, R. Banerjee, S. Kurungot, Chem. Sci., 2014, DOI: 10.1039/C4SC02294G.
P-543: A Covalent Organic Framework–Cadmium Sulfide Hybrid as a Prototype Photocatalyst for Visible-Light-Driven Hydrogen Production
Jayshri Thote, 1 Harshitha Barike Aiyappa, 1 Rahul Banerjee *1
1Physical/Materials Chemistry Division, National Chemical Laboratory, Pune 411008, India
*E-mail: [email protected],
In the present study, CdS nanoparticles is deposited on a highly stable, two dimensional (2D) covalent organic framework (COF) matrix and the hybrid is tested for photocatalytic hydrogen production. The efficiency of the CdS-COF hybrid is investigated by varying the COF counterpart. On introduction of just 1 wt% of COF, a dramatic tenfold increase in the overall photocatalytic activity of the hybrid is observed. Among the various hybrids synthesized, the one with 10 wt% COF, named CdS-COF (90:10), is found to exhibit a steep H2 production amounting to 3678 µmolh-1g-1, significantly higher than that of bulk CdS particles (124 µmolh-1g-1). The presence of π conjugated backbone, high surface area and occurrence of abundant 2D hetero-interface highlights the usage of COFs as effective support material for stabilizing the generated photoelectrons thereby resulting in an efficient and high photocatalytic activity.
Figure1: Comparison of visible-light-induced H2 production using as-synthesized hybrid along with bulk CdS and COF
Reference
1. S. Kandambeth et.al., J. Am. Chem. Soc., 134, 19524, 2012.
2. J.Thote et al., Chem. Eur. J., 2014. DOI: 10.1002/chem.201403800.
P-544: DFT insight of hydrogen bonding influence in the asymmetric cross- aldol and cis/trans isomerisation in δ-lactones.
M. A. Rizvi*, 1 M.V. Mane, 2 M. Kumar, 3
1 Department of Chemistry, University of Kashmir, 190006, India 2 PMC Division, National Chemical Laboratory, Pune 411008, India 3 NPC Division, CSIR-Indian Institute of Integrative Medicine (IIIM), Jammu, 180001, India
*E-mail: [email protected]
The transformation of quantum chemical calculations from a highly specialized branch of theoretical chemistry to a practical tool has vastly developed the field of computational organic chemistry [1]. The high-speed computers and advances in DFT have revolutionized mechanistic understanding of organic reactions [2]. This work utilizes density functional theory (DFT) at PBE/TZVP level for mechanistic insights of enantioselective cross-aldol reactions of acetaldehyde and the formation of α,β-unsaturated δ-lactones, which is proposed to involve thermal trans/cis isomerization of the olefin double bond. DFT calculations suggest that the hydrogen bonding activates the substrate as well as brings the stereo-regulation in the reaction. The optimized transition states depict the enantiofacial discrimination by the bulky aryl rings; for the attack at the Re face, the aryl rings are sufficiently far apart and form a low energy stable adduct (20.9 kcal/mol), whereas for the attack on the Si face, the aromatic groups are close to interact sterically leading to a less stable higher energy (25.6 kcal/mol) adduct (Fig.1) The mechanistic insights of thermal trans/cis isomerisation of the olefin bond in the synthetic methodology of α, β-unsaturated δ-lactone synthesis [3] were also investigated. The calculations predict that the rate of the lactonization reaction depend on the concentration of the Z isomer as well as the comparative rates of cyclization and the reverse isomerisation of E to the Z isomer during the reaction. The availability of the required Z isomer is best achieved by heating at 70 °C as the E isomer cannot be populated thermally due to the high E_Z thermal isomerization barrier (3.3 kcal/mol). Thus, heating to 70 °C establishes a high Z/E ratio that favors the formation of the cyclized product (Fig 2).
Fig.1: Optimized cross aldol transition states. Fig.2: DFT calculated free energies of lactonization process
Reference
1. S. M. Bachrach, Annu. Rep. Prog. Chem., Sect. B: Org. Chem., 108, 334, 2012.
2. R.B Sunoj et al., J. Am. Chem. Soc., 132, 12315, 2010.
3. B.A.Shah et al., Eur. J. Org. Chem, 1, 5247, 2014. P-545: Unusual Reactivity of Nitronates with an Aryl Alkyl Carbonte: Synthesis of Alpha Amino Esters
G. Ramana Reddy, Debopreeti Mukherjee, Arjun Kumar Chittoory, Dr. Sridar Rajaram.
New Chemistry Unit, Jawahar Lal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore, 560064.
Nitronate anions are ambidentnucleophiles, that can react through oxygen atom or carbon atom. In the literature it has been reported that nitronateanions react with electrophiles such as carbonates, chlorformates, and isocyanates to yield nitrile oxides.1In these cases the oxygen atom acts as nucleophile. In order to achieve reaction at carbon atom, the dianionsof nitroalkaneshas to be formed in the reaction mixture. The dianionsof nitroalkaneshas been generated using strong base at low temperature.2 We have found a reaction, were the monoanions of nitroalkanes (generated in situ) react with thebezyl phenyl carbonate in the presence of a nucleophilic catalyst to yield α-nitro ester. These α-nitro esters are readily reduced to α-amino esters. This reaction could be a potential alternative to the Strecker synthesis.
References:
(1) a)Basel,Y.;Hassner,A. Synthesis1997, 309 – 312. b) Shimizu,T.; Hayashi,Y.;Shibafuchi,H.;Teramura, K.Bull. Chem. Soc. Jpn. 1986, 59, 2827 – 2831. c) Mukaiyama,T.;Hoshino, T. J. Am. Chem. Soc.1960, 82, 5339 – 5342.
(2) a) Lehr, F.; Gonnermann, J.; Seebach, D. Helv. Chim.Acta 1979, 62, 2258 – 2275. b) Eyer, M.; Seebach, D. J. Am. Chem. Soc. 1985, 107, 3601 – 3606. c) Ram, S.; Ehrenkaufer, R. E.; Synthesis1986, 133 – 135.
P-546: Unexpected products from p-toluenesulphonic acid catalysed reaction of p-quinones and 3,4-dihyro-2H-pyran – Some novel cascade processes Radhakrishnan Mohan Raj, Kallupattu Kuppusamy Balasubramanian, Deivanayagam Easwaramoorthy Department of chemistry, B. S. Abdur Rahman University, Chennai 600048 E-mail: [email protected], Phone: 81224 02259
The [2+3] cycloaddition reaction of quinones 1 with electron rich olefines like dihydrofuran, dihydropyran (DHP) 2 etc. leading to furo[2,3-b]benzofurans have been extensively studied in literature using Lewis acids as catalysts.[1] During the course of our work on the synthesis of benzofurans annulated to pyranose sugars at 1, 2 positions of pyranoses, using the [2+3] cycloaddition of glycals with p-quinones, we had occasion to examine the reaction of p-quinone 1 with DHP 2 , catalysed by p -toluenesulphonic acid ( p- TSA). In the event, we ended up with totally unexpected findings which we describe in this presentation. Exposure of p-quinone 1 and dihydropuran 2 to p-TSA in dichloromethane resulted in the formation of three products, viz., traces of hydroquinone 3, minor amount of meso–bis tetrahydropyranyl ether 4 of hydroquinone and a novel naphthoquinone derivative 5 as the major product (Scheme 1). The outcome of this p-TSA catalysed reaction is found to depend upon the nature of the quinone. While 2-methyl-1,4-benzoquinone, 1b followed the same course as quinone, 2,5-dichloro-1,4-benzoquinone 1c and 2,5-dimethyl-1,4-benzoquinone 1d exhibited a totally different behavior. In the case of 2,5-dichloro-1,4-benzoquinone 1c the major product turned out to be an interesting tetracyclic compound 6 whereas the major product from the reaction of 2,5- dimethyl-1,4-benzoquinone 1d and DHP 2 is the tricyclic derivative 7 (Scheme 1). In the case of 1,4- napthoquinone 1e, instead of tetrahydropyranyl ether, the mono and bis-C-alkylation of DHP, viz. 8 and 9 were encountered. The mechanism of these transformations will be discussed.
Reference
1. (a) Alvey, Luke.; Prado, Soizic.; Huteau, Valerie.; Saint-Joanis, Brigitte.; Michel, Sylvie.; Koch, Michel.; Cole, Stewart T.; Tillequin, François.; Janin, Yves L. Bioorg. and Med. Chem., 2008, 16, 8264–8272. (b) Zhou, Gang.; Corey, E. J. J. Amer. Chem. Soc. 2005, 127, 11958-11959. (c) Kedrowski, Sean M. A.; Bower, Kiowa S.; Dougherty, Dennis A. Organic Letter, 2007, 9(17), 3205-3207.
P-547: An efficient immobilization of 3-azidocoumarin based fluorescence tag using strain promoted click chemistry
Mohit Chhabra, Priyankar Paira* Pharmaceutical Chemistry Division; School of Advanced Sciences; VIT University Vellore, 632014 Tamil Nadu; India Email: [email protected]
Abstract
Click chemistry is a fashionable approach to the synthesis of functionalized molecules, and emphasizes the use of practical and reliable reactions. Click reactions are selective, quantitative, cost effective, pH-insensitive and also represent a green approach. Therefore, click chemistry can be used for the synthesis of a variety of conjugates. More precisely, the most important characteristic of the Cu catalyzed azide alkyne click reaction (CuAAC) is its unique bioorthogonality, as neither azide nor terminal alkyne functional groups interact with any native biological functional groups. A wide range of biomolecules has thus been labeled to date, including peptides, proteins, polysaccharides, and even entire viruses and cells. The use of this method for DNA modification has been somewhat delayed by the fact that copper ions damage DNA, typically yielding strand breaks. However recently, several paradigms have been published that aim to combine traceless reactions with room-temperature conditions through the application of Cu free strain-promoted alkyne–azide cycloaddition (SPAAC or Huisgen–Bertozzi-type cycloadditions) on the solid surfaces for in vivo applications. However, discovery of highly fluorescent chemical tags is highly warranted. Keeping this stratagem in mind, a new class of imaging probe, a fluorogenic version of 1, 3-dipolar cycloaddition of azides and alkynes, has been developed which has potential for selective immobilization of bioconjugates on solid surface. 3- azidocoumarin based tags might be selectively immobilized on the DBCO modified bead surface via SPAAC and provide direct and strong fluorescence in Fluorescence Microscopy.
Figure 1. Click reaction of 3-Azido Coumarin with DBCO modified PS beads. Fluorescence imaging
Keywords: Click Chemistry, DBCO, Fluorescence, DNA Modification, Bioorthogonal CorrespondingAuthor: Dr. Priyankar Paira; Contact: 8110020748;[email protected] References: [1] H. C Kolb et. al., Angew. Chem. 113, 2056, 2001. [2] C Remzi Becer et. al., Angew. Chem. Int. Ed., 48, 4900, 2009. [3] E. M Sletten et. al., Angew. Chem. 121, 7108, 2009. P-548: Poly (ethylene glycol)-co-Methacrylamide-co-Acrylic acid based biocompatible nanogels for the delivery of doxorubicin
P. Kumar1, G. Behl1, M. Sikka2, A. Chhikara1* and M. Chopra2*
1Department of Chemistry, Dyal Singh College, University of Delhi, Lodhi Road, New Delhi 110003, India. 2Dr. B. R. Ambedkar Center for Biomedical Research, University of Delhi, New Delhi 110007, India.
Presenting author email: [email protected]; Corresponding author email: [email protected], [email protected]
Doxorubicin (Dox) is very effective anticancer drug with wide scope of activity in human cancers, including breast carcinoma, lymphoblastic leukemia and hepatocellular carcinoma but its clinical application is limited because of the harmful side effects such as cardiotoxicity, nausea, vomiting etc. Polymeric system can be used to physically entrap anticancer drug for its sustained release directly at the tumor site to minimize the side effects and improve its therapeutic efficacy. The nanogel synthesis was performed using random copolymerization via cyclohexane-water reverse miniemulsion. The spherical morphology of the nanogels was observed by TEM microgram. The average hydrodynamic diameter determined by DLS was 160.3±46.95 nm. Loading efficiency and loading level of Doxorubicin was determined by UV spectroscopy and was found to be 91.52 and 92.13 weight percent and 4.57 and 9.21 weight percent respectively for 5, 10 drug nanogel weight percent. The Doxorubicin release study was performed at physiological pH (7.4) and 30.11% Dox was released. MTT assay was carried out on Hela cells to evaluate cytotoxicity of blank nanogels and antitumor activity of Dox-loaded nanogels in vitro. The blank nanogels control showed no cytotoxicity on HeLa cells. The Dox- nanogels shows higher cytotoxicity than free Dox, thereby maximizing the therapeutic efficiency. The material may be useful for clinical applications in near future.
a) b)
Figure a) TEM image and b) DLS of the nanogels
P-549: Tandem approach for synthesis of imidazoheterocyclic scaffolds viathree component condensation reactions Suman Swami and Rahul Shrivastava* Department of Chemistry, Manipal University, Jaipur-302007 (Rajasthan) E-mail: [email protected] The imidazohetrocyclic scaffolds one of the most important fused heterocyclic compounds, are attractive for drug discovery, since many compounds incorporating these scaffolds exhibit a wide range of biological, medicinal, and pharmaceutical activities, such as antitumor, anti-inflammatory, antiviral, antiprotozoal, anticonvulsant, anxiolytic, hypnotic, gastrointestinal, antiulcer, and immunomodulatory activities.1,2 Furthermore, imidazohetrocyclic scaffold forms the core structure of several drug molecules like zolpidem used in the treatment of insomnia, alpidem, as an anxiolytic agent, olprinone for the treatment of acute heart failure, minodronic acid useful for the treatment of osteoporosis, and zolimidine used for the treatment of peptic ulcer.3,4In this regard, development of easier and effective synthetic methods, as well as new derivatives with this structure, is important in organic synthesis. Although several methods have been reported for the synthesis of imidazohetrocyclic scaffold, many of these methods are based on multi-step syntheses, and the range of compounds that can be prepared is limited. In this paper, we synthesized some new derivatives having imidazohetrocyclic scaffolds as core structure via Groebke-Blackburn-Bienayme (GBB) reaction disclosed independently in 1998 by three research groups.5 In this reaction, pyrazole substituted aldehyde (1), 2- aminoazine and an isonitrile reacted in presence of suitable catalyst to afford a highly substituted imidazole derivatives (Scheme).
Scheme:Synthesis of the imidazohetrocyclic scaffolds based derivatives
References:
1. M. Lhassani; O. Chavignon; J-M. Chezal; J,-C. Teulade, J.-P Chapat; R. Snoeck; G. Andrei;J. Balzarini; E. De Clerc; A. GueiffierEur. J. Med. Chem.34, 271, 1999; (b) K.C. Rupert; J.R. Henry; J. H. Dodd; S.A.Wadsworth; D.E. Cavender; G. C. Olini; B. Fahmy, J. Bioorg. Med. Chem. Lett.13, 347, 2003; (c) G. Trapani; M. Franco; A. Latrofa; L. Ricciardi; A. Carotti; M. Serra; E. Sanna; G. Biggio; G. Liso. J. Med. Chem.42, 3934, 1999. 2. Howard, A. S. In Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Scriven, E. V. F., Eds.; Pergamon Press: London, 1996; Vol. 8,. Chapter 10, pp 262–274, and references therein. 3. Couty, F.; Evano, G. In Comprehensive Heterocyclic Chemistry III; Katritzky, A. R., Ramsden, C. A., Scriven, E. V. F., Taylor, R. J. K., Eds.; Elsevier Science, Oxford, 2008; Vol. 11,. Chapter 10, pp 409–492, and references therein. 4. C. Enguehard-Gueiffier; A. Gueiffier Mini Rev. Med. Chem.7, 888, 2007.. 5. A. Dömling; I. Ugi. Angew. Chem., Int. Ed.39, 3169, 2000; (b) Y. Rival; G. Grassy; G. MichelChem. Pharm. Bull.40, 1170, 1992.
P-550: Use of Resin as a Mild Base in Wittig Olefination
T. R. Valkute, E. K. Artikatla and A. K. Bhattacharya*
Division of Organic Chemistry, CSIR-National Chemical Laboratory, Pune 411008, India
E-mail: [email protected]
Wittig reaction is one of the most preferred methods for the synthesis of various alkenes due to its wide applicability. It uses a carbonyl compound as an electrophile, which is attacked by a “phosphorus ylide” (the “Wittig reagent”) to furnish olefin. Because of its reliability and wide applicability, the Wittig reaction has become a standard tool for synthetic organic chemists.
We have accomplished a synthetic protocol for the synthesis of olefins by the coupling of stabilized and nonstabilized phosphorus ylides with various carbonyl compounds in presence of resin as a mild base. The details of this synthetic methodology will be discussed in detail.
Scheme 1: Wittig reaction of phoshonium salt with carbonyl compound.
References
1. L. Jedinak et al., J. Org. Chem., 2013, 78, 12224.
2. L. K. Blasdel and A. G. Myers, Org Lett. 2005, 7, 4281.
P-551: Synthesis of Triazole bridged BODIPY-Glycoconjugates-Click Chemistry Approach Velautham Saravanan and Perumal Rajakumar* Department of Organic Chemistry, University of Madras, Guindy Campus, Chennai-25, India E-mail: [email protected]
Dndrimers are structurally nanosized symmetric molecules with well-defined and monodisperse tree like branches.1 Dendrimers have strong potential applications because of their multivalent systems.2 These nanostructures have attracted great interests because of their potential applications in drug delivery, bioimaging, biomimetic catalysts. Carbohydrate– BODIPY hybrids have shown to be a powerful combination for addressing biological studies. Such molecules are used to examine the intracellular trafficking of glycosphingolipids in cells3 and suitable fluorescent nucleotide analogues.4 Click chemistry have been employed mainly to introduce 1,2,3-triazole into the dendritic structure and it would be very interesting and promising candidates for many applications in biology as well as material science. The present investigation is mainly focus on the synthesis of BODIPY-glycoconjugates.
Refference:
1. Tomalia, D. A.;Natlor, A. M.; Goddard, W. A.,Angew. Chem. 1990, 102,119; Angew. Chem. Int. Ed. 1990, 29, 138. 2. Fréchet, J. M. J.; Tomalia, D. A. Dendrimers and Other Dendritic Polymers; John Wiley & Sons, Ltd.: Chichester, 2001. 3. Liu, Y.; Bittman, R.; Chem. Phys. Lipids 2006, 142, 58.; Suzuki, K.; Tobe, A.; Adachi, S.; Daikoku, S.; Hasegawa, Y.; Shioiri, Y.; Kobayashi, M.; Kanie, O. Org. Biomol. Chem. 2009, 7, 4726. 4. Groves, P. ; Strzelecka-Kiliszek, A.; Sekrecka-Belniak, A.; Canales, A.; Jiménez-Barbero, J. Bandorowicz-Pikula, J.; Pikula, S.; Cañada, F. J. Org. Biomol. Chem. 2013, 11, 5332. P-552: Salt (NaBr) Stimulated Micelle to Vesicle transition of Dodecylbenzenesulfonate Based Anionic Surface Active Ionic Liquid in Aqueous Media
Praveen Singh Gehlot, 1 K.Srinivasa Rao, 1 and Arvind Kumar1, 2
1Academy of Scientific and Innovative research
2Salt and Marine Chemical Discipline, CSIR-Central Salt and Marine Chemicals Research Institute, Bhavnagar, Gujarat 364002, India.
E-mail: [email protected]
Room temperature ionic liquids (ILs) are a novel class of molten salt composed of organic cations and inorganic or organic anions, with low melting point (<100oC). Recent studies have shown that some of the ILs possess inherent amphiphilic character and can form aggregates in water [1]. We have synthesized novel dodecylbenezenesulfonate based anionic surfactant like ionic liquids (DBS-ILs) paired with onium cations; n- butyltrimethylammonium (N1114), 1-butyl-3-methylimidazolium (C4mim) and N-butylpyridinium (C4Py). The surface properties such as CMC, adsorption efficiency and thermodynamic parameters of this DBS-ILs have been studied by surface tension and isothermal titration calorimetry. The salt (NaBr) stimulated Micelle to Vesicle Transition has observed in this DBS-ILs system which has been evidenced from dynamic light scattering (DLS), turbidity, 1H- NMR and cryo-TEM techniques. The stimuli responsive transitions in the self-assembly of DBS-ILs will be useful for encapsulation and delivery of active (bio) molecules in the targeted biomedical applications and nanomaterial synthesis [2].
.
Fig1. Cryo-TEM images of C4mimDBS (A) in water (B) in 100 mM NaBr solution
Reference
1. Wang, H. et al., Langmuir 30, 3971, 2014
2. K. S. Rao, et al., Langmuir 27, 9261, 2011 P-553: Electrochemical Studies of aminonaphthoquinone derivatives
Sujit Bhand, Dattatray Chadar, Umesh Kasabe, Sunita Salunke-Gawali* Department of Chemistry, Savitribai Phule Pune University, Pune, Maharashtra-411007 *Email: [email protected]
Key words: Cyclic Voltametry, Aminonaphthoquinone, Quinone
Aminonaphthoquinone moiety is found in a core structure of many medicinally important natural products for example, the antibiotics rifabutin and rifamycin(s), used for treatment of multi drug resistant tuberculosis and hygrosin A and saliniparamycin that exhibit anticancer and antibiotic properties respectively. Quinones are redox susceptible molecules; this could be the prime reason for their wide range of biological functions and pharmacological applications. We engaged in our laboratory in synthesis, characterization, molecular structures of these biologically active aminonaphthoquinone derivatives [1,2]. In present investigation, the synthesis, characterization, molecular structures and electrochemical studies of first eight derivatives 2-(n-alkylamino)-3-methyl-1,4-naphthoquinone have been investigated. Two reversible peaks were observed in cyclic voltammogram of all compounds in DMSO solution ~ E1/2 = -0.6V and E1/2= -1.1V and are respectively assigned to naphthoquinone to naphthosemiquinone and naphthosemiquinone to catechol redox couples. Comparative studies were made with similar derivatives of 2-chloro-3-(n-alkylamino)-1,4- naphthoquinone, 2-bromo-3-(n-alkylamino)-1,4-naphthoquinone and 2-alkylamino-1,4-naphthoquinone.
1.0x10-5
LM-1 5.0x10-6 LM-2 LM-3
I/A 0.0
-5.0x10-6
-1.5 -1.0 -0.5 0.0 0.5 1.0 E/V Vs NHE
Fig. Cyclic Voltammograms of 2-(n-alkylamino)-3-methyl-1,4-naphthoquinone in DMSO. Reference 1. S. Pal, M. Jadhav, T. Weyhermüller, Y. Patil, M. Nethaji, U. Kasabe, L. Kathawate, V. B. Konkimalla, S. Salunke-Gawali, J. Mol. Struct., 1049, 355, 2013. 2. O. Pawar, A. Patekar, A. Khan, L. Kathawate, S. Haram, G. Markad, V. Puranik, S. Salunke-Gawali, J. Mol. Struct., 1059, 74, 2014.
P-554: Metal- Organic Frameworks (MOFs) using Diphenylether Backbone Based Carboxylate Ligand
Rupinder Kaura, Partha Mahata b, Manmohan Chhibbera, Susheel K Mittal*a aSchool of Chemistry & Biochemistry, Thapar University, Patiala, Punjab bDept. of Condensed Matter Physics and Material Sciences, S. N. Bose National Centre for Basic Sciences, Kolkata, West Bengal. Email ID: [email protected]
ABSTRACT: The term metal organic framework (MOFs) has been used to describe such compounds with backbones made by connecting metal ions or metal clusters with organic ligands. The atomic structure of MOFs can be determined by X-ray crystallography, thus the dimensions of the pores or channels can be determined with excellent certainty. [1] The pore sizes/shapes are highly tunable, and larger pore sizes can be synthesized when compared to known zeolites. These frameworks have been useful in separation, detection and catalysis applications.
Mahata and co-workers synthesized a [Co4(triazolate)2(OBA)3], possessing Co4 clusters which are connected together through the triazolate moieties resembling the TiS2 layer. Magnetic studies in the temperature range 1.8−300 K indicate strong antiferromagnetic interactions for Co4 clusters.[4] We propose to extend this work to synthesize new porous MOFs using various diphenyl ethers with metals such as Co, Mn and Zn to explore their properties. Attempts to synthesize and characterize these new MOF’s will be presented.
Keywords: MOFs, Diphenylethers.
References: 1. Xuan, W.; Zhu, C.; Liu, Y.; Cui, Y.,Chem. Soc. Rev.,2012, 41, 1677. 2. Sarma, D., Mahata, P.; Natarajan, S.; Pannisod, P.; Rogez, G.; Drillon, M., Inorg. Chem. 2012, 51, 4495.
P-555: Synthesis of bioionic liquid based nanogel system having prolonged anti-cancer drug delivery ability
Jitkumar Bhatt & Kamalesh Prasad*
Marine Biotechnology and Ecology Discipline, CSIR-Central Salt & Marine Chemicals Research Institute, G. B Marg, Bhavnagar-364002 (Gujarat), India, Email: [email protected] Nanogels are emerging as suitable nanocarrier in the drug delivery applications. Nanogels prepared from polymerizable bioionic liquids due to their biodegradability, cost effective preparation, non-toxic nature may be a good alternative to the existing nanogel systems. Simultaneous polymerization and cross-linking of choline acrylate (a bio-IL) yielded a compound capable of forming nanogel in water with hydrodynamic size of 41±15 nm. Nanogel thus prepared was studied for sustained delivery of an anticancer drug 5-Fluoro Uracil. It was observed that, this gel could efficiently deliver the drug for 10 days at pH 1.2 (pH of stomach) and hence would be useful for the treatment of stomach cancer. 1
Scheme : Slow drug delivery of polymerizable ionic liquid.
Ref.
1. C.Mukesh et.al., Macromol. Chem. Phys., 2014, 215, 1498-15074
P-556: Enhanced energy product in Fe3Se4:Fe3O4 nanocomposite: An Exchange Spring Magnet
Mousumi Sen Bishwas,1,2 Pankaj Poddar* 1,2
1 Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411 008, India, 2Academy of Scientific and Innovative Research, Anusandhan Bhawan, 2 Rafi Marg, New Delhi-110 001 *E-mail: [email protected], Tel.: +91-20-25902580
The dawn of exchange spring magnets has given a new direction to the research in the field of permanent magnets. The exchange coupling between magnetically hard and soft phases leads to enhanced saturation magnetization and reduced effective coercivity. It has been shown that the dimension of the soft phase plays a very crucial role in increasing the magnetization without sacrificing much on coercivity in exchange spring magnets. Ideally, the dimension of the soft phase should be of the order of domain wall width of the hard phase1, 2. The moments at the soft phase interfaces are pinned to the hard phase and at the centre the moments are free to orient with the external field. This results in a small decrease in the effective coercivity of the hard phase and the effective magnetization increases. Both the iron selenide and iron oxide nanoparticles are synthesized by hot colloidal method under 3 inert atmosphere .The exchange coupled Fe3Se4:Fe3O4 nanocomposite is prepared by simple solution method where powder form of both the phases are added to oleyl amine and refluxed under nitrogen atmosphere at 300 °C for 1 h. During refluxing, nanoparticles of both phases come close to each other and oleyl amine forms an overall coating on these nanocomposite particles. In the X-ray diffraction patterns of the nanocomposites all the peaks can be ascribed to diffraction from the crystal planes of Fe3Se4 (JCPDS # 652315) and Fe3O4 (JCPDS # 790416). No additional peaks from any impurity are observed. From the temperature dependent FC and ZFC magnetization curves, transitions at 317 K and ∼110 K are observed which can be attributed to the Curie transition (TC) of Fe3Se4 and blocking temperature (TB) of Fe3O4 respectively. From the M-H studies, we observed, as the ratio of soft phase is increased saturation magnetization increases significantly and coercivity decreases in the nanocomposite. All the hysteresis loops exhibits single phase behavior. The nanocomposite with 10 % Fe3O4 shows 116% increase in energy product over the pure hard phase. A B
Fig 1: Magnetization – T study of nanocomposite with 5 % Fe3O4, (B) Hysteresis behavior of all the nanocomposites, inset shows the behavior of saturation magnetization and coercivity with amount of Fe3O4.
Reference
1. R. Skomski and J. M. D. Coey, Phys. Rev. B, 48, 21, (1993), pp. 15812-16.
2. E. F. Kneller and R. Hawig, IEEE Trans. Magn., 27, (1991), pp. 3588-3600.
3. M. S. Bishwas, R. Das and P. Poddar, J. Phys. Chem. C, 118, (2014), pp. 4016−22. P-557: Fermi Level Equilibration in Semiconductor-Metal Heterojunction Nanostructures
K. Sandeep, Pratheesh V. Nair, and K. George Thomas * School of Chemistry, Indian Institute of Science Education and Research (IISER), Trivandrum 695016, India
Fermi level equilibration in CdSe-Au heterojunction nanostructures formed by CdSe quantum dots and Au nanoparticles was investigated using steady state and femtosecond transient absorption techniques. CdSe-Au heterojunction structures were synthesized using two gold precursors dodecylamine-Au(I) and dodecylthiol-Au(I) complex. Favorable alignment of energy levels makes dodecylthiol a good hole scavenger from CdSe QDs whereas dodecylamine act as a surface passivating agent. The addition of gold precursor, dodecylthiol-Au(I), to the CdSe QDs resulted in a steady decrease in the excitonic absorption of CdSe quantum dots. In contrast excitonic band CdSe QDs remains unaffected upon addition of dodecylamine-Au(I) gold precursor. TEM analysis of the purified QDs after gold complex addition confirmed the formation of CdSe-Au hetero-nanostructures irrespective of the composition of the gold precursor. Femtosecond transient absorption studies of the heterojunction nanostructures showed (i) a faster bleach recovery compared to bare CdSe QDs for the CdSe-Au formed from the dodecylamine-Au(I) precursor, which is attributed to electron transfer from CdSe to gold and (ii) a slower bleach recovery of the CdSe-Au formed from thiolated gold precursor indicating long lived excited state due to the equilibration of energy levels. Au acts as electron as well as hole acceptor in the case of CdSe-Au formed from the dodecylamine-Au(I) gold precursor. thereby preventing the Fermi level equilibration. In contrast, thiol acts as acceptor of holes and Au acts as acceptor of electrons in CdSe-Au formed from the dodecylthiol-Au(I) precursor, resulting in the Fermi level equilibration of the gold CdSe quantum dots. References: 1. Acharya, K. P.; Khnayzer, R. S.; O’Connor, T.; Diederich, G.; Kirsanova, M.; Klinkova, A.; Roth, D.; Kinder, E.; Imboden, M.; Zamkov, M. Nano Lett. 2011, 11, 2919 2. Zhu, H. M.; Song, N. H.; Lv, H. J.; Hill, C. L.; Lian, T. Q. J. Am. Chem. Soc. 2012, 134, 11701 3. Wood, A.; Giersig, M.; Mulvaney, P. J. Phys. Chem. B 2001, 105, 8810– 8815.
P-558: Guest Driven Supramolecular Self-assembly of Phenyleneethynylenes: Engineering the Network Formation on Surfaces
Pratap Zalake and K. George Thomas*
School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram, (IISER-TVM) Trivandrum 695 016, INDIA
Organization of photo- and electroactive molecules on surfaces with atomic level precision provides excellent possibilities for the designing nanoscale optoelectronic devices. Scanning Tunneling Microscopy (STM) has emerged as an excellent tool for probing the organization of such molecules on surfaces, with atomic scale resolution. Among the various molecular building blocks, π- conjugated molecular systems such as oligo(phenyleneethynylene)s have been proposed as elements in optoelectronic devices due to their fascinating structural and optical properties. Functionalized phenyleneethynylenes (1-4) having di- as well as teracarboxylic acid groups at the terminal positions of the ring were synthesized by following a series of the Heck-Cassar-Sonagashira-Hagihara cross- coupling reactions. Highly ordered parallel arrangement, extended over several nanometers, was observed in the case of compounds 1-2. In contrast, the teracarboxylic acid derivative 4 showed a Kagome type structure having periodic hexagonal hydrogen bonded cavity, with diameter of 1.1 nm. Photoactive guest molecules such as coronene and fullerene were inserted in the host cavity and various aspects of host-guest interaction were probed. Another interesting observation is the transformation of molecules 1 and 2 to flower type arrangements on the addition of coronene wherein the guest molecules are inserted in the hexagonal hydrogen bonded cavity. On addition of coronene, tetracarboxylic acid derivative 3 underwent structural transformation from random arrangement to the Kagome type network having the guest molecules in the hexagonal hydrogen bonded cavity. Various forces responsible for the guest driven transformation will be discussed.
3
4
References: Zalake, P.; Thomas, K. G. Langmuir, 2013, 29, 2242−2249.