Synthesis and Characterization of Meso-Substituted A2B Corroles with Extended P-Electronic Structure
Total Page:16
File Type:pdf, Size:1020Kb
Load more
Recommended publications
-
Interstellar Ices and Radiation-Induced Oxidations of Alcohols
The Astrophysical Journal, 857:89 (8pp), 2018 April 20 https://doi.org/10.3847/1538-4357/aab708 © 2018. The American Astronomical Society. All rights reserved. Interstellar Ices and Radiation-induced Oxidations of Alcohols R. L. Hudson and M. H. Moore Astrochemistry Laboratory, NASA Goddard Space Flight Center, Greenbelt, Maryland, 20771, USA; [email protected] Received 2017 May 2; revised 2018 March 8; accepted 2018 March 9; published 2018 April 18 Abstract Infrared spectra of ices containing alcohols that are known or potential interstellar molecules are examined before and after irradiation with 1 MeV protons at ∼20 K. The low-temperature oxidation (hydrogen loss) of six alcohols is followed, and conclusions are drawn based on the results. The formation of reaction products is discussed in terms of the literature on the radiation chemistry of alcohols and a systematic variation in their structures. The results from these new laboratory measurements are then applied to a recent study of propargyl alcohol. Connections are drawn between known interstellar molecules, and several new reaction products in interstellar ices are predicted. Key words: astrochemistry – infrared: ISM – ISM: molecules – molecular data – molecular processes 1. Introduction 668 cm−1 was produced in solid propargyl alcohol’sIR spectrum after the compound was irradiated with 2 keV Interstellar ices are now recognized as an important comp- electrons (Sivaraman et al. 2015, hereafter SMSB from the onent of the interstellar medium (ISM). The results of multiple coauthors final initials). That IR peak was assigned to benzene infrared (IR) surveys have led to over a dozen assignments of (C H ), which was said “to be the major product from spectral features to molecular ices, with the more abundant 6 6 propargyl alcohol irradiation.” However, a full mid-IR interstellar ices being H O, CO, and CO (Boogert et al. -
Enzymatic Encoding Methods for Efficient Synthesis Of
(19) TZZ__T (11) EP 1 957 644 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C12N 15/10 (2006.01) C12Q 1/68 (2006.01) 01.12.2010 Bulletin 2010/48 C40B 40/06 (2006.01) C40B 50/06 (2006.01) (21) Application number: 06818144.5 (86) International application number: PCT/DK2006/000685 (22) Date of filing: 01.12.2006 (87) International publication number: WO 2007/062664 (07.06.2007 Gazette 2007/23) (54) ENZYMATIC ENCODING METHODS FOR EFFICIENT SYNTHESIS OF LARGE LIBRARIES ENZYMVERMITTELNDE KODIERUNGSMETHODEN FÜR EINE EFFIZIENTE SYNTHESE VON GROSSEN BIBLIOTHEKEN PROCEDES DE CODAGE ENZYMATIQUE DESTINES A LA SYNTHESE EFFICACE DE BIBLIOTHEQUES IMPORTANTES (84) Designated Contracting States: • GOLDBECH, Anne AT BE BG CH CY CZ DE DK EE ES FI FR GB GR DK-2200 Copenhagen N (DK) HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI • DE LEON, Daen SK TR DK-2300 Copenhagen S (DK) Designated Extension States: • KALDOR, Ditte Kievsmose AL BA HR MK RS DK-2880 Bagsvaerd (DK) • SLØK, Frank Abilgaard (30) Priority: 01.12.2005 DK 200501704 DK-3450 Allerød (DK) 02.12.2005 US 741490 P • HUSEMOEN, Birgitte Nystrup DK-2500 Valby (DK) (43) Date of publication of application: • DOLBERG, Johannes 20.08.2008 Bulletin 2008/34 DK-1674 Copenhagen V (DK) • JENSEN, Kim Birkebæk (73) Proprietor: Nuevolution A/S DK-2610 Rødovre (DK) 2100 Copenhagen 0 (DK) • PETERSEN, Lene DK-2100 Copenhagen Ø (DK) (72) Inventors: • NØRREGAARD-MADSEN, Mads • FRANCH, Thomas DK-3460 Birkerød (DK) DK-3070 Snekkersten (DK) • GODSKESEN, -
Accurate Enthalpies of Formation of Astromolecules: Energy, Stability and Abundance
Accurate Enthalpies of Formation of Astromolecules: Energy, Stability and Abundance Emmanuel E. Etim and Elangannan Arunan* Inorganic and Physical Chemistry Department, Indian Institute of Science Bangalore, India-560012 *email: [email protected] ABSTRACT: Accurate enthalpies of formation are reported for known and potential astromolecules using high level ab initio quantum chemical calculations. A total of 130 molecules comprising of 31 isomeric groups and 24 cyanide/isocyanide pairs with atoms ranging from 3 to 12 have been considered. The results show an interesting, surprisingly not well explored, relationship between energy, stability and abundance (ESA) existing among these molecules. Among the isomeric species, isomers with lower enthalpies of formation are more easily observed in the interstellar medium compared to their counterparts with higher enthalpies of formation. Available data in literature confirm the high abundance of the most stable isomer over other isomers in the different groups considered. Potential for interstellar hydrogen bonding accounts for the few exceptions observed. Thus, in general, it suffices to say that the interstellar abundances of related species are directly proportional to their stabilities. The immediate consequences of this relationship in addressing some of the whys and wherefores among astromolecules and in predicting some possible candidates for future astronomical observations are discussed. Our comprehensive results on 130 molecules indicate that the available experimental enthalpy -
Exhaustive Product Analysis of Three Benzene Discharges by Microwave Spectroscopy Michael C
pubs.acs.org/JPCA Article Exhaustive Product Analysis of Three Benzene Discharges by Microwave Spectroscopy Michael C. McCarthy,* Kin Long Kelvin Lee, P. Brandon Carroll, Jessica P. Porterfield, P. Bryan Changala, James H. Thorpe, and John F. Stanton Cite This: J. Phys. Chem. A 2020, 124, 5170−5181 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: Using chirped and cavity microwave spectroscopies, automated double resonance, new high-speed fitting and deep learning algorithms, and large databases of computed structures, the discharge products of benzene alone, or in combination with molecular oxygen or nitrogen, have been exhaustively characterized between 6.5 and 26 GHz. In total, more than 3300 spectral features were observed; 89% of these, accounting for 97% of the total intensity, have now been assigned to 152 distinct chemical species and 60 of their variants (i.e., isotopic species and vibrationally excited states). Roughly 50 of the products are entirely new or poorly characterized at high resolution, including many heavier by mass than the precursor benzene. These findings provide direct evidence for a rich architecture of two- and three-dimensional carbon and indicate that benzene growth, particularly the formation of ring−chain molecules, occurs facilely under our experimental conditions. The present analysis also illustrates the utility of microwave spectroscopy as a precision tool for complex mixture analysis, irrespective of whether the rotational spectrum of a product species is known a priori or not. From this large quantity of data, for example, it is possible to determine with confidence the relative abundances of different product masses, but more importantly the relative abundances of different isomers with the same mass. -
One-Step Synthesis of Pyridines and Dihydro- Pyridines in a Continuous Flow Microwave Reactor
One-step synthesis of pyridines and dihydro- pyridines in a continuous flow microwave reactor Mark C. Bagley*1, Vincenzo Fusillo2, Robert L. Jenkins2, M. Caterina Lubinu2 and Christopher Mason3 Full Research Paper Open Access Address: Beilstein J. Org. Chem. 2013, 9, 1957–1968. 1Department of Chemistry, School of Life Sciences, University of doi:10.3762/bjoc.9.232 Sussex, Falmer, Brighton, East Sussex, BN1 9QJ, UK, 2School of Chemistry, Main Building, Cardiff University, Park Place, Cardiff, Received: 05 July 2013 CF10 3AT, UK and 3CEM Microwave Technology Ltd, 2 Middle Slade, Accepted: 11 September 2013 Buckingham, MK18 1WA, UK Published: 30 September 2013 Email: This article is part of the Thematic Series "Chemistry in flow systems III". Mark C. Bagley* - [email protected] Guest Editor: A. Kirschning * Corresponding author © 2013 Bagley et al; licensee Beilstein-Institut. Keywords: License and terms: see end of document. Bohlmann–Rahtz; continuous flow processing; ethynyl ketones; flow chemistry; Hantzsch dihydropyridine synthesis; heterocycles; microwave synthesis; multicomponent reactions; pyridine synthesis Abstract The Bohlmann–Rahtz pyridine synthesis and the Hantzsch dihydropyridine synthesis can be carried out in a microwave flow reactor or using a conductive heating flow platform for the continuous processing of material. In the Bohlmann–Rahtz reaction, the use of a Brønsted acid catalyst allows Michael addition and cyclodehydration to be carried out in a single step without isolation of intermediates to give the corresponding trisubstituted pyridine as a single regioisomer in good yield. Furthermore, 3-substituted propargyl aldehydes undergo Hantzsch dihydropyridine synthesis in preference to Bohlmann–Rahtz reaction in a very high yielding process that is readily transferred to continuous flow processing. -
The Interactions and Reactions of Atoms and Molecules on the Surfaces of Model Interstellar Dust Grains
The Interactions and Reactions of Atoms and Molecules on the Surfaces of Model Interstellar Dust Grains A thesis submitted for the degree of Doctor of Philosophy Helen Jessica Kimber Department of Chemistry University College London 2016 -I, Helen Jessica Kimber, confirm that the work presented in this thesis is my own. Where information has been derived from other sources, I confirm that this has been indicated in the thesis. Signed, i Abstract The elemental composition of the known universe comprises almost exclusively light atoms (~99.9% hydrogen and helium). However, to date, close to 200 different molecules have been detected in the interstellar medium (ISM) where their distribution is far from uniform. The vast majority of these molecules are contained within vast clouds of gas and dust referred to as interstellar clouds. Within these interstellar clouds, many of the molecules present are formed via gas-phase ion-neutral reactions. However, there are several molecules for which known gas-phase kinetics cannot account for observed gas-phase abundances. As a result, reactions occurring on the surface of interstellar dust grains are invoked to account for the observed abundances of some of these molecules. This thesis presents results of experimental investigations into the interaction and reactions of atoms and molecules on the surface of model interstellar dust grains. Chapters three and four present results for the reaction of (3P)O on molecular ices. Specifically, the reaction of (3P)O and propyne or acrylonitrile. After a one hour dosing period, temperature programmed desorption (TPD), coupled with time-of-flight mass spectrometry (TOFMS), are used to identify (3P)O addition products. -
An Efficient Synthesis of Porphyrins with Different Meso Substituents That Avoids Scrambling in Aqueous Media
An Efficient Synthesis of Porphyrins with Different meso Substituents that Avoids Scrambling in Aqueous Media Agnieszka Nowak-Krol, Rémi Plamont, Gabriel Canard, J.A. Edzang, Daniel T. Gryko, Teodor Silviu Balaban To cite this version: Agnieszka Nowak-Krol, Rémi Plamont, Gabriel Canard, J.A. Edzang, Daniel T. Gryko, et al.. An Efficient Synthesis of Porphyrins with Different meso Substituents that Avoids Scrambling inAque- ous Media. Chemistry - A European Journal, Wiley-VCH Verlag, 2015, 21 (4), pp.1488-1498. 10.1002/chem.201403677. hal-01130057 HAL Id: hal-01130057 https://hal.archives-ouvertes.fr/hal-01130057 Submitted on 7 Feb 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. An Efficient Synthesis of Porphyrins with Different Meso Substituents that Avoids Scrambling in Aqueous Media Agnieszka Nowak-Król,a,† Rémi Plamont,b,† Gabriel Canard,b,c Judicaelle Andeme Edzang,b,c Daniel T. Grykoa,* and Teodor Silviu Balabanb,* To the memory of Alan Roy Katritzky, magister of heterocyclic chemistry [a] Institute of Organic Chemistry of the Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland E-mail: [email protected] [b] Aix Marseille Université, Centrale Marseille, CNRS, Institut des Sciences Moléculaires de Marseille (iSm2), UMR 7313, Chirosciences, Avenue Escadrille Normandie Niemen, St. -
Synthesis and Spectroscopic Properties of Β-Meso Directly Linked Porphyrin–Corrole Hybrid Compounds
Synthesis and spectroscopic properties of β-meso directly linked porphyrin–corrole hybrid compounds Baris Temelli* and Hilal Kalkan Full Research Paper Open Access Address: Beilstein J. Org. Chem. 2018, 14, 187–193. Hacettepe University, Department of Chemistry, Beytepe Campus, doi:10.3762/bjoc.14.13 06800, Ankara, Turkey Received: 09 October 2017 Email: Accepted: 05 January 2018 Baris Temelli* - [email protected] Published: 22 January 2018 * Corresponding author Associate Editor: J. Aubé Keywords: © 2018 Temelli and Kalkan; licensee Beilstein-Institut. corrole; hybrid compounds; indium(III) chloride; porphyrin; License and terms: see end of document. porphyrinoids Abstract The preparation of β-meso directly linked porphyrin–corrole hybrids was realized for the first time via an InCl3-catalyzed condensa- tion reaction of 2-formyl-5,10,15,20-tetraphenylporphyrins with meso-substituted dipyrromethanes. Hybrid compounds have been characterized by 1H NMR, 13C NMR, 2D NMR, UV–vis absorption and fluorescence spectroscopy. Introduction Porphyrins and metalloporphyrins play an important role in compounds, corroles, contracted porphyrin analogues [31-33], chemistry, biology, medical and materials sciences because of assumed an important place in porphyrin chemistry due to their their presence in biological compounds such as chlorophyll and small cavities, trianionic characters, high fluorescence quantum heme molecules that have very important functions in the yields and favorable electronic properties. Porphyrin–corrole metabolism of living organisms [1,2]. In recent years, efforts in conjugates have been successfully used as donor–acceptor porphyrin chemistry have been focused on the synthesis of systems in photoinduced charge separation processes. It was multichromophore containing compounds and their potential shown that derivatives of these conjugates could be potentially applications in molecular wires, sensors, nonlinear optical used in photovoltaic applications [21-23]. -
1 INTRODUCTION Corroles Are Tetrapyrrolic Molecules, Maintaining
1 Chapter 1 INTRODUCTION Corroles are tetrapyrrolic molecules, maintaining the skeletal structure of corrin, with its three meso carbon positions and one direct pyrrole-pyrrole linkage, and possessing the aromaticity of porphyrins (see figure 1.1). First reported by Johnson and Kay in 1965[1], corroles were the end product of a many step synthetic scheme, finally being formed by the photocyclization of a,c-biladienes. While this last step was simple, with 20-60% yields, the route to a,c-biladienes was far from easy. Indeed, the overall reaction from readily available starting materials to corrole was a multi-step synthesis, with poor yields in many of the reactions. Thus, while corroles have been known for more than 40 years, research in the field was slow to progress. It wasn’t until the discovery of new synthetic methods for corroles developed in 1999 by different groups working independently that research in this area really started to expand[2]. This is not to say, however, that the field of corrole research was non-existent prior to the development of the new methodologies. While it was slow growing after the initial publication, it was far from stagnant, and many of the interesting properties of corroles were investigated by different groups. Among these properties is their ability to stabilize unusually high formal oxidation states of metal ions, such as iron(IV), cobalt(IV), and cobalt(V)[3, 4]. In fact, one particular corrole available through a method developed by Zeev 2 N N H N N H H N N N N a b N N H H H N N c Figure 1.1. -
Luminescence Features of Neodymium(III) Compounds with Various Tetrapyrrole Macrocycles Люминесцентные Свойс
Porphyrins Paper Порфирины Статья DOI: 10.6060/mhc170621r Luminescence Features of Neodymium(III) Compounds with Various Tetrapyrrole Macrocycles Nikolay N. Semenishyn,a Sergii S. Smola,a Natalya V. Rusakova,a@ Gerbert L. Kamalov,a Yulia G. Gorbunova,b,c and Aslan Yu. Tsivadzeb,c aA.V. Bogatsky Physico-Chemical Institute, 65080 Odessa, Ukraine bA.N. Frumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences, 119071 Moscow, Russia cN.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991 Moscow, Russia @Corresponding author E-mail: [email protected] We considered the changes in the luminescent properties in the series of neodymium(III) complexes of various coordination types with different tetrapyrrole macrocycles (porphyrins, phthalocyanines and corroles): mono- nuclear complexes (metal-ligand ratio 1:1), sandwich type complexes (metal-ligand ratio 1:2 or 2:3), peripheral binding (on the basis of ditopic tetrapyrrole, metal-ligand ratio 1:1). 4f-Luminescence in the near infrared region is observed in all studied Nd-complexes as a result of intramolecular transfer of excitation energy. Each kind of com- plexes has its unique features, which are discussed. The peripheral complexes are dual-emissive: they display both neodymium(III) 4f-emission and molecular fluorescence. The values of quantum yield of molecular fluorescence as well as 4f-luminescence are estimated. It was found that binding type plays a key role in excited state relaxation pathways in the molecule. Corroles have unusual behaviour in terms of Nd sensitization. Keywords: Tetrapyrroles, luminescence, neodymium, porphyrin, phthalocyanine, corrole. Люминесцентные свойства соединений неодима(III) с различными тетрапиррольными макроциклами Н. -
Characterisation, Classification and Conformational Variability Of
Characterisation, Classification and Conformational Variability of Organic Enzyme Cofactors Julia D. Fischer European Bioinformatics Institute Clare Hall College University of Cambridge A thesis submitted for the degree of Doctor of Philosophy 11 April 2011 This dissertation is the result of my own work and includes nothing which is the outcome of work done in collaboration except where specifically indicated in the text. This dissertation does not exceed the word limit of 60,000 words. Acknowledgements I would like to thank all the members of the Thornton research group for their constant interest in my work, their continuous willingness to answer my academic questions, and for their company during my time at the EBI. This includes Saumya Kumar, Sergio Martinez Cuesta, Matthias Ziehm, Dr. Daniela Wieser, Dr. Xun Li, Dr. Irene Pa- patheodorou, Dr. Pedro Ballester, Dr. Abdullah Kahraman, Dr. Rafael Najmanovich, Dr. Tjaart de Beer, Dr. Syed Asad Rahman, Dr. Nicholas Furnham, Dr. Roman Laskowski and Dr. Gemma Holli- day. Special thanks to Asad for allowing me to use early development versions of his SMSD software and for help and advice with the KEGG API installation, to Roman for knowing where to find all kinds of data, to Dani for help with R scripts, to Nick for letting me use his E.C. tree program, to Tjaart for python advice and especially to Gemma for her constant advice and feedback on my work in all aspects, in particular the chemistry side. Most importantly, I would like to thank Prof. Janet Thornton for giving me the chance to work on this project, for all the time she spent in meetings with me and reading my work, for sharing her seemingly limitless knowledge and enthusiasm about the fascinating world of enzymes, and for being such an experienced and motivational advisor. -
5 SYNTHESES While the Initial Synthesis of Corroles Was a Very Long Procedure, the Advent of a One Pot Synthesis by Gross and Co
5 Chapter 2 SYNTHESES While the initial synthesis of corroles was a very long procedure, the advent of a one pot synthesis by Gross and co-workers in 1999 revolutionized the process of making corroles. It is now possible to make hundreds of milligrams of free-base corrole in a single day, compared to weeks or even months of work with the previous methods. Detailed in this chapter are the synthetic methods used for the corroles studied in this work, including two different free-bases; gallium, manganese, and tin complexes of these free-bases; and work done toward the synthesis of an indium corrole. The particular corrole free-bases used in this study were 5,10,15- tris(pentafluorophenyl)corrole, and 2,17-bis(sulfonato)-5,10-15- tris(pentafluorophenyl)corrole. The structures for these two molecules are shown in figure 2.1. General Synthetic Procedures All corroles used in this work are derived from the first of these, 5,10,15- tris(pentafluorophenyl)corrole (1), which in turn is synthesized from pyrrole and pentafluorobenzaldehyde. This can be accomplished by different methods, either involving a solid support, an acid to aid the reaction, or neat. All three methods will be described at the end of this chapter. However, in all cases, the synthesis of 1 is a condensation reaction 6 a b C6F5 C6F5 N N N N H H C F C F C F 6 5 H H 6 5 6 5 H H C6F5 N N N N SO3H SO3H Figure 2.1. Structures of the two free-base corroles used in this study.