DOCSLIB.ORG

Published Version

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

Diss. ETH No. 12700 Reduction of Polyhalogenated Alkanes by an Iron Porphyrin as Electron Transfer Mediator: System and Product Analysis A dissertation submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZURICH for the degree of DOCTOR OF NATURAL SCIENCES presented by JOHANNA BUSCHMANN Dipl. Chem. ETH born February 12, 1969 citizen of Arbon (TG) accepted on the recommendation of Prof. Dr. Rene Schwarzenbach, examiner Dr. Werner Angst, co-examiner Prof. Dr. Bernhard Krautler, co-examiner Zilrich 1998 Der Schauende Ich sehe den Baumen die Sttirme an, die aus laugewordenen Tagen an meine i:ingstlichen Fenster schlagen, und hore die fernen Dinge sagen, die ich nicht ohne Freund ertragen, nicht ohne Schwester lieben kann. Da geht der Sturm, ein Umgestalter, geht <lurch den Wald und <lurch die Zeit, und alles ist wie ohne Alter: die Landschaft, wie ein Vers im Psalter, ist Ernst und Wucht und Ewigkeit. Wie ist das klein, womit wir ringen, was mit uns ringt, wie ist das gross; liessen wir, ahnlicher den Dingen, uns so vom grossen Sturm bezwingen, wir wurden weit und namenlos. Was wir besiegen, ist das Kleine, und der Erfolg selbst macht uns klein. Das Ewige und Ungemeine will nicht von uns gebogen sein. Das ist der Engel, der den Ringern des Alten Testaments erschien: wenn seiner Widersacher Sehnen im Kampfe sich metallen dehnen, fi.ihlt er sie unter seinen Fingern wie Saiten tiefer Melodien. Wen dieser Engel uberwand, wekher so oft auf Kampf verzichtet, der geht gerecht und aufgerichtet und gross aus jener harten Hand, die sich, wie formend, an ihn schmiegte. Die Siege laden ihn nicht ein. Sein W achstum ist: der Tiefbesiegte von immer Crosserem zu sein. Rainer Maria Rilke Acknowledgements I want to thank Prof. Rene Schwarzenbach for letting me work in his group and for advising this research. Special thanks to Dr. Werner Angst and Dr. Judith Perlinger for their discussions where many ideas were evaluated and thought over. I thank Dr. Angst and Prof. Krautler for being my co-examiners. Dr. Angst, Prof. Krautler, Janet Kessel- mann and Prof. Anderson are kindly acknowledged for reviewing this dissertation. I would like to thank people in the ,,Dehalo"-meetings: Guy Glod, Wolfram Schu- macher, Christoph Holliger, Werner Angst, Judith Perlinger and Rene Schwarzenbach. For the interesting presentations and discussions the people from the ,,ET" -meetings are kindly acknowledged: Stephan Hug, Silvio Canonica, Iganz Bilrge, Thomas Hofstetter, Werner Angst and Rene Schwarzenbach. Numerous people assisted me in parts of my work. I would like to acknowledge Adrian Amman and Thomas Ri.ittimann for their help with the IC-measurements, Roland Hany for the NMR-measurements, John Westall for the discussions about the right use of FITEQL, Vesna Klingel for the contributions in her diploma work, Martin Schwarz for his help in the syntheses of the cyclopropanes and Christian Saxer and Etienne Michel for performing a number of kinetic measurements. I would like to express my thanks to the Schwaba-crew for creating a pleasant wor- king atmosphere: Werner Angst, Cedric Arnold, Michael Berg, Thomas Bucheli, Andrea Ciani, Rick Devlin, Dieter Diem, Urs Domman, Martin Elsner, Beate Escher, Claudia Pesch, Guy Glod, Kai-Uwe Goss, Andreas Gerecke, Franca Gri.iebler, Edi Hohn, Stefan Haderlein, Thomas Hofstetter, Rene Hunziker, Jorg Klausen, Markus Meier, Ji.irg Mi.ihle- mann, Markus Millier, Stephan Muller, Klaus Pecher, Judith Perlinger, Csaba Reisinger, Kenny Weissmahr, Markus Ulrich, Thomas Waxweiler, Andre Weidenhaupt and Hans- ruedi Zweifel. I also like to thank Verena Cajochen, Sabine Hilger, Donald Tillman and many others for the common joggings at ,,a quarter to twelve". Warm thanks to my colleages outside EAWAG: Andrea, Annie, Bettina, Birgit, Edmee, Felix, Gabi H. and Gabi A., Marcel, Susi, Ulrich and Ursi. Finally, I would like to express my gratitude to my family for their love and support during all those years. Table of Contents List of Figures V List of Tables VIII Abbreviations X Summary XII Z usammenfassung XV 1. Introduction 1 2. Evaluation of the Iron Porphyrin/ Cysteine System 9 2.1 Introduction 9 2.2 Meso-tetrakis-(N-methyl-pyridyl)iron porphin 9 2.3 Kinetics of PHA reduction: determination of rate constants 12 2.4 Effect of pH on the reduction rates of CC14 and C2Cl6 14 2.4.1 Effect of pH on iron porphyrin with respect to redox potential and spin state 15 2.4.2 Effect of pH on cysteine 16 2.4.3 Buffers 21 2.5 Effect of cysteine and phosphate concentration on the reduction rates of CC14 and C2Cl6 22 2.5.1 Effect of cysteine concentration 22 2.5.2 Effect of phosphate concentration 25 2.6 Ionic strength 28 2.7 Rereduction of the iron porphyrin 31 2.8 Blank reactions 34 2.8.1 Porphyrin ring as electron transfer mediator 35 2.8.2 Reactions without iron porphyrin 36 2.9 Summary and conclusions 38 3. Reaction Intermediates and Reaction Products 39 3.1 Introduction 39 3.2 Degradation of CC14: product analysis 41 II 3.2.1 Product distribution between different phases 43 3.2.2 Ion chromatographic analysis 45 3.2.3 Product analysis by NMR and MS 47 3.3 Degradation of CC14: reaction intermediates 50 3.3.1 Trapping of CC4-radicals 50 3.3.2 Trapping of carbenes 52 3.4 Degradation of CC14: proposed reaction mechanism in the iron porphyrin/ cysteine system 54 3.5 Degradation of CC14: proposed reaction mechanism in the reaction with cysteine (blank system) 57 3.6 Degradation of CBr4, CBr2Cl2, CBrC13: comparison with CC14 58 3.7 Degradation of polyhalogenated methanes containing one hydrogen: CHBr3, CHBr2Cl, CHBrC12 63 3.8 Degradation of fluorinated methanes: CFBr31 CF2Br2, CFC13 66 3.9 Degradation of polyhalogenated ethanes 77 3.10 Summary and conclusions 84 4. Kinetics and Reaction Mechanisms. Structure-Reactivity Considerations 86 4.1 Introduction 86 4.2 Competition 86 4.3 Activation parameters 94 4.4 Comparison of degradation mechanisms of polyhalogenated methanes in different model systems 100 4.5 Structure- Reactivity Considerations 111 4.5.l Polyhalogenated methanes 111 4.5.2 Polyhalogenated ethanes 113 5. Conclusions 114 6. References 117 III Appendix A A-1 Al Chemicals A-1 A.2 Syntheses A-2 A.2.1 Meso-tetrakis(N-methyl-pyridyl)iron porphin A-2 A.2.2 N-formylcysteine A-3 A.2.3 3-methyl-3-butenoic acid A-4 A.2.4 Diazomethane A-4 A.2.5 2-(2,2-dichloro-1-methyl cyclopropyl)-ethanoic acid A-5 A.2.6 2-(2,2-dibromo-1-methyl cyclopropyl)-ethanoic acid A-5 A.2.7 2-(2-bromo-2-chloro-1-methyl cyclopropyl)-ethanoic acid A-6 A.3 Stock solutions and buffers A-6 A.4 Experimental procedures: Kinetic experiments A-7 A.4.1 Standard procedure for kinetic experiments A-7 A.4.2 Determination of rate constants A-10 A.4.3 pH variation A-10 A.4.4 Variation of cysteine concentration A-11 A.4.5 Variation of phosphate concentration A-12 A.4.6 Variation of ionic strength A-12 A.4.7 Variation of ligand concentration A-13 A.4.8 Reactions without porphyrin A-14 A.4.9 Variation of initial concentration of CBr2Cl2 A-15 A.4.10 Competition experiments: CBr2Cl2 versus CBrCl3 A-17 A.4.11 Competition experiments: CC14, CHBrClv CHBr2Cl A-18 A.4.12 Competition experiments: CC14 versus 4-chloro- nitrobenzene A-19 A.4.13 Determination of activation parameters A-20 IV A.5 Experimental procedures: Analysis of products and reaction intermediates A-21 14 A.5.1 Distribution experiments with C-CC14 A-21 13 A.5.2 C-CC14 experiments A-22 A.5.3 D' abstraction experiments A-22 A.5.4 Carbene trap experiments A-23 A.5.5 Quantification of products: methods of analyses A-26 A.5.6 Product studies of polyhalogenated ethanes A-26 A.6 Analytical prodedures A-27 A.6.1 GC-ECD A-27 A.6.2 GC-MS A-27 A.6.3 IC A-28 A.6.4 HPLC A-28 A.6.5 Scintillation counter A-29 A.6.6 NMR A-29 Appendix B B-1 B.1 UV-VIS experiments B-1 B.1.1 Cysteine-ligated iron porphyrin at different pH B-1 B.1.2 Effect of oxygen: Formation of superoxide radical B-2 B.1.3 Azide and cyanide as ligands B-3 B.1.4 Effect of cysteine concentration B-4 B.1.5 Effect of substrates B-4 B.1.6 UV-VIS spectrum of porphyrin ligand B-5 B.2 Polarographic measurements B-6 v List of Figures Figure 1.1: Worldwide production of some polyhalogenated alkanes (Fisher and Midgley, 1993i Rippen, 1988). 2 Figure 1.2: Half-reaction reduction potentials of organic redox couples (left side), various electron transfer mediators (middle) and some biogeochemically important redox couples (right side). Standard reduction potentials are indicated at environmentally relevant conditions: 25°C, pH 7.0, [Ci-)= [HCO;] = 10-3 M, [Br'] = lff' M. (Figure adopted from Schwarzenbach et al., 1997). 3 Figure 1.3: A mediator catalyses the electron transfer from the bulk electron donor to the pollutant. Typical bulk electron donors are iron(O), iron carbonate, hydrogen sulfide, hydrogen or iron sulfides. Mediators include surface- complexed iron, reduced cobalamins, reduced quinones or iron porphyrins. Organic pollutants that can be reduced are for example azo-dyes, nitroaromatic compounds or polyhalogenated alkanes (Figure adorpted from Schwarzenbach et al., 1997). 4 Figure 2.1: Meso-tetrakis(N-methyl-pyridyl)iron porphyin, an artificial water-soluble iron porphyrin.
Recommended publications
  • 1, 1, 1, 3, 3-Pentafluoropropane (HFC-245Fa) (CAS No. 460-73-1)

    1, 1, 1, 3, 3-Pentafluoropropane (HFC-245Fa) (CAS No. 460-73-1)

    1, 1, 1, 3, 3-Pentafluoropropane (HFC-245fa) (CAS No. 460-73-1) JACC Report No. 44 Brussels, June 2004 1, 1, 1, 3, 3-Pentafluoropropane (HFC-245fa) ECETOC JACC REPORT No. 44 © Copyright - ECETOC European Centre for Ecotoxicology and Toxicology of Chemicals 4 Avenue E. Van Nieuwenhuyse (Bte 6), B-1160 Brussels, Belgium. All rights reserved. No part of this publication may be reproduced, copied, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the copyright holder. Applications to reproduce, store, copy or translate should be made to the Secretary General. ECETOC welcomes such applications. Reference to the document, its title and summary may be copied or abstracted in data retrieval systems without subsequent reference. The content of this document has been prepared and reviewed by experts on behalf of ECETOC with all possible care and from the available scientific information. It is provided for information only. ECETOC cannot accept any responsibility or liability and does not provide a warranty for any use or interpretation of the material contained in the publication. ECETOC JACC No. 44 1, 1, 1, 3, 3-Pentafluoropropane (HFC-245fa) 1,1,1,3,3-Pentafluoropropane (HFC-245fa) (CAS No. 460-73-1) CONTENTS EXECUTIVE SUMMARY 1 THE ECETOC SCHEME FOR THE JOINT ASSESSMENT OF COMMODITY CHEMICALS 2 1. SUMMARY AND CONCLUSIONS 3 2. IDENTITY, PHYSICAL, AND CHEMICAL PROPERTIES, ANALYTICAL METHODS 5 2.1 Identity 5 2.2 EC classification and labelling 5 2.3 Physical and chemical properties 5 2.4 Conversion factors 6 2.5 Analytical methods 7 2.5.1 In air 7 2.5.2 In water 7 3.
  • Quantum Chemical Study of the Mechanism of the Catalytic

    Quantum Chemical Study of the Mechanism of the Catalytic

    ISSN 00231584, Kinetics and Catalysis, 2013, Vol. 54, No. 2, pp. 157–167. © Pleiades Publishing, Ltd., 2013. Original Russian Text © D.E. Zavelev, G.M. Zhidomirov, R.A. Kozlovskii, 2013, published in Kinetika i Kataliz, 2013, Vol. 54, No. 2, pp. 166–176. Quantum Chemical Study of the Mechanism of the Catalytic Oxyethylation of Ethylene Glycol on PhosphorusDoped Titanium Dioxide: The Role of the Surface Phosphoryl and Hydroxyl Groups of the Catalyst D. E. Zaveleva,*, G. M. Zhidomirovb,c, and R. A. Kozlovskiid a Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia b Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia c Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia d Mendeleev University of Chemical Technology of Russia, Moscow, 125047 Russia *email: [email protected] Received June 25, 2012 Abstract—DFT calculations of the oxyethylation pathways of monoethylene glycol (MEG) and diethylene glycol (DEG) were performed on a model fragment of phosphorusdoped titanium dioxide (anatase). It was shown that the surface hydroxyl group of titanium dioxide, whose proton initiates C–O bond cleavage in the ethylene oxide molecule, plays the key role in the activation of the molecule. At the same time, the phospho ryl group –P(OH)2O activates the reactant molecule R (MEG, DEG, etc.) and carries out the synchronous proton transfer from R to the hydroxyl oxygen atom of titanium dioxide, thus restoring the catalyst structure and closing the catalytic cycle. This restructuring occurs synchronously in one step. The substitution of the catalyst hydroxyl groups by alkoxyl groups can influence oxyethylation occurring via the bimolecular nucleo philic substitution mechanism and can poison the catalyst in some cases.
  • Assessment of New Persistent Organic Pollutants-Pesticides in Air

    Assessment of New Persistent Organic Pollutants-Pesticides in Air

    ASSESSMENT OF NEW PERSISTENT ORGANIC POLLUTANTS-PESTICIDES IN AIR AND SOIL SAMPLES FROM SITES IN NAIROBI AND MOUNT KENYA BY JULIE KIDAHA (I56/68771/2011) A thesis submitted for Examination in partial fulfilment of the requirements for Award of the Degree of Master of Science in Environmental Chemistry of the University of Nairobi 2015 i DECLARATION I declare that this thesis is my original work and has not been submitted elsewhere for examination, award of a degree or publication. Where other people‟s work, or my own work has been used, this has properly been acknowledged and referenced in accordance with the University of Nairobi‟s requirements.. …………………………………. Date................ JULIE KIDAHA (156/68771/2011) This thesis has been submitted with our approval as university supervisors ……………………………………… Date................ Prof. Shem. O. Wandiga Department of Chemistry, University of Nairobi ………………………………………… Date................ Dr. Deborah A. Abong‟o Department Of Chemistry, University Of Nairobi ii DEDICATION I dedicate this work to my beloved children; Jeanne, Jael, Jerry and Josh. iii ACKNOWLEDGEMENTS My sincere gratitude goes to my supervisors Prof. Shem. O. Wandiga and Dr. Deborah A. Abong‟o for their intellectual input in this work. Their guidance and mentorship is highly appreciated. I am indebted to Dr. Vincent Madadi for his valuable comments that helped me shape my ideas. His selfless commitment in training me during sampling, sample preparation and analysis is highly appreciated. I am grateful to him for the supply of solvents used in this work. I acknowledge my employer, The Teachers‟ Service Commission for granting me study leave with pay. This went along way in ensuring that I met my financial obligations while studying.
  • Maria Goreti Da Silva Monteiro Prof. Doutora Maria Luísa Fernandes

    Maria Goreti Da Silva Monteiro Prof. Doutora Maria Luísa Fernandes

    UNIVERSIDADE DE LISBOA FACULDADE DE LETRAS ÁREA DE LITERATURAS, ARTES E CULTURAS COMUNICAÇÃO EMPRESARIAL, INGLÊS E TRADUÇÃO: UM ESTUDO DO CORREIO ELECTRÓNICO EM EMPRESAS PORTUGUESAS DE MOLDES PARA PLÁSTICOS NO QUADRO DA GRAMÁTICA SISTÉMICO-FUNCIONAL Maria Goreti da Silva Monteiro Dissertação orientada pela Prof. Doutora Maria Luísa Fernandes Azuaga DOUTORAMENTO EM LINGUÍSTICA (Linguística Inglesa) 2010 Em memória de meus pais e de L. J. ii AGRADECIMENTOS O percurso de anos que conduz à conclusão de uma dissertação de doutoramento permite conviver com pessoas que ajudam a reflectir e materializar projectos iniciais, muitas vezes vagos e dispersos. As valiosas colaborações de um número dessas pessoas, bem como o seu incentivo e dedicação não podiam deixar de ser aqui e agora registadas. Agradeço à Prof. Doutora Luísa Azuaga, minha orientadora, em primeiro lugar, não apenas por acompanhar o meu trabalho desde o primeiro momento, mas também pelas palavras de encorajamento, essenciais para a conclusão de cada etapa. Agradeço, ainda, o seu convite para integrar a equipa de pesquisa do CEAUL, um local de estudo e, tão importante, de discussão de saberes. Ao mesmo tempo, não teria sido possível chegar a este ponto sem o apoio do IPL / ESTG, que proporcionou condições indispensáveis a uma maior dedicação ao doutoramento. Para tal, muito colaboraram a Coordenadora do Departamento de Ciências da Linguagem e todos os meus colegas, a quem agradeço de forma muito especial. Não posso deixar de lembrar que este estudo só foi exequível com o particular apoio das empresas que, por motivo de sigilo a elas devido, não são nomeadas, mas que têm a minha permanente gratidão.
  • Novel Synthesis of Partially Fluorinated Ethers

    Novel Synthesis of Partially Fluorinated Ethers

    Issue in Honor of Prof. Sukh Dev ARKIVOC 2003 (iii) 104-119 Alkylation of in situ generated fluorinated alkoxides: novel synthesis of partially fluorinated ethers G. K. Surya Prakash*, Jinbo Hu and George A. Olah Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, CA 90089-1661 E-mail: [email protected] Dedicated to Professor Sukh Dev on the occasion of his 80th birthday (received 07 Jan 03; accepted 24 Feb 03; published on the web 27 Feb 03) Abstract Fluorinated ethers RfCF2OR were prepared from acyl chlorides RfCOCl, alkylating agents (such as dimethyl sulfate, alkyl triflates, alkyl mesylates and tosylates, etc.) and potassium fluoride in diglyme at 80~100 oC. The success and the efficiency of the reaction are affected by two factors: the stability and nucleophilicity of the fluorinated alkoxide generated in situ; and the other is the electrophilicity of the alkylating agents used. Keywords: Fluoroethers, fluoroacyl halides, fluoride ion, alkylation Introduction In general, carbon-fluorine bonds (C-F, ~116 kcal/mol) are stronger than carbon-hydrogen bonds (C-H, ~99 kcal/mol).1 However, not all organofluorine compounds are more stable than their non-fluorinated analogs, and sometimes they are even less stable. For instance, if a partially or fully fluorinated organic compounds contains an acidic hydrogen at the β position, HF elimination is observed. This is the main reason that α-fluoro alcohols are thermally unstable and 2 difficult to be synthesized or isolated. Formation of fluoromethanol (FCH2OH) from ethyl fluoroformate and from formyl fluoride was first reported by Olah and Pavlath3 in 1953, and Weinmayer4 in 1963 claimed the formation of fluoromethanol (25-30% in equilibrium) from a solution of paraformaldehyde in excess hydrogen fluoride.
  • Poly\Arylene Thioetherketone\Compositions Improved in Both Melt Stability and Crystallinity

    Poly\Arylene Thioetherketone\Compositions Improved in Both Melt Stability and Crystallinity

    Europaisches Patentamt J European Patent Office CO Publication number: 0 296 877 Office europeen des brevets A2 EUROPEAN PATENT APPLICATION © Application number: 88305783.8 © int. Ci.4: C08K 5/00 , C08K 3/00 , C08L 81/02 @ Date of filing: 22.06.88 Priority: 22.06.87 JP 154801/87 © Applicant: KUREHA KAGAKU KOGYO 03.09.87 JP 221122/87 KABUSHIKI KAISHA 11.06.88 JP 142772/88 1-9-11, Nihonbashi, Horidome-cho Chuo-ku Tokyo 103(JP) Date of publication of application: 28.12.88 Bulletin 88/52 @ Inventor: Satake, Yoshikatsu 1-6, Ochiai Nishiki-machi Designated Contracting States: Iwaki-shi Fukushima-ken 974(JP) AT BE CH DE ES FR GB GR IT LI LU NL SE Inventor: Kashiwadate, Ken 108-3, Asahidai Kanayama-machi Iwaki-shi Fukushima-ken 974(JP) Inventor: lizuka, Yo 1-36-10, lino Chuodai Iwaki-shi Fukushima-ken 970(JP) Inventor: Katto, Takayuki 1-1-5, Nakaoka-machi Iwaki-shi Fukushima-ken 974(JP) Inventor: Shiiki, Zenya 28-1, Ochiai Nishiki-machi Iwaki-shi Fukushima-ken 974(JP) Inventor: Kouyama, Toshitaka 4-2-12, Nakaoka-machi Iwaki-shi Fukushima-ken 974(JP) ® Representative: Jones, Helen M.M. et al Gill Jennings & Every 53-64 Chancery Lane London WC2A1HN(GB) ® Poly(arylene thioetherketone)compositions improved in both melt stability and crystallinity. CN ^© Disclosed herein is a poly(arylene thioether-ketone) composition improved in melt stability and crystallinity, 1^ which comprises (A) 100 parts by weight of a melt-stable poly(arylene thioether-ketone) (PTK) and (B) 0.1-30 fS parts by weight of at least one basic compound selected from the group consisting of the hydroxides, oxides 00 and aromatic carboxylic acid salts of Group IIA metals of the periodic table other than magnesium and the {Qhydrocarbyl oxides, aromatic carboxylic acid salts, carbonates, hydroxides, phosphates and borates of Group IA G) metals of the periodic table.
  • Fluoro-Silane As a Functional Monomer for Protein Conformational Imprinting

    Fluoro-Silane As a Functional Monomer for Protein Conformational Imprinting

    Utah State University DigitalCommons@USU All Graduate Theses and Dissertations Graduate Studies 5-2011 Fluoro-Silane as a Functional Monomer for Protein Conformational Imprinting Yun Peng Utah State University Follow this and additional works at: https://digitalcommons.usu.edu/etd Part of the Biomedical Engineering and Bioengineering Commons Recommended Citation Peng, Yun, "Fluoro-Silane as a Functional Monomer for Protein Conformational Imprinting" (2011). All Graduate Theses and Dissertations. 906. https://digitalcommons.usu.edu/etd/906 This Dissertation is brought to you for free and open access by the Graduate Studies at DigitalCommons@USU. It has been accepted for inclusion in All Graduate Theses and Dissertations by an authorized administrator of DigitalCommons@USU. For more information, please contact [email protected]. FLUORO-SILANE AS A FUNCTIONAL MONOMER FOR PROTEIN CONFORMATIONAL IMPRINTING by Yun Peng A dissertation submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in Biological Engineering Approved: David W. Britt, Ph.D. Timothy E. Doyle, Ph.D. Major Professor Committee Member Marie K. Walsh, Ph.D. Soonjo Kwon, Ph.D. Committee Member Committee Member Jixun Zhan, Ph.D. Byron Burnham Committee Member Dean of Graduate Studies UTAH STATE UNIVERSITY Logan, Utah 2011 ii Copyright © Yun Peng 2011 All Rights Reserved iii ABSTRACT Fluoro-silane as a Functional Monomer for Protein Conformational Imprinting by Yun Peng, Doctor of Philosophy Utah State University, 2011 Major Professor: Dr. David W. Britt Department: Biological Engineering By using the technology of molecularly imprinted polymer (MIP), we propose to synthesize a protein conformational imprint that also acts as a plastic enzyme, inducing protein structural transitions.
  • (12) United States Patent (10) Patent No.: US 8,501,891 B2 Nozue Et Al

    (12) United States Patent (10) Patent No.: US 8,501,891 B2 Nozue Et Al

    US008501891B2 (12) United States Patent (10) Patent No.: US 8,501,891 B2 NOZue et al. (45) Date of Patent: Aug. 6, 2013 (54) ETHYLENE-o-OLEFIN COPOLYMER AND (56) References Cited MOLDED ARTICLE U.S. PATENT DOCUMENTS (75) Inventors: Yoshinobu Nozue, Ichihara (JP); 5,962,615 A 10/1999 Kojoh et al. Yasutoyo Kawashima, Ichihara (JP); 2002/0143124 A1 10/2002 Ogane 2003/0060579 A1 3/2003 Oshima et al. Naoko Ochi, Chiba (JP) 2006, OO89476 A1 4/2006 Iseki et al. 2006/O199925 A1 9/2006 Matsuura et al. (73) Assignee: Sumitomo Chemical Company, 2007/0093.627 A1 4/2007 Iseki et al. Limited, Tokyo (JP) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this CN 1765943. A 5, 2006 CN 1939.943. A 4/2007 patent is extended or adjusted under 35 EP O339571 A1 11, 1989 U.S.C. 154(b) by 423 days. JP 1-292009 A 11, 1989 JP O7-238114 A 9, 1995 (21) Appl. No.: 12/745,178 JP 08-0597O6 A 3, 1996 JP 2003-0961.25 A 4/2003 JP 2003-171412 A 6, 2003 (22) PCT Filed: Nov. 27, 2008 JP 2005-2333 A 1, 2005 JP 2005-206777 A 8, 2005 (86). PCT No.: PCT/UP2008/072000 JP 2005-24.8013. A 9, 2005 JP 2005-281541. A * 10, 2005 S371 (c)(1), JP 2006-233208 A 9, 2006 (2), (4) Date: Jul. 16, 2010 OTHER PUBLICATIONS (87) PCT Pub. No.: WO2009/069823 Mino et al., (JP 2005-281541) Oct. 13, 2005; abstract and translation in English.* PCT Pub.
  • Reactive Chlorine Compounds in the Atmosphere

    Reactive Chlorine Compounds in the Atmosphere

    CHAPTER 1 Reactive Bromine Compounds O.N.Singh 1 · P.Fabian 2 1 Department of Applied Physics, Institute of Technology, Banaras Hindu University, Varanasi- 221 005, India. E-mail: [email protected] 2 University of Munich, Lehrstuhl für Bioklimatologie und Immissionsforschung, Am Hochanger 13, D-85354 Freising-Weihenstephan, Germany. E-mail: [email protected] Bromine, a minor constituent in the Earth’s atmosphere – with its 50-fold higher efficiency of ozone destruction compared to chlorine – contributes significantly to the ozone hole formation and wintertime stratospheric ozone depletion over northern mid and high latitudes.In addition ozone episodes observed in the Arctic during polar sunrise are solely due to atmospheric bromine.CH3Br, CH2Br2 and CHBr3 are the major brominated gases in the atmosphere, of which CH3Br being most abundant, contributes about 50% and CH2Br2 around 7 to 10% of the total organic stratospheric bromine.Bromocarbons with shorter lifetimes like CHBr3 ,CH2BrCl, CHBr2Cl, CHBrCl2 and CH2BrI decompose before reaching the stratosphere, and are responsible for the ozone episodes.But for 3CHBr, which has also significant anthropogenic sources, all the aforementioned bromocarbons are mostly of marine origin.Halons (H-1211, H-1301, H-2402, H-1202) are solely anthropogenic and are far more stable.They decompose only after reaching the stratosphere.It is estimated that 39% of the stratospheric organic bromine (ª 7 pptv) loading is due to these halons.Increa- ses are being still registered in the atmospheric abundance of halons in spite of production restrictions.Though extensively investigated,the existing knowledge with regard to the pro- duction and degradation of atmospheric bromine gases, is not commensurate with its importance.
  • MALDI Matrix and MALDI Method

    MALDI Matrix and MALDI Method

    (19) & (11) EP 2 060 919 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 20.05.2009 Bulletin 2009/21 G01N 33/68 (2006.01) H01J 49/04 (2006.01) (21) Application number: 07120550.4 (22) Date of filing: 13.11.2007 (84) Designated Contracting States: (72) Inventors: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • Wuijckhuijse, Arjan Laurens HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE 3331 GP Zwijndrecht (NL) SI SK TR • Kientz, Charles Eliza Designated Extension States: 2611 Gl Delft (NL) AL BA HR MK RS (74) Representative: Hatzmann, Martin (71) Applicant: Nederlandse Organisatie voor Vereenigde Toegepast- Johan de Wittlaan 7 Natuurwetenschappelijk Onderzoek TNO 2517 JR Den Haag (NL) 2628 VK Delft (NL) (54) MALDI matrix and MALDI method (57) The invention is directed to a matrix material for wherein X is chosen from S, O or N, and wherein R1 and MALDI mass spectrometry, to a matrix composition for R2 are independently chosen from hydrogen, methyl, MALDI mass spectrometry, in particular for aerosol MAL- methoxy, ethoxy, and propoxy, or wherein R1 and R2 are DI mass spectrometry, to a MALDI mass spectrometry taken together to form an optionally substituted aromatic method, in particular an aerosol MALDI mass spectrom- ring structure, optionally comprising one or more heter- etry method, to the use of a specific compound as a MAL- oatoms, DI matrix material, and to the use of a MALDI matrix com- or a tautomeric form thereof. position in a gas phase coating method.
  • Controlling Transition Metal-Catalyzed Alkyne Annulations Utilizing Polarized Ynol Ethers

    Controlling Transition Metal-Catalyzed Alkyne Annulations Utilizing Polarized Ynol Ethers

    University of Denver Digital Commons @ DU Electronic Theses and Dissertations Graduate Studies 2020 Controlling Transition Metal-Catalyzed Alkyne Annulations Utilizing Polarized Ynol Ethers Brandon L. Coles-Taylor Follow this and additional works at: https://digitalcommons.du.edu/etd Part of the Organic Chemistry Commons Controlling Transition Metal-Catalyzed Alkyne Annulations Utilizing Polarized Ynol Ethers ______________ A Dissertation Presented to the Faculty of the College of Natural Sciences and Mathematics University of Denver ____________ In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy ____________ by Brandon L. Coles-Taylor June 2020 Advisor: Brian Michel, PhD ©Copyright by Brandon L. Coles-Taylor 2020 All Rights Reserved Author: Brandon L. Coles-Taylor Title: Controlling Transition Metal-Catalyzed Alkyne Annulations Utilizing Polarized Ynol Ethers Advisor: Brian Michel, PhD Degree Date: June 2020 Abstract Transition metal-catalyzed alkyne annulations have developed into incredibly powerful synthetic tools over there the past quarter century. These reactions provide rapid access to important organic scaffolds such as indole, quinoline, isoquinoline, indene, and isocoumarin scaffolds. Transition metal mediated alkyne annulations have proven invaluable in synthetic fields, such as natural product total synthesis, by offering efficient pathways to otherwise synthetically difficult to access substrates. Foundational works performed by chemist such as Larock, Ackermann, Satoh, and Miura have been established through relying upon the usage of symmetrical alkynes. When unsymmetrical alkynes are used in annulation processes mixtures of regioisomers are often isolated. While methodologies have been developed which regioselectively deliver annulation products, the regioselective nature of these reactions is often empirically determined and obtained with little synthetic design to impact the alkyne migratory insertion step of the catalytic cycle.
  • In Four Polar Bears (Ursus Maritimus) That Swam Malnourished from East Greenland to Iceland

    In Four Polar Bears (Ursus Maritimus) That Swam Malnourished from East Greenland to Iceland

    Science of the Total Environment 533 (2015) 290–296 Contents lists available at ScienceDirect Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv Polyhalogenated compounds (PCBs, chlordanes, HCB and BFRs) in four polar bears (Ursus maritimus) that swam malnourished from East Greenland to Iceland Walter Vetter a,⁎, Vanessa Gall a, Karl Skírnisson b a University of Hohenheim, Institute of Food Chemistry, Garbenstr. 28, D-70593 Stuttgart, Germany b University of Iceland, Keldur, Institute for Experimental Pathology, IS-112 Reykjavík, Iceland HIGHLIGHTS GRAPHICAL ABSTRACT • Four polar bears swam in malnourished condition from East-Greenland to Iceland. • Organohalogen compounds (PCBs, chlor- dane, PBBs, PBDEs, HCB) were quantified. • Dec-602 was tentatively identified in all tissues and an unknown compound in liver. article info abstract Article history: Levels of organohalogen compounds (PCBs, chlordane, PBB 153, PBDEs, HCB) were determined in adipose tissue, Received 24 March 2015 liver, kidney and muscle of four polar bears which swam and/or drifted to Iceland in extremely malnourished Received in revised form 2 July 2015 condition. Since the colonization in the 9th century polar bears have been repeatedly observed in Iceland. Accepted 3 July 2015 However, in recent years three of the animals have clearly left their natural habitat in poor condition in May or Available online xxxx June, i.e. at the end of the major feeding season. The fourth bear is believed to have drifted with melting ice to Editor: D. Barcelo North-Eastern Iceland in mid-winter. The concentrations of the POPs were within the range or higher than the typical concentrations measured in polar bears from the East Greenland population.