Co-Immobilization of (2,2'-Bipyridyl) (Pentamethylcyclopentadienyl

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Co-Immobilization of (2,2'-Bipyridyl) (Pentamethylcyclopentadienyl Co-immobilization of (2,2’-bipyridyl) (pentamethylcyclopentadienyl)-rhodium complex and NAD-dependent dehydrogenases for enzymatic electrosynthesis Lin Zhang To cite this version: Lin Zhang. Co-immobilization of (2,2’-bipyridyl) (pentamethylcyclopentadienyl)-rhodium complex and NAD-dependent dehydrogenases for enzymatic electrosynthesis. Organic chemistry. Université de Lorraine, 2016. English. NNT : 2016LORR0283. tel-01665493 HAL Id: tel-01665493 https://tel.archives-ouvertes.fr/tel-01665493 Submitted on 16 Dec 2017 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. AVERTISSEMENT Ce document est le fruit d'un long travail approuvé par le jury de soutenance et mis à disposition de l'ensemble de la communauté universitaire élargie. Il est soumis à la propriété intellectuelle de l'auteur. Ceci implique une obligation de citation et de référencement lors de l’utilisation de ce document. D'autre part, toute contrefaçon, plagiat, reproduction illicite encourt une poursuite pénale. Contact : [email protected] LIENS Code de la Propriété Intellectuelle. articles L 122. 4 Code de la Propriété Intellectuelle. articles L 335.2- L 335.10 http://www.cfcopies.com/V2/leg/leg_droi.php http://www.culture.gouv.fr/culture/infos-pratiques/droits/protection.htm Sujet de thèse : Co - immobilisation du complexe (2,2'-bipyridyl) (pentaméthylcyclopentadiényl)-rhodium et de déshydrogénases NAD-dépendantes pour l’électrosynthèse enzymatique énantiosélective Par Lin ZHANG Pour l‟obtention de titre de Docteur Ecole Doctorale : Synthèse, Simulations, Applications: de la Molécule aux Edifices Supramoléculaires (SESAMES), ED 412 Soutenance publique prévue le 15 December 2016 devant le jury composé de : Rapporteurs: Prof. Philip N Bartlett, University of Southampton, United Kingdom Dr. Elisabeth Lojou, BIP, CNRS, Marseille Invités: Dr. Alain Walcarius, LCPME, CNRS, Nancy Prof. François Lapicque, LRGP, CNRS, Nancy Directeur : Dr. Mathieu Etienne, LCPME, CNRS, Nancy Examinateur : Dr. Neus Vila, Université de Lorraine, Nancy Laboratoire de Chimie Physique et Microbiologie pour l’Environnement (LCPME) Unité mixte de recherche – UMR 756 405 Rue de Vandoeuvre, 54600, Villers-lès-Nancy, France Acknowlegements First of all, I would like to give my greatest thanks to my supervisors Mathieu ETIENNE and Neus VILA for their guiding and supporting me during these past three years. Without their constant advice and efforts, this thesis would not have been completed. I feel very lucky to be a student of them. I could still remember at the beginning of my Ph.D when I just enter the field of electrochemistry how they encourage me to go out of frustration when I meet difficulties. Mathieu teach me how to carry out research independently and systematically, giving me the confidence to continue my career in science. Neus not only help me in work, showing me the proper ways to carry out different experiments, but also help me in life when I meet difficulties. There are so many things they have teach me and help me that I‟m not able to list all here, but all the details are kept in my mind, which will become part of my great memories in my life. I would like to acknowledge Alain WALCARIUS who is the director of the lab and our ELAN group for his scientific supports and useful discussions. I would also like to acknowledge Prof. Gert-Wieland KOHRING from Saarland University for his support in biological part of this thesis. I am also very grateful to my friend Ievgen MAZURENKO, who is the former post-doc in ELAN group, he give me detailed guidance at the beginning of my Ph.D, leading me to the field of bioelectrochemistry. I would also like to thank all the members in ELAN Group, present and past, for their selfless support and friendships. They made my life more colorful during the three years. Special thanks to: Cheryl KARMAN, for her generous help when I was sick; Maciej MIERZWA, for being a good partner to have nice lunch time during two years; Mohana AFSHARIAN, for her help when I was looking for an apartment; Martha COLLINS, for her help in some documents preparation; Lukasz POLOTORAK, for his warm-hearted assistance. There are also many people in LCPME who have help me from time to time, I‟m not able to thank them one by one here, I will always remember their kindness to me. Here I also want to thank my Master supervisor Eric GRELET in Bordeaux, he teach me the right attitude toward science, which has influenced me on way of research. I would like to thank my family, especially my parents for their constant support since I go abroad, I could always get sense of security from them no matter how difficult situation I was in. I would also like to thank my father in law for his advices for my scientific career. At last, I would like to express my thanks to my husband Zhanming for his love, it‟s very important that we hold each other‟s hand, sharing the happiness and facing the difficulties together. Table of content Abstract .................................................................................................................................................. 1 Résumé ................................................................................................................................................... 2 General introduction ............................................................................................................................. 3 Chapter 1. Literature survey ................................................................................................................ 7 1.1 Introduction ........................................................................................................................... 8 1.2 Enzymatic systems, cofactor recycling and target reactions ........................................... 12 1.2.1 NAD(P)-dependent-redox enzymes ............................................................................ 12 1.2.2 Flavoenzymes ............................................................................................................... 16 1.2.3 Metalloproteins ............................................................................... 错误!未定义书签。 1.2.4 Electrode materials ...................................................................................................... 19 1.2.4.1 Metals ....................................................................................................................... 19 1.2.4.2 Metal oxides ............................................................................................................. 20 1.2.4.3 Carbon materials ..................................................................................................... 20 1.3 Immobilization of enzymes on electrodes .......................................................................... 21 1.3.1 Membrane confinement with membranes ................................................................. 22 1.3.2 Chemical bonding ........................................................................................................ 25 1.3.2.1 Carbodiimide activation ......................................................................................... 25 1.3.2.2 Glutaraldehyde crosslinking................................................................................... 27 1.3.2.3 Self-assembled monolayer (SAM) .......................................................................... 27 1.3.3 Encapsulation ............................................................................................................... 29 1.3.3.1 Nafion coating .......................................................................................................... 29 1.3.3.2 Surfactant and lipidic layers................................................................................... 30 1.3.3.3 Alginate-based gel and sol-gel silica ....................................................................... 31 1.3.3.4 Conducting polymers .............................................................................................. 33 1.4 Immobilization of mediators .............................................................................................. 34 1.4.1 Methyl-viologen ........................................................................................................... 35 1.4.2 [Cp*Rh(bpy)Cl]+ .......................................................................................................... 35 1.5 Conclusions .......................................................................................................................... 37 Chapter 2. Immobilization of cysteine-tagged proteins on electrode surfaces by thiol-ene click chemistry .............................................................................................................................................. 47 2.1 Introduction ......................................................................................................................... 48 2.2 Experimental .......................................................................................................................
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