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391	Isolated Graphene Edge Nanoelectrodes: Fabrication, Selective Functionalization, and Electrochemical Sensing Yadav, Anur 03 August 2021 (has links) Diese Arbeit präsentiert eine einfache eine einfache, auf Photolithographie basierende Methode zur Darstellung einer isolierten Graphenkante (oder GrEdge) einer Monolage als Nanoelektrode auf einem isolierenden Substrat vorgestellt. Trotz ihrer Millimeter-Länge verhält sich die nur einen Nanometer breite GrEdge-Elektrode wie ein Nanodraht mit einem hohen Seitenverhältnis von 1000000 zu 1. Des Weiteren wird der Einsatz von elektrochemischer Modifikation (ECM) demonstriert, um die GrEdge selektiv mit Metall-Nanopartikeln und organischen Schichten nicht-kovalente oder kovalente zu funktionalisieren, wodurch die Chemie der Kante verändert werden kann. Durch die Anbringung von Metall-Nanopartikeln kann zusätzlich oberflächenverstärkte Raman-Spektroskopie (SERS) genutzt werden, um die chemische Beschaffenheit sowohl der unberührten als auch der funktionalisierten GrEdge zu charakterisieren. Die GrEdge weist sehr hohe Mass-entransportraten auf, was charakteristisch für Nanoelektroden ist. Dementsprechend wird die voltammetrische Antwort von der Kinetik des heterogenen Elektrontransfers (HET) diktiert. An der GrEdge-Elektrode werden hohe HET-Raten beobachtet: mindestens 14 cm/s für Außensphäre sonde Ferrocenmethanol (FcMeOH) mit einem quasi-Nernst'schen Verhalten und 0,06 cm/s oder höher für innere Sphäre sonde Ferricyanide ([Fe(CN)6]3-) mit einer kinetisch kontrollierten Reaktion. Nach der selektiven Modifikation der Kante mit Goldnanopartikeln erweist sich der HET als reversibel, mit einer massentransportbegrenztes Nernst‘sches Verhalten aufweisen für beide Redoxmoleküle. Darüber hinaus ermöglicht die schnelle HET-Kinetik die Detektion der reduzierten Form von Nicotinamid-Adenin-Dinukleotid (NADH) und Flavin-Adenin-Dinukleotid (FAD) mit niedrigen Ansatzpotentialen und hinunter bis zu niedrigen mikromolaren Konzentrationen. Entsprechend verbessert die vorliegende Arbeit das Verständnis der Kante von Graphen und deren Chemie. / This thesis presents a simple photolithography-based method to realize the isolated monolayer graphene edge (or GrEdge) nanoelectrode on an insulating substrate. The millimeter-long and a nanometer-wide GrEdge is found to behave like a nanowire with a high aspect ratio of 1000000-to-1. Further, the use of electrochemical modification (ECM) is demonstrated to selectively functionalize the GrEdge with metal nanoparticles and organic moieties in a non-covalent/ covalent manner to tune the chemistry of the edge. The attachment of metal nanoparticles was used to exploit surface-enhanced Raman scattering (SERS) to characterize the chemistry of both the pristine and the functionalized GrEdge. The GrEdge electrodes were found to exhibit very high mass transport rates, characteristic of nanoelectrodes. Accordingly, the voltammetric response is found to be dictated by the kinetics of heterogeneous electron transfer (HET), attributed to the nanoscale geometry and a unique diffusional profile at such electrodes. At the GrEdge electrode, high HET rates are observed: at least 14 cm/s for outer-sphere probe, ferrocenemethanol (FcMeOH) with a quasi-Nernstian behavior; and 0.06 cm/s or higher for inner-sphere probe, ferricyanide ([Fe(CN)6]3-) with a kinetically controlled response. Upon selective modification of the edge with gold nanoparticles, the HET is found to be reversible, with a mass-transport-limited Nernstian response for both probes. Furthermore, the fast HET kinetics enables the sensing of the reduced form of nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) with low onset potentials and down to low micromolar concentrations. Hence, this thesis improves the understanding of the edges of graphene and their chemistry. It also realizes isolated GrEdge as a new class of nanoelectrode which forms an important basis within the fields of fundamental electrochemistry and analytical sciences. Graphen Graphenkante chemische Funktionalisierung Elektrochemie elektrochemischer Modifikation (ECM) Nanoelektroden Ultramikroelektroden (UME) heterogener Elektronentransfer (HET) HET-Kinetik elektrochemischer Sensorik graphene graphene edge chemical functionalization electrochemistry electrochemical modification (ECM) nanoelectrodes ultramicroelectrodes (UME) heterogeneous electron transfer (HET) HET kinetics electrochemical sensing 543 Analytische Chemie 541 Physikalische Chemie VK 7720 VG 9307 UP 3150 VE 6307 VG 6847 ddc:543 ddc:541
392	Energetic and Microscopic Characterization of the Primary Electron Transfer Reaction in the (6-4) Photolyase Repair Reaction Oßwald, Mara 17 April 2024 (has links) Wird DNA mit UV-Licht bestrahlt, kommt es zur Bildung von Photoschäden, die zu Zelltod oder Krebs führen können. In dieser Arbeit wird die primäre Elektronentransferreaktion des lichtaktivierten Reparaturprozesses des (6-4)-Schadens in Drosophila melanogaster charakterisiert. Der katalytische Reparaturzyklus wird durch das Flavoprotein (6-4)-Photolyase (PL) realisiert. Der Elektronentransfer (ET) vom Flavin-Adenin-Dinukleotid (FADH⁻) Kofaktor zum Schaden initiiert die molekularen Umlagerungen. Diese Arbeit charakterisiert die primäre ET Reaktion mithilfe von molekulardynamischen Langzeitsimulationen (µs) in Kombination mit Quantenmechanik/Molekularmechanik-Simulationen. Ab initio lokale Coupled-Cluster- und Dichtefunktionaltheorierechnungen wurden angewendet, um die relative Energetik von lokal angeregten und Ladungstransferzuständen des (6-4)-Reparaturkomplexes zu charakterisieren. Es zeigt sich, dass die Reduktion des (6-4)-Schadens durch einen Ladungstransferzustand ermöglicht wird an dem die Adeninstruktur des FADH⁻ -Kofaktors beteiligt ist. Über die Simulationen wird ein mikroskopisches Bild der Reaktionskoordinate der Elektronentransferreaktion im Marcusbild entwickelt. Diese ist nicht vollständig durch parabolische freie Energiekurven beschrieben sondern wird, durch Wechselwirkungen in der aktiven Tasche, ein Multiminima-Reaktionspfad ausgebildet. Hierbei hat die Rotation der Seitenkette der benachbarten, geladenen Aminosäure Lys246 dominanten Einfluss. Dies legt nahe, dass die primäre ET Reaktion der (6-4) Schadensreparatur, einen vom Adenin unterstützten ET Weg von der PL zur 5’ Seite des Schadens nimmt. Dieser Prozess wird durch benachbarte Aminosäuren und einer Stärkung der Wasserstoffbrücken mit Wassermolekülen stabilisiert. Die Ergebnisse dieser Arbeit zeigen, dass ET-Reaktionen in komplexen enzymatischen Systemen nicht im Kontinuumsbild von ET beschrieben werden können, da lokale Wechselwirkungen drastischen Einfluss auf die ET Reaktionen haben. / UV-light irradiation of DNA leads to the formation of photolesions that can cause cell death and cancer. This thesis aims at the characterization of the primary electron transfer (ET) reaction in the photoactivated repair process of the (6-4) lesion in Drosophila melanogaster. The catalytic repair cycle is realized by a flavoprotein called photolyase (PL). The ET from the fully reduced flavin-adenine-dinucleotide (FADH⁻) cofactor of the PL to the lesion initiates molecular rearrangements. In this thesis fluctuation properties of the enzyme environment on the excited states are considered by conducting long-time (µs) molecular dynamics simulations combined with extensive quantum mechanical/molecular mechanical simulations. Ab initio local coupled cluster simulations and density functional theory are applied to characterize the relative energetics of locally excited and charge transfer (CT) states in the (6-4) lesion repair complex. Reduction of the (6-4) lesion is found to be enabled by a CT state involving the adenine moiety of the FADH⁻ cofactor. Microscopic characterization of a Marcus-type free energy reaction coordinate reveals that it cannot be fully described by parabolic free energy curves. Specifically, rotation of the side chain of nearby charged amino acid Lys246 imposes a double-well character on the potential energy surface along the reaction coordinate of the ET. For the ET reaction triggering the catalytic (6-4) lesion repair, the findings of this thesis suggest an ET pathway to the 5’ side of the (6-4) lesion mediated by the adenine moiety. The process is stabilized by neighboring amino acids and a strengthening of hydrogen bonds with water molecules. The presented results demonstrate that ET reactions in complex enzymatic systems cannot be described within the continuum ET picture, as local interactions drastically tune the ET reaction. DNS Photoschaden Quantenchemie Molekulardynamik Elektronentransfer Marcus Theorie (6-4) Schaden (6-4) Photoprodukt Photolyase Reparaturprozess QM/MM DFT Dichtefunktionaltheory DNA photolesion quantum chemistry molecular dynamics electron transfer Marcus theory (6-4) lesion (6-4) photoproduct photolyase repair process QM/MM DFT density functional theory 530 Physik 541 Physikalische Chemie ddc:530 ddc:541
393	Hydroxyamidinates et polymères de coordination : suspicions et valences mixtes Leblanc, Mathieu 07 1900 (has links) Dans un contexte où l’énergie représente un enjeu majeur pour les pays et organisations à économies émergentes et développées, la recherche de nouvelles sources renouvelables et la démocratisation des vecteurs énergétiques permettant l’approvisionnement mondial de façon durable constitue un devoir pour la communauté scientifique internationale. D’ailleurs, il serait essentiel que les nombreuses disciplines de la chimie concertent leurs efforts. Plus particulièrement, la croissance de la recherche en chimie de coordination orientée vers la photosynthèse artificielle ainsi que le développement de matériaux fonctionnels démontre l’importance indéniable de ce champ de recherche. Ce travail présente dans un premier temps l’étude des différentes voies de synthèse d’hydroxyamidines, un ligand chélatant aux propriétés de coordination prometteuses ne recevant que très peu d’attention de la part de la communauté scientifique. Dans un deuxième temps, nous présenterons le développement d’une stratégie d’assemblage de leurs complexes supramoléculaires impliquant des métaux de transition abondants et peu dispendieux de la première rangée. Dans un troisième temps, il sera question de l’investigation de leurs propriétés photophysiques et électrochimiques à des fins d’applications au sein de matériaux fonctionnels. Pour ce faire, les différentes voies de synthèse des hydroxyamidines et de leurs amidines correspondantes qui ont précédemment été étudiées par les membres du groupe seront tout d’abord perfectionnées, puis investiguées afin de déterminer leur versatilité. Ensuite, les propriétés de complexation des amox résultantes comportant des motifs sélectionnés seront déterminées pour enfin étudier les propriétés photophysiques et électrochimiques d’une série de complexes de métaux de transition de la première rangée. En somme, plusieurs designs qu’offrent les amox et bis-amox sont étudiés et les propriétés des architectures résultantes de leur auto-assemblage sont déterminées. / In a context where energy supply represents a major challenge for countries and organizations with emerging and developed economies, the search for new renewable resources and the democratization of energy vectors allowing sustainable worldwide supply is a responsibility for the international scientific community. Besides, it would be essential that the many disciplines of chemistry concerted their efforts. In particular, the growth of research in coordination chemistry oriented toward artificial photosynthesis and the development of functional materials demonstrates the undeniable importance of this field of research. The first part of the work presents different synthetic routes to hydroxyamidines, a chelating ligand with promising properties and receiving very little attention from the scientific community. Secondly, we present the development of a strategy of assembly of their supramolecular complexes involving abundant and cheap first row transition metal. Thirdly, we will discuss the investigation of their photophysical and electrochemical properties for their purposes in functional materials applications. To do this, the different synthesis routes of hydroxyamidines and their corresponding amidines which have previously been studied by other members of the group will first be improved then investigated to determine their versatility. Next, the complexing properties of the resulting amox having selected patterns will be determined to finally study the photophysical and electrochemical properties of a series of first row transition metal complexes. In sum, the various designs offered by amox and the bis-amox complexes are studied and the properties of the resulting architectures of their self-assemblies are determined. Hydroxyamidine Synthèse de ligand Amidine Ligand bidentate Ligand pontant Ligand bis-bidentate PPSE m-CPBA N,O ligand Polymère de coordination Transfert d’électron Photophysique Électrochimie Nickel Cuivre Cobalt Classification Robin-Day Ligand innocent Valence mixte Ligand synthesis Bidentate ligand Bridging ligand Bis-bidentate ligand Coordination polymer Electron transfer Photophysic Electrochemistry Density Functional Theory Robin-Day classification Innocent ligand Mixed valence
394	Emulsion polymerization in the presence of reactive PEG-based hydrophilic chains for the design of latex particles promoting interactions with cellulose derivatives / Polymérisation en émulsion en présence de chaînes polymères hydrophiles réactives à base de PEG pour la conception de particules de latex permettant des interactions avec des dérivés cellulosiques Griveau, Lucie 07 December 2018 (has links) Dans cette thèse, des particules de polymère fonctionnalisées en surface avec des groupes poly (éthylène glycol) (PEG) ont été synthétisées pour favoriser leur interaction avec les dérivés cellulosique via liaisons hydrogène intermoléculaires. Deux voies de synthèse ont été proposées pour obtenir ses composites cellulose/latex.La première voie est basée sur l'auto-assemblage induit par polymérisation (PISA) pour former des nanoparticules fonctionnalisées avant leur adsorption sur un substrat cellulosique. La PISA tire profit de la formation de copolymères blocs amphiphiles dans l'eau en combinant la polymérisation en émulsion avec les techniques de polymérisation radicalaire contrôlées (RDRP). Ces dernières sont utilisées pour synthétiser des polymères hydrophiles agissant à la fois comme précurseur pour la polymerization en émulsion d'un monomère hydrophobe, et comme stabilisant des particules de latex obtenues. Deux techniques de RDRP ont été étudiées : les polymérisations RAFT et SET-LRP. Des polymères hydrophiles à base de PEG de faible masse molaire ont été synthétisés en utilisant ses deux techniques qui sont ensuite utilisés pour la polymérisation d'un bloc hydrophobe dans l'eau. Le transfert de l'agent de contrôle au site de la polymérisation était difficile en utilisant la SET-LRP en émulsion, conduisant à la formation de larges particules. En utilisant la RAFT en émulsion, des particules nanométriques ont été obtenues, avec un changement morphologique observé en fonction de la taille du segment hydrophobe, puis adsorbées sur des nanofibrilles de cellulose (CNF).La seconde voie utilise la polymérisation en émulsion classique réalisée en présence de nanocristaux de cellulose (CNC) conduisant à une stabilisation Pickering des particules de polymère. L'interaction cellulose/particule est assurée grâce à l'ajout d’un comonomère à type PEG. Une organisation a été visualisé dans laquelle plusieurs particules de polymère recouvrent chaque CNC / In this thesis, polymer particles surface-functionalized with poly(ethylene glycol) (PEG) groups were synthesized to promote their interaction with cellulose derivatives via intermolecular hydrogen bond. Two synthetic routes were proposed to obtain such cellulose/latex composites.The first route was based on the polymerization-induced self-assembly (PISA) to form functionalized polymer nanoparticles prior to adsorption onto cellulosic substrate. PISA takes advantage of the formation of amphiphilic block copolymers in water by combining emulsion polymerization with reversible-deactivation radical polymerization (RDRP) techniques. The latter were used to synthesize well-controlled hydrophilic polymer chains, acting as both precursor for the emulsion polymerization of a hydrophobic monomer, and stabilizer of the final latex particles. Two RDRP techniques were investigated: reversible addition-fragmentation chain transfer (RAFT), and single electron transfer-living radical polymerization (SET-LRP). Low molar mass PEG-based hydrophilic polymers have been synthesized using both techniques, used for the polymerization of a hydrophobic block in water. The transfer of controlling agent at the locus of the polymerization was challenging for SET-LRP in emulsion conditions leading to surfactant-free large particles. Nanometric latex particles were obtained via RAFT-mediated emulsion polymerization, with morphology change from sphere to fibers observed depending on the size of the hydrophobic segment, which were then able to be adsorbed onto cellulose nanofibrils (CNFs).The second route used conventional emulsion polymerization performed directly in presence of cellulose nanocrystals (CNCs) leading to Pickering-type stabilization of the polymer particles. Cellulose/particle interaction was provided thanks to the addition of PEG-based comonomer. Original organization emerged where CNCs were covered by several polymer particles Poly(éthylène glycol) (PEG) Polymerisation en émulsion Nanofibrilles de cellulose (CNF) Nanocristaux de cellulose (CNC) Poly(ethylene glycol) (PEG) Emulsion polymerization Cellulose nanofibrils (CNFs) Cellulose nanocrystals (CNCs) 540
395	Identifikation von Genen und Mikroorganismen, die an der dissimilatorischen Fe(III)-Reduktion beteiligt sind / Isolation of Genes and Microorganisms Involved in Dissimilatory Fe(III)-Reduction Özyurt, Baris 21 January 2009 (has links) No description available. 500 Naturwissenschaften allgemein Mathematics and Computer Science Metagenomik dissimilatorische Fe(III)-Reduktion Dissimilatory iron reduction DIR dissimilatory oxido-reduction of iron dissimilatory iron(III) reduction metal reduction ferricironreduction microbial iron respiration bacterial respiration microorganisms for energy production dissimilatory iron reducing bacteria dissimilatory metal reducing bacteria DMRB energy production electricity energy transduction microbial electricity electron donor electron acceptor electron transfer carbon source carbohydrate mannit mannitol biofilm mineral mineral formation microbial degradation ribosomal proteins cytochromes hypothetical proteins enzymes oxidation reduction ferric iron iron oxide Fe(II) Fe(III) soluble iron insoluble iron ferric reductase activity iron mineral formation mineralisation <i>E. coli</i> Escherichia coli environmental microorganisms life in extreme environments uncultivable bacteria soil microbial ecology anaerobic growth anaerobic incubation environmental sequences environmental DNA DNA extraction functional screening metagenomic metagenome meta-genome microbial ecology environmental genomics soil metagenome BACs sequencing bioinformatics microbial communities 16S rRNA phylogenetics 30 42.30 42.30 58.30 42.49 58.30 42.13 RA W
396	Electron Transfer and Other Reactions Using Atomic Metal Anions Butson, Jeffery M. 04 February 2014 (has links) The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-. Metal Anion Metal Anion Atomic Atomic Metal Anion Atomic Metals Atomic Metal Anions Anions Metals Mass Spectrometer Triple Quadrupole Rb Cs Fe Cu Ag Cs- Rb- Fe- Cu- Ag- pentafluoroaniline pentafluorophenol nitrogen dioxide sulfur dioxide nitrogen oxide nitrogen monoxide oxygen oxalic oxalic acid gas phase electrospray ionization electrospray ionization electro-spray ionization electro-spray hexafluorobenzene 1,2,3-trifluorobenzene 1,2,4-trifluorobenzene 1,3,5-trifluorobenzene fluorine E-octafluoro-butene octafluoro-butene octafluoro butene CBS-4M abstraction hydrogen abstraction fluorine abstraction hydride fluoride metal hydride metal fluoride caesium fluoride rubidium fluoride iron fluride copper fluoride rubidium caesium iron copper silver iron anion copper anion rubidium anion caesium anion silver anion cesium cesium anion atomic caesium anion atomic cesium anion atomic rubidium anion atomic iron anion atomic copper anion atomic silver anion 1,2,3 trifluorobenzene 1,2,4 trifluorobenzene 1,3,5 trifluorobenzene copper fluoride anion iron fluoride anion copper difluoride copper difluoride anion iron difluoride iron difluoride anion iron trifluoride iron trifluoride anion cesium fluoride cesium fluoride anion caesium difluoride anion caesium difluoride cesium difluoride cesium difluoride anion caesium fluoride anion nitrogen monoxide anion sulfur dioxide anion nitrogen dioxide anion copper oxide copper oxide anion copper dioxide copper dioxide anion iron oxide iron oxide anion iron dioxide iron dioxide anion iron trioxide iron trioxide anion electron transfer
397	Electron Transfer and Other Reactions Using Atomic Metal Anions Butson, Jeffery M. January 2014 (has links) The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-. Metal Anion Metal Anion Atomic Atomic Metal Anion Atomic Metals Atomic Metal Anions Anions Metals Mass Spectrometer Triple Quadrupole Rb Cs Fe Cu Ag Cs- Rb- Fe- Cu- Ag- pentafluoroaniline pentafluorophenol nitrogen dioxide sulfur dioxide nitrogen oxide nitrogen monoxide oxygen oxalic oxalic acid gas phase electrospray ionization electrospray ionization electro-spray ionization electro-spray hexafluorobenzene 1,2,3-trifluorobenzene 1,2,4-trifluorobenzene 1,3,5-trifluorobenzene fluorine E-octafluoro-butene octafluoro-butene octafluoro butene CBS-4M abstraction hydrogen abstraction fluorine abstraction hydride fluoride metal hydride metal fluoride caesium fluoride rubidium fluoride iron fluride copper fluoride rubidium caesium iron copper silver iron anion copper anion rubidium anion caesium anion silver anion cesium cesium anion atomic caesium anion atomic cesium anion atomic rubidium anion atomic iron anion atomic copper anion atomic silver anion 1,2,3 trifluorobenzene 1,2,4 trifluorobenzene 1,3,5 trifluorobenzene copper fluoride anion iron fluoride anion copper difluoride copper difluoride anion iron difluoride iron difluoride anion iron trifluoride iron trifluoride anion cesium fluoride cesium fluoride anion caesium difluoride anion caesium difluoride cesium difluoride cesium difluoride anion caesium fluoride anion nitrogen monoxide anion sulfur dioxide anion nitrogen dioxide anion copper oxide copper oxide anion copper dioxide copper dioxide anion iron oxide iron oxide anion iron dioxide iron dioxide anion iron trioxide iron trioxide anion electron transfer

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