Global ETD Search
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Showing 1 to 20 of 36 for “"PCET"”.
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Mechanistic Studies of Interfacial Proton-Coupled Electron Transfer to Molecularly Defined Surface Sites
… interfacial proton-coupled electron transfer (I PCET) reaction. Whether as an intermediate step in electrocatalysis or a stoichiometric charging step in a psuedocapacitor, regardless if involved in product formation or solution degradation, I PCET can occur in any protic electrolyte. Despite …
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Proton-coupled electron transfer : from basic principles to small molecule activation
Proton-coupled electron transfer (PCET) is the basic mechanism for bioenergetic conversion. Hallmark examples of such reactivities include water oxidation which is coupled to photosynthesis and oxygen reduction which is coupled to ATP generation by respiration. These two complementary energy …
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Proton-coupled electron transfer in molecular and material catalysis
Proton-coupled electron transfer (PCET) plays an important role in a variety of electrochemical and photo-excited reactions occurring in molecular, material, and biological systems. In this thesis, the role of PCET in hydrogen evolution molecular electrocatalysts, and iron-doped nickel-oxyhydroxide …
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Spectroscopic investigation of photo-induced proton-coupled electron transfer and Dexter energy transfer in model systems
… photo-induced proton coupled electron transfer (PCET) and proton-coupled (through-bond) energy transfer (PCEnT) are presented. PCET is ubiquitous in Nature, where it is at the heart of bioenergy conversion and catalysis (Chapter I). Systems of relevance to mechanistic studies of PCET and PCEnT …
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Small-molecule activation chemistry catalyzed by proton-coupled electron transfer
Proton-coupled electron transfer (PCET) is the basic mechanism for bioenergetic conversion. Consummate examples include water oxidation in photosynthesis and oxygen reduction in respiration. Despite the importance of PCET in such catalytic bond-making and bond-breaking reactions, the underlying …
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Kinetics and dynamics controlling proton-coupled electron transfer in ribonucleotide reductase
Proton-coupled electron transfer (PCET) reactions comprise a fundamental mechanism for energy transduction in nature. In catalyzing the conversion of ribonucleotides to deoxyribonucleotides, ribonucleotide reductase (RNR) performs reversible, long-range PCET over a pathway of redox active amino …
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Photochemical ribonucleotide reductase for the study of proton-coupled electron transfer
… with proton-coupled electron transfer (PCET), which intrinsically is a quantum mechanical effect as both the electron and proton tunnel. The caveat to PCET is that proton transfer (PT) is fundamentally limited to short distances relative to electron transfer (ET). This predicament is …
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Photoinitiated proton-coupled electron transfer and radical transport kinetics in class la ribonucleotide reductase
Proton-coupled electron transfer (PCET) is a critical mechanism in biology, underpinning key processes such as radical transport, energy transduction, and enzymatic substrate activation. Ribonucleotide reductases (RNRs) rely on PCET to mediate the rate-limiting step in the synthesis of DNA …
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Electron-proton nonadiabaticity: characterization and development of non-Born-Oppenheimer electronic structure methods
… such as proton-coupled electron transfer (PCET), which are integral to various electrocatalytic applications and bioenzymatic processes. The breakdown of the Born-Oppenheimer approximation between electronic and nuclear motions engenders the need for accurate characterization of the degree …
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Mechanistic studies of photo-induced proton-coupled electron transfer and oxygen atom transfer reactions in model systems
… photo-induced proton-coupled electron transfer (PCET) and oxygen atom transfer (OAT) reactions, both of which are important to energy conversion chemistry (Chapter I). The effect of coupling proton transfer (PT) to electron transfer (ET) depends on their spatial configuration, thus model PCET …
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Access policy and practice in further and higher education: investigating “success” as access turns into widening participation
… on post compulsory education and training (PCET) of the 1970s and 80s and even from earlier periods. This research focuses on the underrepresented student experience and perceptions of success within the PCET system. It uses a mainly qualitative approach to analyse the experience of staff …
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Proton-coupled electron transfer reactions in bio-inspired catalysis
… Often proton-coupled electron transfer (PCET) is central to the interconversion of energy. Consequently, understanding the role of PCET in the mechanisms of bio-inspired catalysts can aid in the design of next generation catalysts and the elucidation of guiding design principles. In …
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Theoretical studies of proton-coupled electron transfer in interfacial and photochemical energy conversion processes
… of proton-coupled electron transfer (PCET) reactions in electro- and photochemical energy conversion processes are presented. A Co complex that performs highly selective, low-overpotential oxygen reduction to hydrogen peroxide was analyzed with density functional theory calculations. …
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Mechanistic studies of proton-coupled electron transfer in aminotyrosine- and fluorotyrosine- substituted class Ia Ribonucleotide reductase
… of reversible proton-coupled electron transfer (PCET) to propagate a stable tyrosyl radical (Yi22-) in P2 over a distance of >35 A to an active site cysteine (C4 3 9) in a2 on each turnover. Generation of the cysteinyl radical (C4 3 9-) initiates active site nucleotide reduction. Radical …
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Mechanistic studies of the class I ribonucleotide reductases from S. cerevisiae and E. coli.
… step prior to proton-coupled electron transfer (PCET), nucleotide reduction, and reverse PCET. These results provide a crucial first step in understanding radical initiation over 35 [angstroms].
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Transuranic Imidophosphorane Chemistry
… a firstorder proton-coupled electron transfer (PCET) reaction and we demonstrate PCET reactivity as a measure of covalency for this imidophosphorane family.
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Theoretical study of the cytochrome bc1 complex reaction mechanism
… as a proton-coupled electron transfer (PCET) reaction, we focused our efforts on obtaining the reaction rate constant. For this purpose, we established the adiabaticity of the PCET reaction, as well as other parameters. These included the vibronic couplings (electronic coupling and …
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Mechanistic investigations of the radical transport pathway in fluorotyrosine-substituted class Ia ribonucleotide reductases
… via multiple proton-coupled electron transfer (PCET) steps through conserved aromatic amino acid residues: Y₁₂₂* <-> [W₄₈] <-> Y₃₅₆ in [beta]2 to Y₇₃₁ <-> Y₇₃₀ <-> C₄₃₉ in [alpha]2. The transient C₄₃₉* is responsible for initiating nucleotide reduction. Long-range radical transport (RT) and …
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Mechanistic investigations of the radical initiation pathway of class I ribonucleotide reductase from Escherichia coli
… long-range proton-coupled electron transfer (PCET) pathway over 35 A. This pathway is thought to involve specific amino acid radical intermediates (Y22-> W48-> Y356 within R2 to Y731-> Y730-> C439 within R1). In an effort to study radical initiation, we used intein technology to …
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Building model systems to understand Proton-Coupled Electron Transfer in heme : spectroscopic investigation of charge transfer to axially bound diimide acceptors
Proton-Coupled Electron Transfer (PCET) is an important mechanistic motif in chemistry, which allows for efficient charge transport in many biological systems. We seek to understand how the proton and electron motions are coupled in a bidirectional system allowing for individual turning of the …
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