PCET proton-coupled electron

ACP = acyl carrier protein ACPA D = ACPA desat-urase AlkB = octane 1-monooxygenase AOX = alternative oxidase DMQ hydroxylase = 5-demethoxyquinone hydroxylase EXAFS = extended X-ray absorption fine structure spectroscopy FMN = flavin mononucleotide FprA = flavoprotein A (flavo-diiron enzyme homologue) Hr = hemerythrin MCD = magnetic circular dichroism MME hydroxylase = Mg-protophorphyrin IX monomethyl ester hydroxylase MMO = methane monooxygenase MMOH = hydroxylase component of MMO NADH = reduced nicotinamide adenine dinucleotide PAPs = purple acid phosphatases PCET = proton-coupled electron transfer, PTOX = plastid terminal oxidase R2 = ribonucleotide reductase R2 subunit Rbr = rubrerythrin RFQ = rapid freeze-quench RNR = ribonucleotide reductase ROO = rubredoxin oxygen oxidoreductase XylM = xylene monooxygenase. 

The reported work by Nocera and coworkers concerning the dissolution and redeposition of MnO to form self-healing stable electrocatalysts under acidic, neutral, and basic conditions not only supported that manganese(iii) underwent disproportionation in acidic medium, whereas the one-electron-one-proton PCET (proton-coupled electron transfer) pathway is dominant under alkaline conditions, but resulted in a Tafel slope of 60 mV dec in alkaline pH regime.Apart from the usually discussed overpotential of electrochemical water oxidation, the kinetics of the reaction has also been considered for an efficient electrocatalyst. It is well known that the higher the Tafel slope value, the higher the energy needed to reach maximum current density. 

Comproportionation between cA-RuIV(bpy)2(py)02 + and cis- Run(bpy)2(py)(H20)2+ takes place by proton-coupled electron transfer (PCET) and exhibits a KIE of 16.1. Other PCET reactions of these and related ruthenium and osmium complexes also feature large KIEs. For example, oxidations of H202 by RuIV(bpy)2 (py)O2 + and by Ruin(bpy)2(py)OH2 + have KIEs of22.1 and 16.7, respectively. Oxidation of benzyl... 

The tris-carbene ligand family with fac geometry points its three wingtip groups downwards around the metal shielding it effectively from the approach of any but small substrates. Its main application is therefore the activation of small molecules, including the activation of dioxygen and proton coupled electron transfer (PCET), a reaction normally performed by certain enzymes [70,71],... 

The original reaction is between a MnOH species and a tyrosine radical forming a MnO moiety. The process is known as a proton coupled electron transfer (PCET) and this reaction step is modelled by the process depicted in Figure 3.131. 

In 2001, Itoh and coworkers reexplored the mechanism of ortAo-phenol hydroxylations using [ Cu°(L ) 2(02)] " (7, Figure 10). This complex contains a deutero-benzyl-amine moiety, and can undergo hgand auto-oxidation, forming benzaldehyde, through a proton-coupled electron transfer (PCET) reaction with the peroxo ligand. 

RNRs catalyze the reduction of ribonucleotides to deoxyribonucleotides, which represents the first committed step in DNA biosynthesis and repair.These enzymes are therefore required for all known life forms. Three classes of RNRs have been identified, all of which turn out to be metalloenzymes. The so-called class I RNRs contain a diiron site (see Cobalt Bn Enzymes Coenzymes and Iron-Sulfur Proteins for the other two types of RNRs). As diagrammed in Figure 5, these enzymes generate first a tyrosyl radical proximal to the diiron site in the protein subunit labeled R2, and then a thiyl radical in an adjacent subunit (Rl) that ultimately abstracts a hydrogen atom from the ribonucleotide substrate. This controlled tyrosine/thiol radical transfer must occur over an estimated distance of 35 A, and a highly choreographed proton-coupled electron transfer (PCET) mechanism across intervening aromatic residues has been proposed. Perhaps, even more remarkably,... 

Proton-coupled electron transfer (PCET) reactions play a vital role in a wide range of chemical and biological processes. For example, PCET is required for the conversion of energy in photosynthesis [1] and respiration [2], In particular, the coupling between proton motion and electron transfer is involved in the pumping of protons across biological membranes in photosynthetic reaction centers [1] and in the conduction of electrons in cytochrome c [3]. In addition to biological processes, PCET is also important in electrochemical processes [4, 5] and in solid state materials [6]. 

Figure 7. Proposed proton-coupled electron transfer (PCET) pathway between the R2 and R1 subunits of the E. coli ribonucleotide reductase (RNR) complex. The conserved amino acids are shown schematically E. coli numbering).

Hammes-Schiffer expounds in Ch. 16 her group s theoretical formulation for proton-coupled electron transfer (PCET) mechanism and rates, pointing out the similarities with the separate spedal limits of electron transfer and (tunneling) proton transfer, and emphasizing the new features of PCET. The latter include the... 

Aminyl radicals have also been detected indirectly during the reaction of hydroxyl radicals (HO ) or their conjugated base ( 0 ) with the free amino group of amino acids (Reactions (3.9) and (3.10)) [40-43], and identified by time-resolved EPR experiments [44]. Similar reactions may be expected for peptides. While Reactions (3.9) and (3.10) show a net hydrogen transfer, they likely proceed via a stepwise electron-transfer and proton-transfer (Reaction (3.11)), a reaction commonly referred to as proton-coupled electron transfer (PCET). Proton transfer from the ami-nium radical cation to the base (OH ) will likely occur within the solvent cage. 

Oxidative cleavage can occur with some radicals, such as when H02 is oxidized to 02 + H +. Oxidative cleavage of H02 is actually a form of proton-coupled electron transfer (PCET), discussed below. It occurs in the reaction of H02 with Cu2 +, 32 Ce4 +, Am4+, various Ni(III) complexes, and [Ru(bpy)3]3 +, 19... 

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