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#2Yingming WangH-Index: 6
Last. Lin ZhuangH-Index: 56
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The understanding of the electrode-polyelectrolyte interface is important for the development of devices using polyelectrolyte, such as polymer electrolyte fuel cells (PEFCs), solid polymer electrolyte water electrolyzers and CO2 reduction eletrolyzers. In the past decade, the invention of shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) has greatly widened the application of surface-enhanced Raman spectroscopy (SERS) on the electrode-solution interface research, but the study o...
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The nonheme iron(IV)-oxido complex trans-N3-[(L1)FeIV=O(Cl)]+, where L1 is a derivative of the tetradentate bispidine 2,4-di(pyridine-2-yl)-3,7-diazabicyclo[3.3.1]nonane-1-one, has an S = 1 electronic ground state and is the most reactive nonheme iron model system known so far, of a similar order of reactivity as nonheme iron enzymes (C-H abstraction of cyclohexane, 90 °C (propionitrile), t1/2 = 3.5 sec). The reaction with cyclohexane selectively leads to chlorocyclohexane, but “cage escape” at...
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The concept of “OXO-WALL” was conceived about 60 years ago by Harry B. Gray, which is found to be related to the non-existence of high-valent M-Oxo species in +IV oxidation state in a tetragonal geometry beyond group 8 in the periodic table. Several efforts have been made in the past decades to test and find examples that violate this theory. Several claims of violation in the past were attributed to the difference in the geometries/coordination number and, therefore, these are not examples of t...
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#1David ParkerH-Index: 88
#2Jack D. FradgleyH-Index: 4
Last. Matthieu StarckH-Index: 12
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The relative sensitivity of structurally related Eu(III) complexes to quenching by electron and energy transfer processes has been compared. In two sets of 9-coordinate complexes based on 1,4,7-triazacyclonane, the Eu emission lifetime decreased as the number of conjugated sensitising groups and the number of unbound ligand N atoms increased, consistent with photoinduced electron transfer to the excited Eu(III) ion that is suppressed by N-protonation. Quenching of the Eu 5D0 excited state may al...
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#1Sk AmanullahH-Index: 6
#2Paramita SahaH-Index: 3
Last. Abhishek DeyH-Index: 47
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Iron porphyrins are synthesized by systematically introducing electron withdrawing groups (EWGs) on pyrroles to evaluate the relationship between rate (k) and overpotential (η). The results indicate that while EWGs lead to a rise in the thermodynamic FeIII/II reduction potential (E0), the potential of O2 reduction reaction (ORR) does not scale with E0. More importantly, the iron porphyrins with higher E0 shows an order of magnitude higher rate of ORR than unsubstituted iron tetraphenyl porphyrin...
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Methanotrophic bacteria utilize methane monooxygenase (MMO) to carry out the first step in metabolizing methane. The soluble enzymes employ a hydroxylase component (sMMOH) with a nonheme diiron active site that activates O2 and generates a powerful oxidant capable of converting methane to methanol. It is proposed that the diiron(II) center in the reduced enzyme reacts with O2 to generate a diferric-peroxo intermediate called P that then undergoes O–O cleavage to convert into a diiron(IV) derivat...
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#1Peter J. LindleyH-Index: 2
#2Alison ParkinH-Index: 25
Last. Paul H. WaltonH-Index: 35
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The active site of the polysaccharide-degrading lytic polysaccharide monooxygenase (LPMO) enzymes features a single copper ion coordinated by a histidine brace. The primary coordnation sphere of the copper contains several ligating atoms which are bonded to ionisable protons (e.g. OH2, NH2), the pKas of which are unknown. Using a combination of CW-EPR X-band spectroscopy over a range of pH and DFT calculations, we show that the active site of a chitin-active AA10 LPMO can exist in three differen...
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This article is based on the Concluding Remarks lecture given at the Faraday Discussion meeting on Peptide-Membrane Interactions, held online, 8-10th September 2021
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#2Anca PordeaH-Index: 12
Last. Christof M. JägerH-Index: 15
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Artificial metalloenzymes (ArMs) confer non-biological reactivities to biomolecules, whilst taking advantage of the biomolecular architecture in terms of selectivity and of renewable origin. In particular, ArMs design by supramolecular anchoring of metal catalysts to protein hosts provide flexible and easy to optimise systems. The use of cofactor dependent enzymes as hosts gives the advantage of both a (hydrophobic) binding site for the substrate and a cofactor pocket to accommodate the catalyst...
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#1Hiroki OnodaH-Index: 5
#2Shota TanakaH-Index: 2
Last. Osami ShojiH-Index: 21
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CYP152A1 (Cytochrome P450BSβ) is a fatty acid peroxygenase, which specifically catalyses the oxidation of long-chain fatty acids using hydrogen peroxide as an oxidant. We have found that CYP152A1 possesses catalase activity, which competes with the hydroxylation of long-chain fatty acids, oxidation of non-native substrates, and haem degradation. Using hydrogen peroxide, Compound I of CYP152A1 could not be observed, due to its swift decomposition via catalase activity, where Compound I reacts wit...
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