FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2069803492> ?p ?o ?g. }

• W2069803492 endingPage "7102" @default.
• W2069803492 startingPage "7094" @default.
• W2069803492 abstract "In this paper we present theoretical calculations on model biomimetic systems for quinol oxidation. In these model systems, an excited-state [Ru(bpy)2(pbim)]+ complex (bpy = 2,2′-dipyridyl, pbim = 2-(2-pyridyl)benzimidazolate) oxidizes a ubiquinol or plastoquinol analogue in acetonitrile. The charge transfer reaction occurs via a proton-coupled electron transfer (PCET) mechanism, in which an electron is transferred from the quinol to the Ru and a proton is transferred from the quinol to the pbim− ligand. The experimentally measured average kinetic isotope effects (KIEs) at 296 K are 1.87 and 3.45 for the ubiquinol and plastoquinol analogues, respectively, and the KIE decreases with temperature for plastoquinol but increases with temperature for ubiquinol. The present calculations provide a possible explanation for the differences in magnitudes and temperature dependences of the KIEs for the two systems and, in particular, an explanation for the unusual inverse temperature dependence of the KIE for the ubiquinol analogue. These calculations are based on a general theoretical formulation for PCET reactions that includes quantum mechanical effects of the electrons and transferring proton, as well as the solvent reorganization and proton donor−acceptor motion. The physical properties of the system that enable the inverse temperature dependence of the KIE are a stiff hydrogen bond, which corresponds to a high-frequency proton donor−acceptor motion, and small inner-sphere and solvent reorganization energies. The inverse temperature dependence of the KIE may be observed if the 0/0 pair of reactant/product vibronic states is in the inverted Marcus region, while the 0/1 pair of reactant/product vibronic states is in the normal Marcus region and is the dominant contributor to the overall rate. In this case, the free energy barrier for the dominant transition is lower for deuterium than for hydrogen because of the smaller splittings between the vibronic energy levels for deuterium, and the KIE increases with increasing temperature. The temperature dependence of the KIE is found to be very sensitive to the interplay among the driving force, the reorganization energy, and the vibronic coupling in this regime." @default.
• W2069803492 created "2016-06-24" @default.
• W2069803492 creator A5037207994 @default.
• W2069803492 creator A5041302371 @default.
• W2069803492 creator A5089895073 @default.
• W2069803492 date "2009-04-07" @default.
• W2069803492 modified "2023-09-27" @default.
• W2069803492 title "Theoretical Analysis of the Unusual Temperature Dependence of the Kinetic Isotope Effect in Quinol Oxidation" @default.
• W2069803492 cites W1633047509 @default.
• W2069803492 cites W1966141392 @default.
• W2069803492 cites W1968276670 @default.
• W2069803492 cites W1972040015 @default.
• W2069803492 cites W1975456658 @default.
• W2069803492 cites W1975982434 @default.
• W2069803492 cites W1976945994 @default.
• W2069803492 cites W1978936677 @default.
• W2069803492 cites W1981844110 @default.
• W2069803492 cites W1984876499 @default.
• W2069803492 cites W1996408951 @default.
• W2069803492 cites W1998906836 @default.
• W2069803492 cites W2004814599 @default.
• W2069803492 cites W2007062401 @default.
• W2069803492 cites W2007933544 @default.
• W2069803492 cites W2010149747 @default.
• W2069803492 cites W2011031998 @default.
• W2069803492 cites W2012661941 @default.
• W2069803492 cites W2013032090 @default.
• W2069803492 cites W2013410957 @default.
• W2069803492 cites W2021502908 @default.
• W2069803492 cites W2022092718 @default.
• W2069803492 cites W2023271753 @default.
• W2069803492 cites W2023657151 @default.
• W2069803492 cites W2031904472 @default.
• W2069803492 cites W2068617439 @default.
• W2069803492 cites W2074399070 @default.
• W2069803492 cites W2079642199 @default.
• W2069803492 cites W2088607843 @default.
• W2069803492 cites W2093061534 @default.
• W2069803492 cites W2095474273 @default.
• W2069803492 cites W2099322728 @default.
• W2069803492 cites W2101221049 @default.
• W2069803492 cites W2112482206 @default.
• W2069803492 cites W2142966903 @default.
• W2069803492 cites W2143981217 @default.
• W2069803492 cites W2148284063 @default.
• W2069803492 cites W2151334055 @default.
• W2069803492 cites W2479406102 @default.
• W2069803492 cites W2614884730 @default.
• W2069803492 cites W4211091797 @default.
• W2069803492 doi "https://doi.org/10.1021/ja9001184" @default.
• W2069803492 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/2710000" @default.
• W2069803492 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19351186" @default.
• W2069803492 hasPublicationYear "2009" @default.
• W2069803492 type Work @default.
• W2069803492 sameAs 2069803492 @default.
• W2069803492 citedByCount "38" @default.
• W2069803492 countsByYear W20698034922012 @default.
• W2069803492 countsByYear W20698034922014 @default.
• W2069803492 countsByYear W20698034922015 @default.
• W2069803492 countsByYear W20698034922016 @default.
• W2069803492 countsByYear W20698034922017 @default.
• W2069803492 countsByYear W20698034922018 @default.
• W2069803492 countsByYear W20698034922019 @default.
• W2069803492 countsByYear W20698034922020 @default.
• W2069803492 countsByYear W20698034922021 @default.
• W2069803492 countsByYear W20698034922022 @default.
• W2069803492 crossrefType "journal-article" @default.
• W2069803492 hasAuthorship W2069803492A5037207994 @default.
• W2069803492 hasAuthorship W2069803492A5041302371 @default.
• W2069803492 hasAuthorship W2069803492A5089895073 @default.
• W2069803492 hasBestOaLocation W20698034922 @default.
• W2069803492 hasConcept C121332964 @default.
• W2069803492 hasConcept C123669783 @default.
• W2069803492 hasConcept C14471203 @default.
• W2069803492 hasConcept C147789679 @default.
• W2069803492 hasConcept C178790620 @default.
• W2069803492 hasConcept C184779094 @default.
• W2069803492 hasConcept C185592680 @default.
• W2069803492 hasConcept C26873012 @default.
• W2069803492 hasConcept C2777463227 @default.
• W2069803492 hasConcept C2778777121 @default.
• W2069803492 hasConcept C2779892579 @default.
• W2069803492 hasConcept C28859421 @default.
• W2069803492 hasConcept C29311851 @default.
• W2069803492 hasConcept C54516573 @default.
• W2069803492 hasConcept C55493867 @default.
• W2069803492 hasConcept C58364064 @default.
• W2069803492 hasConcept C62520636 @default.
• W2069803492 hasConcept C69928629 @default.
• W2069803492 hasConcept C75473681 @default.
• W2069803492 hasConcept C97355855 @default.
• W2069803492 hasConceptScore W2069803492C121332964 @default.
• W2069803492 hasConceptScore W2069803492C123669783 @default.
• W2069803492 hasConceptScore W2069803492C14471203 @default.
• W2069803492 hasConceptScore W2069803492C147789679 @default.
• W2069803492 hasConceptScore W2069803492C178790620 @default.
• W2069803492 hasConceptScore W2069803492C184779094 @default.
• W2069803492 hasConceptScore W2069803492C185592680 @default.

• next