FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2005696210> ?p ?o ?g. }

• W2005696210 endingPage "981" @default.
• W2005696210 startingPage "973" @default.
• W2005696210 abstract "Chlorite dismutase (Cld) is a heme-dependent enzyme that catalyzes the decomposition of toxic chlorite (ClO2−) into innocuous chloride and O2. In this paper, using the hybrid B3LYP density functional theory (DFT) method including dispersion interactions, the Cld reaction mechanism has been studied with a chemical model constructed on the X-ray crystal structure. The calculations indicate that the reaction proceeds along a stepwise pathway in the doublet state, i.e. a homolytic O–Cl bond cleavage of the substrate leading to an O–Fe(heme) species and a ClO˙ radical, followed by a rebinding O–O bond formation between them. The O–Fe(heme) species is demonstrated to be a low-spin triplet-state Fe(IV)O diradicaloid. A low-spin singlet-state Fe(IV)O is much less stable than the former, with an energy difference of 9.2 kcal mol−1. The O–Cl bond cleavage is rate-limiting with a barrier of 10.6 kcal mol−1, in good agreement with the experimental reaction rate of 2.0 × 105 s−1. Furthermore, a heterolytic O–Cl bond dissociation in the initial step is shown to be unreachable, which ensures the high efficiency of the Cld enzyme by avoiding the generation of chlorate byproduct observed in the reactions of synthetic Fe porphyrins. Also, the pathways in the quartet and sextet states are unfavorable for the Cld reaction. The present results reveal a detailed mechanism III (defined in the text) including an interesting di-radical intermediate composed of a low-spin triplet-state Fe(IV)O and a ClO˙ radical. Compared to a competitive heterolytic Cl–O cleavage in synthetic Fe porphyrins, the revelation of the domination of homolysis in Cld indicates not only the high efficiency of enzyme, but also the sensitivity of a heme and the significance of the enzymatic active-site surroundings (the His170 and Arg183 residues in the present case), which gives more insights into heme chemistry." @default.
• W2005696210 created "2016-06-24" @default.
• W2005696210 creator A5045114803 @default.
• W2005696210 creator A5074195688 @default.
• W2005696210 creator A5083524268 @default.
• W2005696210 date "2014-01-01" @default.
• W2005696210 modified "2023-09-27" @default.
• W2005696210 title "A dominant homolytic O–Cl bond cleavage with low-spin triplet-state Fe(<scp>iv</scp>)O formed is revealed in the mechanism of heme-dependent chlorite dismutase" @default.
• W2005696210 cites W1525122215 @default.
• W2005696210 cites W1965625909 @default.
• W2005696210 cites W1966182479 @default.
• W2005696210 cites W1968400590 @default.
• W2005696210 cites W1970257119 @default.
• W2005696210 cites W1973741311 @default.
• W2005696210 cites W1975163298 @default.
• W2005696210 cites W1975262546 @default.
• W2005696210 cites W1978431190 @default.
• W2005696210 cites W1981072723 @default.
• W2005696210 cites W1982018391 @default.
• W2005696210 cites W1982356449 @default.
• W2005696210 cites W1983106803 @default.
• W2005696210 cites W1993966918 @default.
• W2005696210 cites W1996115908 @default.
• W2005696210 cites W1996309167 @default.
• W2005696210 cites W1998018235 @default.
• W2005696210 cites W1998170982 @default.
• W2005696210 cites W1999089069 @default.
• W2005696210 cites W2000583718 @default.
• W2005696210 cites W2004741748 @default.
• W2005696210 cites W2005401205 @default.
• W2005696210 cites W2009156354 @default.
• W2005696210 cites W2011358384 @default.
• W2005696210 cites W2015388145 @default.
• W2005696210 cites W2023271753 @default.
• W2005696210 cites W2024423513 @default.
• W2005696210 cites W2027994152 @default.
• W2005696210 cites W2030795020 @default.
• W2005696210 cites W2033990154 @default.
• W2005696210 cites W2034289054 @default.
• W2005696210 cites W2036162627 @default.
• W2005696210 cites W2042128296 @default.
• W2005696210 cites W2043929927 @default.
• W2005696210 cites W2044591029 @default.
• W2005696210 cites W2046412723 @default.
• W2005696210 cites W2047601015 @default.
• W2005696210 cites W2048474265 @default.
• W2005696210 cites W2049557754 @default.
• W2005696210 cites W2053023593 @default.
• W2005696210 cites W2054889291 @default.
• W2005696210 cites W2057363122 @default.
• W2005696210 cites W2059045499 @default.
• W2005696210 cites W2060871162 @default.
• W2005696210 cites W2062131561 @default.
• W2005696210 cites W2064246194 @default.
• W2005696210 cites W2065898375 @default.
• W2005696210 cites W2069471905 @default.
• W2005696210 cites W2070366769 @default.
• W2005696210 cites W2073637781 @default.
• W2005696210 cites W2078531329 @default.
• W2005696210 cites W2079108392 @default.
• W2005696210 cites W2079874097 @default.
• W2005696210 cites W2082345487 @default.
• W2005696210 cites W2082373606 @default.
• W2005696210 cites W2086341147 @default.
• W2005696210 cites W2091255526 @default.
• W2005696210 cites W2093377100 @default.
• W2005696210 cites W2095124085 @default.
• W2005696210 cites W2111032848 @default.
• W2005696210 cites W2112862672 @default.
• W2005696210 cites W2115492740 @default.
• W2005696210 cites W2119292856 @default.
• W2005696210 cites W2120968281 @default.
• W2005696210 cites W2131101323 @default.
• W2005696210 cites W2136419697 @default.
• W2005696210 cites W2138989353 @default.
• W2005696210 cites W2140886907 @default.
• W2005696210 cites W2143981217 @default.
• W2005696210 cites W2147899939 @default.
• W2005696210 cites W2154273436 @default.
• W2005696210 cites W2155308177 @default.
• W2005696210 cites W2159746325 @default.
• W2005696210 cites W2162109874 @default.
• W2005696210 cites W2164102479 @default.
• W2005696210 cites W2164626973 @default.
• W2005696210 cites W2169478189 @default.
• W2005696210 cites W2314715282 @default.
• W2005696210 cites W2317736694 @default.
• W2005696210 cites W2320600715 @default.
• W2005696210 cites W2323481972 @default.
• W2005696210 cites W2427298572 @default.
• W2005696210 cites W2952895369 @default.
• W2005696210 cites W2952900127 @default.
• W2005696210 cites W4383700819 @default.
• W2005696210 doi "https://doi.org/10.1039/c3dt52171k" @default.
• W2005696210 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/24162174" @default.
• W2005696210 hasPublicationYear "2014" @default.
• W2005696210 type Work @default.
• W2005696210 sameAs 2005696210 @default.

• next