Reactivity of the binuclear non-heme iron active site of delta(9) desaturase studied by large-scale multireference ab initio calculations

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F14%3A00436895" target="_blank" >RIV/61388963:_____/14:00436895 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/14:00436895

Výsledek na webu

<a href="http://dx.doi.org/10.1021/ja506934k" target="_blank" >http://dx.doi.org/10.1021/ja506934k</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/ja506934k" target="_blank" >10.1021/ja506934k</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Reactivity of the binuclear non-heme iron active site of delta(9) desaturase studied by large-scale multireference ab initio calculations

Popis výsledku v původním jazyce

The results of density matrix renormalization group complete active space self-consistent field (DMRG-CASSCF) and second-order perturbation theory (DMRG-CASPT2) calculations are presented on various structural alternatives for the OO and first CH activating step of the catalytic cycle of the binuclear nonheme iron enzyme Delta(9) desaturase. This enzyme is capable of inserting a double bond into an alkyl chain by double hydrogen (H) atom abstraction using molecular O-2. The reaction step studied here ispresumably associated with the highest activation barrier along the full pathway; therefore, its quantitative assessment is of key importance to the understanding of the catalysis. The DMRG approach allows unprecedentedly large active spaces for the explicit correlation of electrons in the large part of the chemically important valence space, which is apparently conditio sine qua non for obtaining well-converged reaction energetics. The derived reaction mechanism involves protonation of

Název v anglickém jazyce

Reactivity of the binuclear non-heme iron active site of delta(9) desaturase studied by large-scale multireference ab initio calculations

Popis výsledku anglicky

The results of density matrix renormalization group complete active space self-consistent field (DMRG-CASSCF) and second-order perturbation theory (DMRG-CASPT2) calculations are presented on various structural alternatives for the OO and first CH activating step of the catalytic cycle of the binuclear nonheme iron enzyme Delta(9) desaturase. This enzyme is capable of inserting a double bond into an alkyl chain by double hydrogen (H) atom abstraction using molecular O-2. The reaction step studied here ispresumably associated with the highest activation barrier along the full pathway; therefore, its quantitative assessment is of key importance to the understanding of the catalysis. The DMRG approach allows unprecedentedly large active spaces for the explicit correlation of electrons in the large part of the chemically important valence space, which is apparently conditio sine qua non for obtaining well-converged reaction energetics. The derived reaction mechanism involves protonation of

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GA14-31419S" target="_blank" >GA14-31419S: Počítačový design minimalistických metalopeptidů jako cesta k rozluštění katalytické účinnosti metaloproteinů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2014

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

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Svazek periodika

136

Číslo periodika v rámci svazku

45

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

15

Strana od-do

15977-15991

Kód UT WoS článku

000344906100037

EID výsledku v databázi Scopus

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