Hydrogen Abstraction of Camphor Catalyzed by Cytochrome P450cam

A QM/MM Study

Rui Lai, Hui Li

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

A combined quantum mechanics and molecular mechanics (QM/MM, QM = UB3LYP-D3, MM = AMBER) method is used to study the hydrogen abstraction reaction in P450cam catalyzed hydroxylation of camphor in the quartet state. Compared to QM/MM calculations in the literature, this study uses larger basis sets for the most important atoms at the active site and QM/MM Hessian harmonic frequency calculations to determine the standard Gibbs free energy of activation and kinetic isotope effect. The QM/MM covalent boundary is treated with a capping hydrogen atom method, which is simple and robust. An energy barrier of 21.3 kcal/mol and a standard free energy of activation of 16.8 kcal/mol are obtained for this hydrogen abstraction reaction. These values are similar to those reported in the literature, suggesting that when a general protocol is followed, QM/MM results are reproducible. It is found that using a sufficiently large basis set is important to minimize basis set errors.

Original languageEnglish (US)
Pages (from-to)12312-12320
Number of pages9
JournalJournal of Physical Chemistry B
Volume120
Issue number48
DOIs
StatePublished - Dec 8 2016

Fingerprint

Camphor 5-Monooxygenase
Camphor
camphor
cytochromes
Cytochromes
Hydrogen
activation
Mechanics
Proteins
hydrogen
Gibbs free energy
Chemical activation
isotope effect
Amber
quantum mechanics
hydrogen atoms
Atoms
Hydroxylation
Molecular mechanics
Quantum theory

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Hydrogen Abstraction of Camphor Catalyzed by Cytochrome P450cam : A QM/MM Study. / Lai, Rui; Li, Hui.

In: Journal of Physical Chemistry B, Vol. 120, No. 48, 08.12.2016, p. 12312-12320.

Research output: Contribution to journalArticle

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