Stereoelectronic control in carbon-oxygen and phosphorus-oxygen bond breaking processes. ab initio calculations and speculations on the mechanism of action of ribonuclease A, staphylococcal nuclease, and lysozyme

David G. Gorenstein, John B. Findlay, Bruce A. Luxon, Debojyoti Kar

Research output: Contribution to journalArticle

94 Citations (Scopus)

Abstract

Ab initio molecular orbital calculations on dimethyl phosphate monoanion and dimethoxymethane demonstrate that antiperiplanar ester oxygen lone pairs significantly perturb the X-O (X = P or C) bond overlap populations. Specifically molecules in a gauche,trans conformation are "activated" for cleavage of the trans X-O bond. Other consequences of this torsional activation are discussed and presented in the context of a mechanism of action of ribonuclease A, staphylococcal nuclease, and lysozyme.

Original languageEnglish (US)
Pages (from-to)3473-3479
Number of pages7
JournalJournal of the American Chemical Society
Volume99
Issue number10
StatePublished - 1977
Externally publishedYes

Fingerprint

Micrococcal Nuclease
Orbital calculations
Pancreatic Ribonuclease
Molecular orbitals
Muramidase
Phosphorus
Conformations
Esters
Phosphates
Carbon
Enzymes
Chemical activation
Oxygen
Molecules
Population
dimethoxymethane
dimethyl phosphate
Ribonucleases

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Stereoelectronic control in carbon-oxygen and phosphorus-oxygen bond breaking processes. ab initio calculations and speculations on the mechanism of action of ribonuclease A, staphylococcal nuclease, and lysozyme. / Gorenstein, David G.; Findlay, John B.; Luxon, Bruce A.; Kar, Debojyoti.

In: Journal of the American Chemical Society, Vol. 99, No. 10, 1977, p. 3473-3479.

Research output: Contribution to journalArticle

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