Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Theoretical Study of Enzyme Promiscuity: Mechanisms of Hydration and Carboxylation Activities of Phenolic Acid Decarboxylase
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Number of Authors: 2
2017 (English)In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 7, no 3, 1733-1741 p.Article in journal (Refereed) Published
Abstract [en]

The cofactor-free phenolic acid decarboxylases (PADs) catalyze the nonoxidative decarboxylation of phenolic acids to their corresponding p-vinyl derivatives. Since these compounds are useful industrially, PADs have potential applications as biocatalysts. Recently, PADs have been reported to also catalyze the hydration and carboxylation of hydroxystyrenes, increasing further their biocatalytic utility. We have used quantum chemical methodology to investigate the detailed mechanisms of both promiscuous reactions. A large model of the active site is designed starting from the crystal structure of PAD from Bacillus subtilis. The calculations suggest new mechanisms, quite different from the literature proposals. For the carboxylation reaction, a carbon dioxide molecule is proposed to be generated from bicarbonate first and then act as the source for the carboxylate group of the product. For the hydration activity, the reaction is suggested to start with the formation of a quinone methide intermediate by protonation of the C=C double bond of the p-vinylphenol substrate. A water molecule then attacks the alpha-carbon to generate the alcohol product. The enantioselectivity of the hydration reaction is also investigated in this study, and the calculations are able to reproduce and rationalize the observed experimental outcome.

Place, publisher, year, edition, pages
2017. Vol. 7, no 3, 1733-1741 p.
Keyword [en]
reaction mechanism, enantioselectivity, enzyme promiscuity, density functional theory, quantum chemistry, cluster approach
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-142485DOI: 10.1021/acscatal.6b03249ISI: 000395726500028OAI: oai:DiVA.org:su-142485DiVA: diva2:1095960
Available from: 2017-05-16 Created: 2017-05-16 Last updated: 2017-05-16Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Sheng, XiangHimo, Fahmi
By organisation
Department of Organic Chemistry
In the same journal
ACS Catalysis
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 175 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf