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A quantum chemical ...
A quantum chemical study of the ω-transaminase reaction mechanism
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- Engelmark Cassimjee, Karim (författare)
- Stockholms universitet,Institutionen för organisk kemi
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- Manta, Bianca (författare)
- Stockholms universitet,Institutionen för organisk kemi
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- Himo, Fahmi (författare)
- Stockholms universitet,Institutionen för organisk kemi
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(creator_code:org_t)
- 2015
- 2015
- Engelska.
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Ingår i: Organic and biomolecular chemistry. - : Royal Society of Chemistry (RSC). - 1477-0520 .- 1477-0539. ; 13:31, s. 8453-8464
- Relaterad länk:
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https://doi.org/10.1...
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https://pubs.rsc.org...
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https://urn.kb.se/re...
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Abstract
Ämnesord
Stäng
- ω-Transaminases are valuable tools in biocatalysis due to their stereospecificity and their broad substrate range. In the present study, the reaction mechanism of Chromobacterium violaceum ω-transaminase is investigated by means of density functional theory calculations. A large active site model is designed based on the recent X-ray crystal structure. The detailed energy profile for the half-transamination of (S)-1-phenylethylamine to acetophenone is calculated and the involved transition states and intermediates are characterized. The model suggests that the amino substrate forms an external aldimine with the coenzyme pyridoxal-5′-phosphate (PLP), through geminal diamine intermediates. The external aldimine is then deprotonated in the rate-determining step, forming a planar quinonoid intermediate. A ketimine is then formed, after which a hemiaminal is produced by the addition of water. Subsequently, the ketone product is obtained together with pyridoxamine-5′-phosphate (PMP). In the studied half-transamination reaction the ketone product is kinetically favored. The mechanism presented here will be valuable to enhance rational and semi-rational design of engineered enzyme variants in the development of ω-transaminase chemistry.
Ämnesord
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
Nyckelord
- organisk kemi
- Organic Chemistry
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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