Projects per year
Abstract
Understanding the mechanisms of enzymatic
hydride transfer with nicotinamide coenzyme
biomimetics (NCBs) is critical to the enhanced performance
of nicotinamide coenzyme dependent biocatalyts.
Here the temperature dependence of kinetic isotope effects
(KIEs) for hydride transfer between “Better than
Nature” nicotinamide coenzyme biomimetics and several
ene reductase (ER) biocatalysts is used to indicate
transfer by quantum mechanical tunneling (QMT). A
strong correlation between rate constants and the temperature
dependence of the KIE (ΔΔH‡) for H/D transfer
implies that faster reactions with NCBs are associated
with enhanced donor-acceptor distance sampling. Our
analysis provides the first mechanistic insight into how
NCBs can outperform their natural counterparts and emphasizes
the need to optimize donor-acceptor distance
sampling to obtain high catalytic performance from Htransfer
enzymes.
hydride transfer with nicotinamide coenzyme
biomimetics (NCBs) is critical to the enhanced performance
of nicotinamide coenzyme dependent biocatalyts.
Here the temperature dependence of kinetic isotope effects
(KIEs) for hydride transfer between “Better than
Nature” nicotinamide coenzyme biomimetics and several
ene reductase (ER) biocatalysts is used to indicate
transfer by quantum mechanical tunneling (QMT). A
strong correlation between rate constants and the temperature
dependence of the KIE (ΔΔH‡) for H/D transfer
implies that faster reactions with NCBs are associated
with enhanced donor-acceptor distance sampling. Our
analysis provides the first mechanistic insight into how
NCBs can outperform their natural counterparts and emphasizes
the need to optimize donor-acceptor distance
sampling to obtain high catalytic performance from Htransfer
enzymes.
| Original language | English |
|---|---|
| Journal | Journal of the American Chemical Society |
| Volume | 138 |
| Issue number | 35 |
| Early online date | 23 Aug 2016 |
| DOIs | |
| Publication status | Published - 2016 |
Fingerprint
Dive into the research topics of 'Donor–Acceptor Distance Sampling Enhances the Performance of “Better than Nature” Nicotinamide Coenzyme Biomimetics.'. Together they form a unique fingerprint.Projects
- 1 Finished
-
Manchester Synthetic Biology Research Centre for Fine and Speciality Chemicals
Scrutton, N. (PI), Azapagic, A. (CoI), Balmer, A. (CoI), Barran, P. (CoI), Breitling, R. (CoI), Delneri, D. (CoI), Dixon, N. (CoI), Faulon, J.-L. (CoI), Flitsch, S. (CoI), Goble, C. (CoI), Goodacre, R. (CoI), Hay, S. (CoI), Kell, D. (CoI), Leys, D. (CoI), Lloyd, J. (CoI), Lockyer, N. (CoI), Martin, P. (CoI), Micklefield, J. (CoI), Munro, A. (CoI), Pedrosa Mendes, P. (CoI), Randles, S. (CoI), Salehi Yazdi, F. (CoI), Shapira, P. (CoI), Takano, E. (CoI), Turner, N. (CoI) & Winterburn, J. (CoI)
14/11/14 → 13/05/20
Project: Research