Journal
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
Volume 29, Issue 4, Pages 185-189Publisher
WILEY
DOI: 10.1002/poc.3515
Keywords
catalysis; enzyme design; hydrophobic interactions; Kemp elimination; micelles
Categories
Funding
- Howard Hughes Medical Institute through the Pre-college & Undergraduate Science Education Program
- IDeA grant from NIGMS/NIH [P20GM103499]
- URCA
- MRI from the National Science Foundation [1429308]
- Cottrell College Science Award from Research Corporation for Science Advancement [22490]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1429308] Funding Source: National Science Foundation
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The Kemp elimination is prototypical reaction used to study proton abstraction from carbon. Several hydrophobic systems are known to accelerate this reaction, including two classes of computationally designed enzymes. However, it is unclear whether these computationally designed enzymes establish specific interactions with their substrates, as natural enzymes do, or if most of the rate acceleration is due to the hydrophobicity of the substrate. We used a simple system composed of cationic micelles and a long chain base (such as lauryl phosphate or lauric acid) to measure the rate acceleration for the Kemp elimination. Remarkably, we found that this simple system can accelerate the reaction by four orders of magnitude, approaching the rates of more complex designed systems. Use of different substrates suggests that the reaction takes place at the interface between the micellar head and water (the Stern layer) with the long-chain base embedded in the micelle and the substrate in the aqueous solution. Thus, we suggest that significant rate accelerations can be achieved regardless of the precise positioning of substrates. Because natural enzymes use specific interactions to position their substrates, we propose that acceleration of the Kemp elimination is not a suitable benchmark for the success of the design process, and we suggest that more complex reactions should be used. Copyright (c) 2015 John Wiley & Sons, Ltd.
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