Extreme electric fields power catalysis in the active site of ketosteroid isomerase

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Science  19 Dec 2014:
Vol. 346, Issue 6216, pp. 1510-1514
DOI: 10.1126/science.1259802

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Stark influence on reaction rates

Enzymes accelerate chemical processes by coaxing molecules into just the right reactive states. Fried et al. now elucidate the way the enzyme ketosteroid isomerase pushes its substrate toward product through exertion of a local electric field (see the Perspective by Hildebrandt). First the authors calibrated the shifts in molecular vibrational frequencies, known as Stark shifts, that fields of varying strength impose on a substrate analog; then they measured the vibrational spectrum of that compound in the enzyme's active site. The experiment uncovered an unusually strong field that the local enzyme structure directed to the precise spot where the substrate would react.

Science, this issue p. 1510; see also p. 1456