Dielectric dispersion interpretation of single enzyme dynamic disorder, spectral diffusion, and radiative fluorescence lifetime

Abstract

A formulation based on measurable dielectric dispersion of enzymes is developed to estimate fluctuations in electrostatic interaction energy on time scales as long as milliseconds to seconds at a local site in enzymes. Several single molecule experimental observations occur on this time scale, currently unreachable by real time computational trajectory simulations. We compare the experimental results on the autocorrelation function of the fluctuations of catalysis rate with the calculations using the dielectric dispersion formulation. We also discuss the autocorrelation functions of the fluorescence lifetime and of spectral diffusion. We use a previously derived relation between the observables and the electric field fluctuations and calculate the latter using dielectric dispersion data for the proteins and the Onsager regression hypothesis.

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