Time scales hydration layer dynamics

In sharp contrast to the large number of experimental and computer simulation studies reported in literature, there have been relatively few analytical or model dependent studies on the dynamics of protein hydration layer. A simple phenomenological model, proposed earlier by Nandi and Bagchi [4] explains the observed slow relaxation in the hydration layer in terms of a dynamic equilibrium between the bound and the free states of water molecules within the layer. The slow time scale is the inverse of the rate of bound to free transition. In this model, the transition between the free and bound states occurs by rotation. Recently Mukherjee and Bagchi [14] have numerically solved the space dependent reaction-diffusion model to obtain the probability distribution and the time dependent mean-square displacement (MSD). The model predicts a transition from sub-diffusive to super-diffusive translational behaviour, before it attains a diffusive nature in the long time. However, a microscopic theory of hydration layer dynamics is yet to be fully developed. 

Molecular dynamics (MD) simulations [29-31], coupled with experimental observations, have played an important role in the understanding of protein hydration. They predicted that the dynamics of ordered water molecules in the surface layer is ultrafast, typically on the picosecond time scales. Most calculated residence times are shorter than experimental measurements reported before, in a range of sub-picosecond to 100 ps. Water molecules at the surface are very mobile and are in constant exchange with bulk water. For example, the trajectory study of myoglobin hydration revealed that among 294 hydration sites, the residence times at 284 sites (96.6% of surface water molecules) are less than lOOps [32]. Furthermore, the population time correlation functions... 

The robust observation of surface hydration dynamics on two time scales and a series of correlations with protein properties provides a molecular picture of water motions and their coupling with protein fluctuations in the layer, as shown in Fig. 46. The dynamic exchange of hydration layer water with outside bulk... 

There have been two different interpretations of the slow dynamics observed in the SD of the lysozyme hydration layer. The first attributes the intermediate time-scales (30 0 ps) to slow water. Bagchi and co-workers employed the dynamic exchange model to relate the observed slow dynamics to the timescale of the fluctuation of water in the hydration layer [11]. In an alternative interpretation. Song et al. used the formulation developed by Song and Marcus that relates the solvation time correlation function to the DR of the medium. They attributed the... 

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