Dynamical heterogeneity, slow relaxation

Garrahan and Chandler [230] have recently attempted to rationalize the string-like motion in supercooled liquids based on a completely different concept of dynamic facilitation, derived from the study of magnetic spin models originally developed by Fredrickson and Anderson [231]. Although these spin models seem to exhibit dynamic heterogeneity of some kind and slow relaxation processes, the slowing down of the dynamics in these models is entirely decoupled from the spin model s thermodynamics [116, 230]. In view... 

Molecular dynamics simulations were employed to explore the dynamic heterogeneity in water motion around a protein-DNA complex. The complex chosen was the DNA-binding domain of human TRFl protein and a telomeric DNA (see Figure 11.1). It was observed that the slow water dynamics correlated with the relaxation time of HBs of the water molecules connected with the protein and the DNA. The restricted motion of such water molecules led to sluggish rotational and translational dynamics of the hydration layer near the protein and DNA molecules in their complexed forms as well as in their free forms (see Figure 11.2). 

The well-known continuum models and also the microscopic theories of solvation dynamics suggest a close relation between solvation dynamics and DR. This is expressed as tl = (soo/so)td where tl is the longitudinal relaxation time and td is the Debye relaxation time. However, the solvation dynamics of an ion at the protein surface is difficult to understand because of the heterogeneous environment of the protein surface. Therefore, a straightforward application of the continuum model with a multiexponential description of DR is not possible. The continuum theory suggests that at short length scales, the relaxation time is essentially given by the DR time. Therefore, we certainly expect a slow component in the solvation dynamics. 

Mechanical Load. Static mechanical load by strain leads to stretching of random-coil polymer chains in the direction of sample elongation and chain compression in the orthogonal directions. The value of the residual dipolar and quadrupolar couplings is increased by the mechanical load, and moreover, the distribution of the correlation times is also modifled. Therefore, many NMR parameters sensitive to the residual dipolar couplings and slow motions can be used for characterization of the local strain-stress effects in heterogeneous elastomers (158,160,161,179). Dynamics mechanical load leads to sample heating where the temperature distribution in dynamic equilibrium is determined by the temperature-dependent loss-modulus and the thermal conductivity of the sample. Because transverse relaxation rate (approximated by the T2 relaxation) scales with the temperature for carbon fllled SBR, a T2 map provides a temperature map of the sample. Such temperature maps have been measured for carbon-black filled SBR cylinders for different filler contents and mechanical load (180). 

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