Relaxation, molecular

In the last chapter we saw that the molecular relaxation time is the yardstick against which times are measured. The experimental relaxation time plays a similar role. This is easily seen by an examination of Fig. 3.8b. For... 

During the photoelectron emission event there are electronic relaxation effects occurring, which are usually divided into intra- and inter-molecular relaxation effects. These effects can be rationalized in a classical picture as follows. An elec-... 

Goldflam R., Kouri D. J. On accurate quantum mechanical approximations for molecular relaxation phenomena. Averaged... 

Tobolsky, A. V. and DuPre, D. B. Macro molecular Relaxation in the Damped Torsional Oscillator and Statistical Segment Models. VoL 6, pp. 103-127. 

Due to the retractive forces in stretched mbber, the aldehyde and zwitterion fragments are separated at the molecular-relaxation rate. Therefore, the ozonides and peroxides form at sites remote from the initial cleavage, and underlying mbber chains are exposed to ozone. These unstable ozonides and polymeric peroxides cleave to a variety of oxygenated products, such as acids, esters, ketones, and aldehydes, and also expose new mbber chains to the effects of ozone. The net result is that when mbber chains are cleaved, they retract in the direction of the stress and expose underlying unsaturation. Continuation of this process results in the formation of the characteristic ozone cracks. It should be noted that in the case of butadiene mbbers a small amount of cross-linking occurs during ozonation. This is considered to be due to the reaction between the biradical of the carbonyl oxide and the double bonds of the butadiene mbber [47]. 

When (DEB), is much smaller than unity, the polymer relaxation is relatively rapid compared to diffusion. In this case, conformational changes take place instantaneously and equilibrium is attained after each diffusional jump. This is the type of diffusion encountered ordinarily and is called viscous diffusion. Therefore, the transport will obey classical theories of diffusion. When (DEB), is much larger than unity, the molecular relaxation is very slow compared to diffusion and there are no conformational changes of the medium within the diffusion time scale. In this case, Fick s law is generally valid, but no concentration dependence of the diffusion coefficient is expected. This is termed elastic diffusion. When (DEB), is in the neighborhood of unity, molecular rearrangment... 

Fig. 1 Simplified energy diagram showing the influence of molecular relaxations (with lifetime tr) on the energies of LE and ICT states. The ICT states can be strongly stabilized in polar media by orientation of surrounding dipoles resulting in substantial shifts of fluorescence spectra to lower energies (longer wavelengths)...

Molecular Relaxation and Dynamics of Dipoles in the Protein Globule... 

As shown above, the intrinsic fluorescence spectra of proteins as well as coenzyme groups and probes shift within very wide ranges depending on their environment. Since the main contribution to spectral shifts is from relaxational properties of the environment, the analysis of relaxation is the necessary first step in establishing correlations of protein structure with fluorescence spectra. Furthermore, the study of relaxation dynamics is a very important approach to the analysis of the fluctuation rates of the electrostatic field in proteins, which is of importance for the understanding of biocatalytic processes and charge transport. Here we will discuss briefly the most illustrative results obtained by the methods of molecular relaxation spectroscopy. 

A. P. Demchenko, Fluorescence molecular relaxation studies of protein dynamics. The probe binding site ofmelittin is rigid on the nanosecond time scale, FEBSLett. 182, 99-102 (1985). 

Figure 3 Molecular relaxivities of liposomes with different Gd-containing membranotropic chelators. Liposomes (egg lecithin cholesterol chelator = 72 25 3) were prepared by consecutive extrusion of lipid suspension in HEPES buffered saline, pH 7.4, through the set of polycarbonate filters with pore size of 0.6, 0.4, and 0.2 mm. Liposome final size was between 205 and 225 nm. Gd content determination was performed by Galbraith Laboratories, Inc. The relaxation parameters of all preparations were measured at room temperature using a 5-MHz RADX nuclear magnetic resonance proton spin analyzer. The relaxivity of liposomes with polymeric chelators is noticeably greater because of the larger number of Gd atoms bound to a single lipid residue [16].

---