Swollen chain dynamics

Solid-state NMR magnetisation relaxation experiments provide a good method for the analysis of network structures. In the past two decades considerable progress has been made in the field of elastomer characterisation using transverse or spin-spin (T2) relaxation data [36-42]. The principle of the use of such relaxation experiments is based on the high sensitivity of the relaxation process to chain dynamics involving large spatial-scale chain motion in elastomers at temperatures well above the Tg and in swollen networks. Since chain motion is closely coupled to elastomer structure, chemical information can also be obtained in this way. 

In a subsequent communication, Elliott and coworkers found that uniaxially oriented membranes swollen with ethanol/water mixtures could relax back to an almost isotropic state. In contrast, morphological relaxation was not observed for membranes swollen in water alone. While this relaxation behavior was attributed to the plasticization effect of ethanol on the fluorocarbon matrix of Nafion, no evidence of interaction between ethanol and the fluorocarbon backbone is presented. In light of the previous thermal relaxation studies of Moore and co-workers, an alternative explanation for this solvent induced relaxation may be that ethanol is more effective than water in weakening the electrostatic interactions and mobilizing the side chain elements. Clearly, a more detailed analysis of this phenomenon involving a dynamic mechanical and/ or spectroscopic analysis is needed to gain a detailed molecular level understanding of this relaxation process. 

The heterogeneous structure of the swollen B. mori silk fibroin membrane was clarified from the complicated ESR spectra of the spin-labeled silk fibroin membranes. Spin-label ESR methods are useful for dynamic analysis of silk fibroin because of the inherent high sensitivity of ESR observation and the wide detectable range of the motion of the spin-labeled site, from 10 to lO " s. The hydroxy group of the Tyr side-chain is active and thus it can be labeled with nitroxide radical compounds as shown in Fig. 31. ... 

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