Conformational transition chains

Having been extensively applied to characterize polymers, FTIR spectroscopy complements other teehniques in providing detailed information on the chain conformation transition and crystallinity of a polymer with nondestructive charaeteristies. ° The ehanges of chain conformation and crystallinity can be charaeterized by identifying FTIR spectral features of intensity, bandwidth, and position. 

In some of these models (see Sec. Ill) the surfactants are still treated as flexible chains [24]. This allows one to study the role of the chain length and chain conformations. For example, the chain degrees of freedom are responsible for the internal phase transitions in monolayers and bilayers, in particular the hquid/gel transition. The chain length and chain architecture determine the efficiency of an amphiphile and thus influence the phase behavior. Moreover, they affect the shapes and size distributions of micelles. Chain models are usually fairly universal, in the sense that they can be used to study many different phenomena. 

The possibility of conformational changes in chains between chemical junctions for weakly crosslinked CP in ionization is confirmed also by the investigation of the kinetic mobility of elements of the reticular structure by polarized luminescence [32, 33]. Polarized luminescence is used for the study of relaxation properties of structural elements with covalently bonded luminescent labels [44,45]. For a microdisperse form of a macroreticular MA-EDMA (2.5 mol% EDMA) copolymer (Fig. 9 a, curves 1 and 2), as compared to linear PM A, the inner structure of chain parts is more stable and the conformational transition is more distinct. A similar kind of dependence is also observed for a weakly crosslinked AA-EDMA (2.5 mol%) copolymer (Fig. 9b, curves 4 and 5). 

Plotting U as a function of L (or equivalently, to the end-to-end distance r of the modeled coil) permits us to predict the coil stretching behavior at different values of the parameter et, where t is the relaxation time of the dumbbell (Fig. 10). When et < 0.15, the only minimum in the potential curve is at r = 0 and all the dumbbell configurations are in the coil state. As et increases (to 0.20 in the Fig. 10), a second minimum appears which corresponds to a stretched state. Since the potential barrier (AU) between the two minima can be large compared to kBT, coiled molecules require a very long time, to the order of t exp (AU/kBT), to diffuse by Brownian motion over the barrier to the stretched state at any stage, there will be a distribution of long-lived metastable states with different chain conformations. With further increases in et, the second minimum deepens. The barrier decreases then disappears at et = 0.5. At this critical strain rate denoted by ecs, the transition from the coiled to the stretched state should occur instantaneously. 

In other cases the conformational changes are small, but in the sense of lengthening of the unit height in the chain conformation. This has been for instance, recently observed for s-PB. The transition from form I (s(2/l)2 helices) toward form II (s(5/3)2 helices (see Sect. 2.2) occurs under tensile stress and involves only... 

Figure 2 compares the conformational transition curves of wild-type yeast glucan (branch frequency = 0.20) and PGG (branch frequency = 0.50). Wild-type yeast glucan required approximately 0.1M NaOH to disrupt the triple helical conformation, whereas this transition is observed at approximately 0.04 M NaOH with PGG. This trend is consistent with the observation that curdlan, an entirely linear p-D(l-3)-linked glucan, requires approximately 0.25M NaOH to disrupt the ordered conformation (76). Hence, it is concluded that the highly branched PGG molecules only form weak inter-chain associations resulting in the formation of predominantly single-helical zones. 

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