Structure kinetic trapping

The phase diagram in Fig. 56 reveals an irreversible temperature-induced OOT between C and G, with the former being the low-temperature phase, which differs from previous studies on PS-fr-PI/PS or PI blends [10]. The irreversibility of the OOT was attributed to a kinetic effect. At temperatures between ODT and OOT the system assembles in a G morphology. This structure is kinetically trapped and persists at temperatures below OOT, where cylinders are expected to be formed. 

The process opposite to vesicle division is that of fusion, when two or more vesicles come together and merge with each other, yielding a larger vesicle. As outlined in the previous chapter, vesicle fusion is generally not a spontaneous process. If two populations of POPC liposomes with different average dimensions are mixed with each other, they do not fuse to produce a most stable intermediate structure - they stay in the same solution as stable, distinct species. This is connected to the notion of kinetic traps, as discussed previously, and is supported by theoretical and experimental data from the literature (for example, Hubbard etal, 1998 Olsson and Wennerstrom, 2002 Silin et al, 2002). 

In the structure of the apo-form of HIV PR, the flaps from both monomers are related by crystallographic two-fold symmetry and can be considered as being in an open conformation. In the structures of related proteases from Rous Sarcoma Virus and HIV-2, the flaps are either crystallographically disordered or in a partly closed conformation [18]. This suggests that, in solution, in the absence of ligands, the flaps are rather flexible and that the stable conformation of the flaps observed in the crystal structure of the apo-enzyme of HIV PR could be considered to result from kinetic trapping during the crystallization process. 

It is also known that a rod structure is generated in compact DNA under some conditions. However, it was not clear whether the rod-like structure is a thermodynamically stable state or a kinetically trapped metastable state (Chattoraj et al., 1978 Eickbush and Moudrianakis, 1978 Grosberg, 1979 Arscott et al., 1990 Plum etal., 1990 Perales et al., 1994). 

Another contribution to variations of intrinsic activity is the different number of defects and amount of disorder in the metallic Cu phase. This disorder can manifest itself in the form of lattice strain detectable, for example, by line profile analysis of X-ray diffraction (XRD) peaks [73], 63Cu nuclear magnetic resonance lines [74], or as an increased disorder parameter (Debye-Waller factor) derived from extended X-ray absorption fine structure spectroscopy [75], Strained copper has been shown theoretically [76] and experimentally [77] to have different adsorptive properties compared to unstrained surfaces. Strain (i.e. local variation in the lattice parameter) is known to shift the center of the d-band and alter the interactions of metal surface and absorbate [78]. The origin of strain and defects in Cu/ZnO is probably related to the crystallization of kinetically trapped nonideal Cu in close interfacial contact to the oxide during catalyst activation at mild conditions. A correlation of the concentration of planar defects in the Cu particles with the catalytic activity in methanol synthesis was observed in a series of industrial Cu/Zn0/Al203 catalysts by Kasatkin et al. [57]. Planar defects like stacking faults and twin boundaries can also be observed by HRTEM and are marked with arrows in Figure 5.3.8C [58],... 

Microstmctures are frequently present in a kinetically trapped nonequilibrium state, and their structures depend on the components and colloidal interactions based on their different chemical and physical properties, as well as on the procedure by which these components have been assembled. These structures are thermodynamically unstable and tend to reduce their free energy (surface area) with time. On the contrary, self-assembly nanostructures are thermodynamically stable, unless the molecules react with the environment or degrade. Most food systems are based on an interplay of kinetically stabilized and thermodynamic equilibrium structures. Some typical examples of structures at different length scales formd in food systems are shown in Figure 11.1. 

The depletion mechanism can be of interest to create new food structures resulting in novel texture properties if one gets control of the dynamics and finds ways to kinetically trap the separation process (Aichinger 2005). For the study of such... 

The use of monomers bearing more than two associating groups is a straightforward way to introduce a controlled amount of branches or crosshnks in a supramolecular polymer structure [6,58,121,123-127]. The improvement of the mechanical properties can be spectacular. For instance, trifunctional monomer 17 (Fig. 21) forms highly viscous solutions in chloroform, and is a viscoelastic material in the absence of solvent [124]. The reversibly cross-linked network displays a higher plateau modulus than a comparable covalently cross-linked model. This is explained by the fact that the reversibly cross-hnked network can reach the thermodynamically most stable conformation, whereas the covalent model, which has been cross-linked in solution and then dried, is kinetically trapped. 

Manoj, R, Kasapis, S., and Hember, M. W. N. 1997. Sequence-dependent kinetic trapping of biphasic structures in maltodextrin-whey protein gels. Carbohydr. Polym. 32 141-153. 

Beyond the thermodynamic control, the kinetics of chain rearrangement can dramatically influence the phase behavior leading to kinetically trapped structures, which do not necessarily correspond to an absolute free energy minimum of the system. Thus, the formation of block copolymer vesicles, from a kinetic point of view, can be a result of a transition from rod-like aggregates via flat, nonclosed lamellar structures. The kinetics of such transitions has been explored in [8], The transition steps are represented as follows ... 

Furthermore, long-lived meta stable energy minima might exist in relation to the isomeric state of a critical peptide bond [184]. In the metastable state in which the folded forms of a polypeptide chain have similar structural characteristics but differ in their free energy level, the kinetically trapped species could demonstrate properties of a high energy peptide bond isomer [185]. 

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