Diagram of state of stiff amphiphilic macromoleculesстатья

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[1] Diagram of state of stiff amphiphilic macromolecules / V. A. Markov, V. V. Vasilevskaya, P. G. Khalatur et al. // Macromolecular Symposia. — 2007. — Vol. 252. — P. 24–35. We studied coil-globule transitions in stiff-chain amphiphilic macromolecules via computer modeling and constructed phase diagrams for such molecules in terms of solvent quality and persistence length. We showed that the shape of the phase diagram essentially depends on the macromolecule degree of polymerization. Relatively short amphiphilic molecules always form a spherical globule in a poor solvent, and the coil-globule transition includes one or two intermediate conformations, depending on the chain's stiffness. These are a disk-like globule in case of high enough Kuhn segment length, and a pearl necklace-like structure of spherical micelles and a disk-like globule in case of relatively flexible chains. The phase diagram of a long stiff amphiphilic chain was found to be more complex still. Thus three specific regions can be distinguished in the poor solvent region, depending on the chain stiffness. These correspond to a cylindrical globule without any specific backbone ordering, a cylindrical globule containing blobs with collagen-like ordering of the chain, and co-existence of collagen-like and toroidal globules. in the intermediate transition region in this case, apart from the pearl necklace-like conformations with spherical micelles, necklace conformations can be also observed where the polymeric chain has collagen-like ordering within each bead. [ DOI ]

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