Supermolecular

Macromolecular stmcture and supermolecular organization also affect dye affinity. Drawn (oriented) nylon-6 has more of a random open stmcture than nylon-6,6 (172). Nylon-6, therefore, dyes more rapidly than nylon-6,6, but is also more susceptible to color crocking, especially with disperse dyes. 

SAMs are ordered molecular assembHes formed by the adsorption (qv) of an active surfactant on a soHd surface (Fig. 6). This simple process makes SAMs inherently manufacturable and thus technologically attractive for building supedattices and for surface engineering. The order in these two-dimensional systems is produced by a spontaneous chemical synthesis at the interface, as the system approaches equiHbrium. Although the area is not limited to long-chain molecules (112), SAMs of functionalized long-chain hydrocarbons are most frequently used as building blocks of supermolecular stmctures. 

The characterization of copolymers must distinguish copolymers from polymer blends and the various types of copolymers from each other (97,98). In addition, the exact molecular stmcture, architecture, purity, supermolecular stmcture, and sequence distribution must be determined. 

The molecular stmcture of the copolymers is also important. Molecular-weight measurements (osmometry, gpc) and functional group analysis are useful. Block copolymers require supermolecular (morphological) stmctural information as well. A listing of typical copolymer characterization tools and methods is shown in Table 6. 

Solvation effects on the molecular vibrations of 128 were studied by SCRF methods and by supermolecular approaches of 128 with one water molecule [97JPC(B) 10923, 98JPC(A)6010]. Correlations between the N—H (uracil) and O—H (water) bond elongations and the corresponding frequency shifts of the stretching vibrations are reported as... 

The introduction of large gas phase volumes into the polymer alters the physical characteristics of the material volume weight, permeability to fluids and gases, and physico-mechanical properties. Moreover, the properties of the polymer matrix itself are changed (owing to orientation effects, supermolecular structure of the polymer in the walls, ribs and tension bars of cells), which drives up the value of specific strength on impact, and results in anisotropy of elasticity. 

The processes of ordering in polymer systems consisting of linear polymers are related, at least on one level of supermolecular organization, to the development of a predominant localization of macromolecules (or their parts) along some directions the orientation axes, i.e. to the transition of the system into the oriented state. The most simple and most widely spread type of polymer orientation is the uniaxial orientation, i.e. the one-dimensional orientation in the direction of the axes of macromolecules. 

Fig. 3a-e. Supermolecular structures of polymers crystallized in various force fields a structure of the shish-kebab type, b structure formed during crystallization in a capillary with a conical inlet and c structure of a polymer crystallized at hydrostatic compression at 4 x 108 Pa... 

Marikhin, V. A., Myasnikova, L. P. Supermolecular structure of polymers (in Russian), Leningrad Khimiya 1977... 

C. Carrageenan and gellan gum gelation mechanism and supermolecular structure... 

As is apparent from the above definitions, each of these effective matrices depend on basis sets and molecular orbitals of both fragments. It is also important to observe that these matrices possess a correct asymptotic behavior as at large interfragment distances they become the usual overlap and Fock matrices of the separate fragments, while the paired secular systems uncouple and converge to the separate Roothaan equations for the single monomers. Finally, as it is usual in a supermolecular approach, the interaction energy is expressed as... 

Development and Characterization of Solid State Molecular and Supermolecular Structure... 

What is meant by the term supermolecular structure when describing polymers ... 

Nylon crystallites consist of sheets of chains that are hydrogen-bonded to their neighbors. On a supermolecular scale, crystallites have a lamellar structure, that is they are many times longer and broader than they are thick. When nylon crystallizes from an isotropic molten state, it generally forms spherulites, which consist of ribbon-like lamellae radiating in all directions... 

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