Polymers microheterogeneity

C1.5.4.5 CONJUGATED POLYMERS, CHROMOPHORE AGGREGATES, AND MICROHETEROGENEOUS MATERIALS... 

Wang H, Bardo A M, Collinson M M and Higgins D A 1998 Microheterogeneity in dye-doped silicate and polymer films J. Chem. Phys. B 102 7231-7... 

The microheterogeneity coefficient was introduced only for the description of the microstructure of binary copolymers with symmetric units. At increased number of unit types and/or when account is taken of structural isomerism, the role of Km will be performed by other parameters analogous to it. A general strategy for the choice of these latter has been elaborated in detail [12], while their values have been measured via NMR spectroscopic techniques for a variety of polycondensation polymers [13]. 

When a system contains a fluorophore in different environments (e.g. a fluo-rophore embedded in microheterogeneous materials such as sol-gel matrices, polymers, etc.) or more than one fluorophore (e.g. different tryptophanyl residues of a protein), the preceding relations must be modified. If dynamic quenching is predominant, the Stem-Volmer relation should be rewritten as... 

R. K. Guo and S. Tazuke, Microheterogeneity oflocal segment mobility in solid polymethacrylates as studied by a polymer-bound twisted intramolecular charge transfer chromophore, Macromolecules 22, 3286 (1989). 

Deviations are also observed in some copolymerizations where the copolymer formed is poorly soluble in the reaction medium [Pichot and Pham, 1979 Pichot et al., 1979 Suggate, 1978, 1979]. Under these conditions, altered copolymer compositions are observed if one of the monomers is preferentially adsorbed by the copolymer. Thus for methyl methacrylate (M1 )-/V-vinylcarbazole (M2) copolymerization, r — 1.80, r2 = 0.06 in benzene but r — 0.57, > 2 0.75 in methanol [Ledwith et al., 1979]. The propagating copolymer chains are completely soluble in benzene but are microheterogeneous in methanol. /V-vinylcarba-zole (NVC) is preferentially adsorbed by the copolymer compared to methyl methacrylate. The comonomer composition in the domain of the propagating radical sites (trapped in the precipitating copolymer) is richer in NVC than the comonomer feed composition in the bulk solution. NVC enters the copolymer to a greater extent than expected on the basis of feed composition. Similar results occur in template copolymerization (Sec. 3-10d-2), where two monomers undergo copolymerization in the presence of a polymer. Thus, acrylic acid-2-hydroxyethylmethacrylate copolymerization in the presence of poly(V-vinylpyrrolidone) results in increased incorporation of acrylic acid [Rainaldi et al., 2000]. 

The configuration of bovine serum albumin isolated from milk has not been investigated, but extensive investigations of this protein isolated from bovine blood serum have been made. The protein exhibits at least three different kinds of heterogeneity (1) due to polymer formation, (2) related to the sulfur linkages in the molecule, and (3) microheterogeneity. Fractionation of bovine serum albumin on DEAE-Sephadex A-50 resulted in a monomer and two dimer fractions (Janatova et al. 1968),... 

Next, we would like to stress that adhesion is not linked to the strength of the polymer, determined by various methods (Ref.66), p. 142). Destruction of an adhesion joint never occurs strictly at the phase boundary. If the microheterogeneity of energy states of a living tissue surface is considered, then an adhesion joint can be presented... 

It is a routine SFM experiment to investigate the heterogeneous structure of polymer blends and composites containing micrometer sized domains [69]. A less trivial problem is to resolve and characterise the features on the nanometer scale (around 10 nm), which are comparable to the tip size and the contact area. Typical systems, which demonstrate microheterogeneous structures, are block copolymers consisting of chemically different and physically incompatible blocks, e.g. A and B. As a result of the interconnectivity of the blocks, block copolymers undergo microphase separation, where the size of the microdomains is restricted to the molecular dimensions. One can distinguish between AB diblock copolymers and triblock copolymers (ABA and ABC). 

Multicomponent polymeric materials with microheterogeneous mophologies include a number of polymer blends and block copolymers, however, an especially easy way to bring about the desired morphology is through interpenetrating polymer networks. Several papers in the symposium are concerned with IPN s and related materials. 

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