Proteinlike copolymers were first predicted by the computer-aided biomimetic design (Physica A 1998, 249, 253-261). These copolymers consist of comonomer units of differing hydrophilicity/ hydrophobicity. Heterogeneous blockiness, characteristic for such copolymers, facilitates chain folding with the formation of specific spatial packing: a dense core consisting of hydrophobic units and a polar shell formed by hydrophilic units. This paper describes the synthesis of N-vinylcaprolactam/Nvinylimidazole copolymers via the redox-initiated radical copolymerization in the medium of 10% aqueous DMSO at the temperatures both below and above the phase separation threshold. The synthesized macromolecular products were separated into thermally precipitating and nonprecipitating fractions. Their molecular weight characteristics were evaluated using size-exclusion chromatography; their comonomer composition was determined from 1 H NMR spectra of copolymers dissolved in DMSO-d6. The temperature-dependent behavior of copolymer macromolecules in water was investigated by thermonephelometry, high-sensitivity differential scanning calorimetry, and 1 H NMR spectroscopy of the copolymers dissolved in D2O. It was shown that thermally nonprecipitating copolymer fractions obtained at initial comonomer molar ratios of 85:15 and 90:10 can be identified as proteinlike copolymers.
SYNOPSISThe influence of the presence of some polyols in initial poly(viny1 alcohol) aqueous solutions on rheological and thermal properties of the cryogels, which were produced by the freezingthawing method, was investigated. The polyol additives (cosolvents) were as follows: glycerol, propylene glycol, mono-, di-, and triethylene glycols, and oligoethylene glycols (PEG-400 and PEG-1000). It was shown that the introduction of glycerol, propylene, or ethylene glycols into the polymer solution resulted in a decrease of cryogel's shear modulus and fusion temperature, whereas the use of triethylene and higher ethylene glycol oligomers as cosolvents gave rise to an increase in the gel's strength and thermostability, and diethylene glycol exhibited a transitional influence. The possible mechanism of the action of reinforcing cosolvents is discussed.
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