No abstract

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.

35Cl, (79,81)Br, and (127)I NQR (nuclear quadrupole resonance) spectroscopy in conjunction with X-ray crystallography is potentially one of the best ways of characterizing secondary bonding of metal cations such as Ag(+) to halogen donor atoms on the surfaces of very weakly coordinating anions. We have determined the X-ray crystal structure of Ag(O(3)SCH(2)Cl) (a = 13.241(3) A; b = 7.544(2) A; c = 4.925(2) A; orthorhombic; space group Pnma; Z = 4) and compared it with the known structure of Ag(O(3)SCH(2)Br) (Charbonnier, F.; Faure, R.; Loiseleur, H. Acta Crystallogr., Sect. B 1978, 34, 3598-3601). The halogen atom in each is apical (three-coordinate), being weakly coordinated to two silver ions. (127)I NQR studies on Ag(O(3)SCH(2)I) show the expected NQR consequences of three-coordination of iodine: substantially reduced NQR frequencies nu(1) and nu(2) and a fairly small NQR asymmetry parameter eta. The reduction of the halogen NQR frequency of the coordinating halogen atom in Ag(O(3)SCH(2)X) becomes more substantial in the series X = Cl < Br < I, indicating that the coordination to Ag(+) strengthens in this series, as expected from hard-soft acid-base principles. The numbers of electrons donated by the organic iodine atom to Ag(+) have been estimated; these indicate that the bonding to the cation is weak but not insignificant. We have not found any evidence for the bonding of these organohalogen atoms to another soft-acid metal ion, thallium. A scheme for recycling of thallium halide wastes is included.