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Two series of highly charged linear aliphatic polymerssodium polystyrene-4-sulfonate and random copolymer of N-methyl-N-vinylacetamide and N-methyl-N-vinylamine hydrochloridewere studied in water solution without added salts and in solutions containing up to 5 M NaCl. Intrinsic viscosity in salt-free solutions was estimated by a method proposed earlier [Pavlov et al. Russ. J. Appl. Chem. 2006, 79, 1407−1412. Molecular characteristics were obtained in 0.2 M NaCl. The polyelectrolytes were studied in more than 10-fold range of molar mass. Qualitatively, the conformational status of the polyelectrolyte chains in different ionic strength was defined with the Kuhn−Mark−Houwink−Sakurada plots normalized by the value of linear chain density. In salt-free solution both polyelectrolytes could be attributed to extra rigid chains with the statistical segment length of 650 nm for sodium polystyrene-4-sulfonate and 100 nm for copolymer chains. Such statistical segment lengths are provided by short-range electrostatic intrachain interactions and are comparable with the Debye screening length. At extremely high NaCl concentration polyelectrolyte chains became discriminated by their degree of hydrophobicity. Chains of hydrophobic nature are compacted up to preglobular state, whereas the chains of the hydrophilic nature stay in the conformation of swelling coils at the highest concentration of NaCl.

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