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Chain dimensions, intermolecular structure and hydration of a series of uncharged and cationic poly(vinyl amine) [PVAm] linear polymers having hydrophobic substituent methyl, n-propyl, and isopropyl in the monomer are studied in aqueous solution by molecular dynamics simulations. A conformational transition occurs in the degree of ionization, α, range 0.3 to 0.4. Among the polymers studied, isopropyl substituted PVAm is most hydrophobic and methyl substituted PVAm is the least. The extent of hydrophobicity of the chemical structure is directly correlated to the size of the polymer chain. Conformational dynamics become slower with increase in the degree of charge of the chain and with the size of the substituent side group. The significant hydration of the polymers takes place for 0 ≤ α ≤ 0.5. While the number of H-bonds is not affected significantly by the chemical structure of the chain the relaxation dynamics of polymer-water H-bonds is significantly affected, with the more hydrophobic polymer showing the slowest dynamics. The steric hindrance provided by the hydrophobic substituent groups is responsible for slowing of water orientation dynamics in the vicinity of the polymer. The counter-ion condensation is clearly better and the bound water content is less for the relatively more hydrophobic polymer. The overall behavior of structure and dynamics is in qualitative agreement with that known for other types of polyelectrolytes and solutes in aqueous solution., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The intermolecular structure and solvation enthalpy of anionic polyelectrolyte atactic Na + -polyethacrylate (PEA) in aqueous solution, as a function of added salt concentration C s (dilute to concentrated) and valency (NaCl versus CaCl 2 ), were investigated via molecular dynamics simulations with explicit-ion-solvent and atomistic polymer description. An increase in C s leads to a decrease in α, which stabilizes to a constant value beyond critical C s . A significant reduction in R g in the presence of CaCl 2 salt was observed, due to ion bridging of PEA by Ca 2+ ions, in agreement with results available in literature on other similar polycarboxylates. An increase in salt valency reduces the value of critical C s for the onset of stabilization of the overall size and shape of the polymer chain. The critical C s ratio for the divalent to monovalent salt case is in excellent agreement with results of Langevin dynamics studies on model systems available in the literature. PEA-water H-bond half-life increases with C s for CaCl 2 , but no appreciable effect is seen for NaCl. The hydration of PEA becomes stronger in the presence of divalent salt. The strength of H-bond interaction energy is greater for cations as compared to anions of the salt. The salt cation effect in displacing water molecules from the vicinity of PEA, with increase in C s , is greater for NaCl solution. The decrease in water coordination to PEA carboxylate groups, due to increased C s , is more pronounced in NaCl solution. The nature of the behavior of the solvation enthalpy of PEA and the type of intermolecular interactions contributing to it, is in agreement with experimental observations from the literature. The hydration enthalpy of PEA in divalent CaCl 2 aqueous salt solution is more exothermic compared to monovalent NaCl salt solution, in agreement with experimental data. The solvation of PEA is thermodynamically more favorable in the case of CaCl 2 solution. The exothermic solvation enthalpy, H-bond lifetime, number of H-bonds and H-bond interaction energy are greater in magnitude in CaCl 2 aqueous solution.