Thermodynamics of noncovalent interactions in hydrophobically-substituted water-soluble polymers from intrinsic viscosity measurements: Application to nucleobase-substituted pullulans

Abstract

Hydrophobically substituted water-soluble polymers (HSWSP) act as associative thickeners through the reversible crosslinking from noncovalent interactions between the various groups on the polymer chains in aqueous solution. This article shows how the intrinsic viscosity (IV) of nonionic HSWSP can be used to define the thermodynamics of these interactions. Literature data on the IV of pullulans substituted by nucleobase ester groups (thyminylbutyryl and adeninylbutyryl) (Mocanu et al., Can J Chem, 1995, 73, 1933) are used as an exemplar of these procedures. The intramolecular crosslinking in these substituted pullulans is deduced to be “unimolecular” (association constant K1 = 1 M−1), as contrasted with the “bimolecular” behavior expected from the stacking of the free nucleobases; evidently the crosslinking results from hydrophobic interactions between the butyryl linking groups and the main chain. The results are compared with those from other HSWSP, and from cosolute binding systems. The use of the water–octanol partition coefficients of model systems to elucidate hydrophobic interactions in HSWSP, and of denaturant cosolutes (especially urea) to diagnose the presence and strength of these interactions, are also discussed. Emphasis is placed on the need for further such studies to identify the interactions underlying the rheological behavior of the nonionic HSWSP, and of the more common ionic types. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011