1D and 2D NMR investigations of the interaction between oppositely charged polymers and surfactants

Proton chemical shifts and two-dimensional COSY and NOE spectroscopy (NOESY) experiments have been used to examine the interaction of various oppositely charged surfactant and polyelectrolyte systems, namely, the cationic surfactant dodecyltrimethyammonium bromide (DTAB) and a series of alkanediyl- , -bis(alkyldimethylammonium bromide) surfactants (Gem 12-s-12, where s is the length of the methylene spacer group) with the anionic polyelectrolyte poly(styrene sulfonate) or PSS. In all cases, we observe substantial aromatic-solute-induced chemical shifts (ASIS) in the surfactant peaks of the polymer/surfactant complexes versus that of the pure surfactant spectra. In the case of the DTAB/PSS system, the chemical-shift changes as a function of changing ratio of surfactant to polymer are interpreted in terms of structural changes that occur in the complex with increasing polymer concentration. For the Gem 12-s-12/PSS systems, the interaction of these gemini surfactants with the anionic polyelectrolyte, as deduced from the interpretation of the 1 H ASIS shifts and the NOESY cross peaks, is dependent on the length of the methylene spacer. From the NOESY experiments, we observed significant NOESY cross peaks that correlated well with the expected mechanism of interaction as observed in the literature for the single-tailed surfactant/polymer system. NMR techniques are shown to provide information on the molecular arrangement of these molecules in aqueous solution.