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-α,ω-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 dedu...