Molecular interaction of Congo Red with conventional and cationic gemini surfactants

Interaction of tetradecyltrimethylammonium bromide (TTAB), octylophenylpolyoxyethylene ether (TX-100), sodium dodecylsulfate (SDS), N,N′-ditetradecyl-N,N,N′,N′-tetramethyl-N,N′-butanediyl-diammonium dibromide (14,4,14) and N,N′-didodecyl-N,N,N′,N′-tetramethyl-N,N′-butanediyl-diammonium dibromide (12,4,12) with an anionic diazo dye, Congo Red, was investigated using conductometry, spectroscopy, tensiometry, and pulsed field gradient NMR (PFG-NMR). The formation of dye–surfactant ion pairs, their small mixed aggregates (below the critical micelle concentration (CMC) of these surfactants) and surfactant micelles were detected successfully. Above the CMC, the dye reverted to its monomeric state and solubilized in the micelles. Job's method was used to determine the stoichiometric ratio of dye and surfactant in ion pairs and revealed the formation of more hydrophile ion pairs for geminis compared to their conventional analogs. Quantitative results obtained from tensiometry indicated the existence of considerable synergism for cationic surfactants and antagonism for anionic SDS. In addition, the synergism observed for TX-100 revealed the effect of π–π stacking and hydrophobic forces on ion pair and mixed micelle formation. The increase of dye–surfactant interactions by increasing the electrical charge and chain length of cationic surfactants confirmed the importance of both electrostatic and hydrophobic forces in binary dye/surfactant systems. The hydrodynamic radii of the micelles were determined by self-diffusion coefficient measurements. The average size of the cationic and nonionic micelles increased in the presence of CR molecules.

The formation of stable surface monolayer composed of D2S2− ion pairs and S2+ gemini surfactant molecules in the presence of Congo Red.Figure optionsDownload as PowerPoint slideHighlights
► Ion pairs are mainly formed in oppositely charged systems and affect the surface tension of solution.
► CR molecules tend to form H-aggregates in the presence of small amounts of oppositely charged surfactants.
► Hydrophobic interactions as well as electrostatics contribute to dye/surfactant interactions.
► Incorporation of CR molecules to pure surfactant micelle increases its size.