Influence of three anionic gemini surfactants with different chain lengths on the optical properties of a cationic polyfluorene.

The effects of three sulfonate gemini surfactants with different hydrophobic chain lengths (8, 10, and 12 carbon atoms) on the optical properties of a fluorene-based conjugated cationic polymer poly{[9,9-bis(6'-N,N,N-trimethylammonium)hexyl]-fluorene-phenylene} bromide (PFP) dissolved in DMSO-water solutions (4% v/v) or water were investigated, respectively. When surfactants with PFP dissolved in DMSO-water solutions (4% v/v) are incubated, a decrease in photoluminescence (PL) intensity and a red shift of emission maxima are obtained at low surfactant concentrations. Intriguingly, two different Stern-Volmer constants (KSV1 and KSV2) are obtained and analyzed in detail for the first time. Further increase in the surfactant concentration enhanced PL intensity, and distinct blue shifts of both absorption and emission maxima are observed. Importantly, the turning point between the emission quenching and enhancement is closely related to the hydrophobic chain length: the longer the chain length, the earlier the turning point appears. Simulation studies provide strong evidence to explain these phenomena. Surface tension measurements show more insight on the interactions between PFP and surfactant. On the contrary, no emission quenching is obtained at low surfactant concentrations for PFP dissolved in water.

Synthesis of three novel anionic gemini surfactants and comparative studies of their assemble behavior in the presence of bovine serum albumin.

Three novel anionic sulfonate gemini surfactants, sodium 4,4'-(10,19-dioxo-9,11,18,20-tetraazaoctacosane-9,20-diyl) dibenzenesulfonate (Surfactant I), sodium 4,4'-(12,21-dioxo-11,13,20,22-tetraazadotriacontane-11,22-diyl) dibenzenesulfonate (Surfactant II), and sodium 4,4'-(14,23-dioxo-13,15,22,24-tetraazahezatriacontane-13,24-diyl) dibenzenesulfonate (Surfactant III), with different lengths of hydrophobic tail have been synthesized, and their assembly behavior in the presence of bovine serum albumin (BSA) has been studied using spectral methods and molecular modeling methods at physiological pH and 298 K. Critical micelle concentrations (CMCs) of the three surfactants have been determined by surface tension measurements. Despite the obvious decrease of CMC with the increase of tail length, fluorescence spectra have shown much closer CAC in the presence of BSA. Surfactant II shows the highest CAC of 3.19 × 10(-5) mol L(-1) compared with the other two. The polarity of the microenvironment in BSA-surfactant systems has been investigated using pyrene as the probe. In addition, far-UV CD spectra studied the change of the secondary structure content of BSA caused by the three surfactants. The features of the assembly behavior were discussed by three concentration regions. Surfactant II could unfold the protein much more efficiently than the other two surfactants at low concentration, but at high concentration, the change of the secondary structure and the formation of hydrophobic microenvironment show a direct relationship to the length of the hydrophobic tail with the increase of the surfactant concentration.