Unusual micellar properties of multiheaded cationic surfactants in the presence of strong charge neutralizing salts.

The aggregation properties of single-chain surfactants bearing one (H1), two (H2), and three (H3) trimethylammonium head groups have been studied by small-angle neutron scattering (SANS). Growth of aggregates was observed to decrease dramatically with an increase in the number of head groups in the surfactants. The micelles grow progressively smaller with every increase in the number of head groups of the surfactants. Aggregation number (N) continuously decreases and the fractional charge (alpha) gradually increases with the increase in the number of head groups. The semiminor axis (a) and semimajor axis (b=c) of the micelle decrease strongly with the increase in the number of head groups. In the case of H1, dramatic micellar growth is observed on addition of salts such as KBr and sodium salicylate, but this type of micellar growth is not observed in the cases of H2 and H3 when the above salts are added to their micellar solutions. Aggregation number and size of the micelles remain almost the same, even after addition of KBr at a concentration as high as 100 mM. This observation with multiheaded cationic surfactants is unusual. Clearly, the charge density at the head group level of surfactants markedly influences their micellar aggregation properties.

Aggregation and Polymerization of PEG-Based Macromonomers with Methacryloyl Group as the Only Hydrophobic Segment.

Aggregation behavior in aqueous solution of a series of poly (ethylene glycol) (PEG)-based macromonomers with methacryloyl group as the only hydrophobic segment has been investigated using surface tension, steady-state and time-resolved fluorescence spectroscopy using pyrene as a probe, and small-angle neutron scattering techniques. The general formula of these macromonomers is CH(2)&dbond;C(CH(3))-CO-O-E(m)-CH(3), where E is the ethylene glycol unit and m=8 (ME(8)), 18 (ME(18)), 49 (ME(49)), and 120 (ME(120)). The results indicate that a macromonomer with 8 ethylene glycol units forms as an aggregate above a certain critical concentration, which can be defined as critical aggregation concentration. The observed high value of I(1)/I(3) in pyrene emission spectra at the interface of these aggregates and the inability to scatter a neutron beam by these aggregates indicate that the hydrophobic cluster formed by this macromonomer is remarkably solvated. ME(18) has a tendency to aggregate but others do not form any hydrophobic cluster. The homopolymerization behaviors of these macromonomers in an aqueous medium at 70 degrees C are consistent with these possibi- lities. Copyright 2001 Academic Press.