Hydrophobic terminal group of surfactant initiating micellization as revealed by^1H NMR spectroscopy

The critical aggregation concentration（CAC） of four with three kinds of conventional surfactants, namely,two cationic surfactants [hexadecyltrimethyl ammonium bromide（CTAB） and tetradecyltrimethyl ammonium bromide（TTAB）], one anionic surfactant [sodium dodecyl sulfate（SDS）], and a nonionic surfactant [Triton X-100（TX-100）], were determined by variation of ^1H chemical shifts with surfactant concentrations. Results show that the CAC values of protons at different positions of the same molecule are different, and those of the terminal methyl protons are the lowest, respectively, which suggests that the terminal groups of the alkyl chains aggregates first during micellization. Measurement of the transverse relaxation time（T2） of different protons in SDS also show that the terminal methyl protons start to decrease with the increase in concentration first, which supports the above mentioned tendency.

To gel or not to gel：A prior prediction of gelation in solvent mixtures

The gelation behaviours of low molecular weight gelators 1,3：2,5：4.6-tris（3,4-dichlorobenzylidene）-Dmannitol（G1） and 2,4-（3.4-dichlorobenzylidene）-N-（3-aminopropyl）-D-gluconamide（G2） in 34 solvents have been studied.We found that sample dissolved at low concentrations may become a gel or precipitate at higher concentrations.The Hansen solubility parameters（HSPs） and a Teas plot were employed to correlate the gelation behaviours with solvent properties,but with no success if the concentration of the tests was not maintained constant.Instead,on the basis of the gelation results obtained for the G1 and G2 in single solvents,we studied the gelation behaviours of G1 and G2 in23 solvent mixtures and found that the tendency of a gelator to form a gel in mixed solvents is strongly correlated with its gelation behaviours in good solvents.If the gelation occurs in a good solvent at higher concentrations,it will take place as well in a mixed solvent（the good solvent plus a poor solvent） at a certain volume ratio.In contrast,if the gelator forms a precipitate in a good solvent at higher concentrations,no gelation is to be observed in the mixed solvents.A gelation rule for mixed solvents is thus proposed,which may facilitate decision making with regard to solvent selection for gel formation in the solvent mixtures in practical applications.