Nakamura Shohei, Kobayashi Lisa, Tanaka Ryo, Isoda-Yamashita Teruyo, Motomura Konomi, Moroi Yoshikiyo
Daiichi College of Pharmaceutical Sciences, 22-1 Tamagawamachi, Minami-ku, Fukuoka, Japan.
Langmuir. 2008 Jan 1;24(1):15-8. doi: 10.1021/la702820h. Epub 2007 Dec 6.
Solubilization of benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, n-pentylbenzene, and n-hexylbenzene into micelles of decanoyl-N-methylglucamide (Mega-10) was studied, where equilibrium concentrations of the above solubilizates were determined spectrophotometrically at 303.2 K. The concentration of the above solubilizates remained constant below the critical micelle concentration (cmc) and increased linearly with an increase in Mega-10 concentration above the cmc. The Gibbs free energy change of the solubilizates from the aqueous bulk to the liquid solubilizate phase was evaluated from the dependence of their aqueous solubility on the alkyl chain length of the solubilizates, which leads to -3.46 kJ mol-1 for DeltaG(0)(CH), the energy change per CH2 group of the alkyl chain. The first stepwise solubilization constant (K(overline)1 ) was evaluated from the slope of the change of solubilizate concentration versus Mega-10 concentration. The Gibbs free energy change (DeltaG(0,s)) for the solubilization decreased linearly with the carbon number of the alkyl chain of the solubilizates, from which DeltaG(0,s)(CH2) as evaluated to be -2.71 kJ mol-1. The similar values above clearly indicate that the location of the alkyl chain is a hydrophobic micellar core, which is also supported by the absorption spectrum of the solubilized molecules.
研究了苯、甲苯、乙苯、正丙苯、正丁苯、正戊苯和正己苯在癸酰基-N-甲基葡糖酰胺(Mega-10)胶束中的增溶作用,其中上述增溶物的平衡浓度在303.2 K下通过分光光度法测定。上述增溶物的浓度在临界胶束浓度(cmc)以下保持恒定,而在cmc以上随Mega-10浓度的增加呈线性增加。根据增溶物在水中的溶解度对增溶物烷基链长度的依赖性,评估了增溶物从水相主体到液体增溶物相的吉布斯自由能变化,得到ΔG(0)(CH)为-3.46 kJ mol-1,即烷基链每个CH2基团的能量变化。根据增溶物浓度相对于Mega-10浓度变化的斜率评估了第一步增溶常数(K(overline)1)。增溶作用的吉布斯自由能变化(ΔG(0,s))随增溶物烷基链的碳原子数呈线性下降,由此评估得到ΔG(0,s)(CH2)为-2.71 kJ mol-1。上述相似的值清楚地表明,烷基链位于疏水的胶束核心中,这也得到了增溶分子吸收光谱的支持。