Nakahara Hiromichi, Kojima Yui, Moroi Yoshikiyo, Shibata Osamu
Department of Biophysical Chemistry, Faculty of Pharmaceutical Sciences, Nagasaki International University ; 2825-7 Huis Ten Bosch, Sasebo, Nagasaki 859-3298, Japan.
Langmuir. 2014 May 27;30(20):5771-9. doi: 10.1021/la501519a. Epub 2014 May 14.
Solubilization of benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, and n-pentylbenzene into micelles of decanediyl-1-10-bis(dimethyltetradecylammonium bromide) (14-10-14,2Br(-)) has been investigated in the temperature range from 288.2 to 308.2 K. The equilibrium concentrations of all the solubilizates are determined spectrophotometrically. The concentration of the solubilizates remains constant below the critical micelle concentration (cmc) and increases linearly with an increase in 14-10-14,2Br(-) concentration above the cmc. Compared to the mother micelle, the solubilized micelles indicate much larger hydrodynamic diameters, which are determined by dynamic light scattering. Therefore, the Gibbs energy change for the solubilization of n-alkylbenzenes has been evaluated by the partitioning of the solubilizates between the aqueous and micellar phases. Furthermore, the enthalpy and entropy changes for the solubilization could be calculated from temperature dependence of the Gibbs energy change. From the thermodynamic parameters, it is found that the solubilization for the present system is entropy-driven and that the location of the solubilizates moves into the inner core of the micelle with an elongation of their alkyl chains. The movement on the location is also supported by the results of absorption spectra, Fourier transform infrared (FTIR) spectra, and two-dimensional nuclear Overhauser effect spectroscopy (2-D NOESY).
在288.2至308.2 K的温度范围内,研究了苯、甲苯、乙苯、正丙苯、正丁苯和正戊苯在癸二基-1,10-双(二甲基十四烷基溴化铵)(14-10-14,2Br(-))胶束中的增溶作用。所有增溶物的平衡浓度通过分光光度法测定。在临界胶束浓度(cmc)以下,增溶物的浓度保持恒定,而在cmc以上,增溶物的浓度随14-10-14,2Br(-)浓度的增加呈线性增加。与母体胶束相比,增溶后的胶束显示出大得多的流体动力学直径,这是通过动态光散射测定的。因此,通过增溶物在水相和胶束相之间的分配来评估正烷基苯增溶的吉布斯自由能变化。此外,增溶的焓变和熵变可以从吉布斯自由能变化的温度依赖性计算得出。从热力学参数发现,本体系的增溶是由熵驱动的,并且随着增溶物烷基链的伸长,其在胶束中的位置向内核移动。吸收光谱法、傅里叶变换红外(FTIR)光谱法和二维核Overhauser效应光谱法(2-D NOESY)的结果也支持了这种位置上的移动。