开发了一种矩分析方法,用于研究球形分子聚集体界面处的溶质渗透。起初,开发了新的矩方程,用于从使用高效液相色谱(HPLC)测量的洗脱峰的第一绝对(μ1A)和第二中心(μ2C)矩确定溶质的分配平衡常数(Kp)和渗透速率常数(kin和kout)。然后,该方法用于分析三种溶质的传质现象,即,对苯二酚,间苯二酚,和邻苯二酚,在十二烷基硫酸钠(SDS)胶束的界面。通过使用ODS柱和磷酸盐缓冲液水溶液(pH=7.0)作为流动相溶剂来测量HPLC数据。在ODS固定相表面被SDS单体动态包被的条件下,在改变流动相中SDS浓度(5-20mmoldm-3)的同时进行了脉冲响应实验。为了证明使用HPLC的矩分析方法的有效性,Kp的值,亲属,和kout分别确定为35-69、2.4×10-8-1.4×10-6ms-1和7.0×10-10-2.1×10-8ms-1。它们的值随着溶质疏水性的增加而增加。该方法对于研究分子聚集体的界面溶质渗透具有一定的优势。例如,当使用HPLC测量洗脱峰时,既不需要固定也不需要对溶质分子和分子聚集体进行化学修饰。界面溶质渗透发生在流动相中,对分子聚集体没有任何化学反应或物理作用。Kp的值,亲属,和kout是通过使用矩方程从μ1A和μ2C的分析确定的。由于HPLC的通用性极高,因此这项研究的结果必须有助于向许多研究人员传播研究分子聚集体界面溶质渗透的机会。
A moment analysis method was developed for the study of solute permeation at the interface of spherical molecular aggregates. At first, new moment equations were developed for determining the partition equilibrium constant (Kp) and permeation rate constants (kin and kout) of solutes from the first absolute (μ1A) and second central (μ2C) moments of elution peaks measured by using high-performance liquid chromatography (HPLC). Then, the method was applied to the analysis of mass transfer phenomena of three solutes, i.e., hydroquinone, resorcinol, and catechol, at the interface of sodium dodecylsulfate (SDS) micelles. HPLC data were measured by using an ODS column and an aqueous phosphate buffer solution (pH = 7.0) as the mobile phase solvent. Pulse response experiments were conducted while changing SDS concentration (5 - 20 mmol dm-3) in the mobile phase under the conditions that the surface of ODS stationary phase was dynamically coated by SDS monomers. In order to demonstrate the effectiveness of the moment analysis method using HPLC, the values of Kp, kin, and kout were determined for the three solutes as 35 - 69, 2.4 × 10-8 - 1.4 × 10-6 m s-1, and 7.0 × 10-10 - 2.1 × 10-8 m s-1, respectively. Their values increase with an increase in the hydrophobicity of the solutes. The method has some advantages for the study of interfacial solute permeation of molecular aggregates. For example, neither immobilization nor chemical modification of both solute molecules and molecular aggregates is required when elution peaks are measured by using HPLC. Interfacial solute permeation takes place in the mobile phase without any chemical reaction or physical action on molecular aggregates. The values of Kp, kin, and kout were analytically determined from those of μ1A and μ2C by using the moment equations. The results of this study must contribute to the dissemination of an opportunity for studying the interfacial solute permeation of molecular aggregates to many researchers because of extremely high versatility of HPLC.