Department of Organic Chemistry, Indian Institute of Science, Bangalore 560012, India.
J Phys Chem B. 2012 Nov 8;116(44):13239-47. doi: 10.1021/jp304700t. Epub 2012 Oct 30.
Planar imidazolium cation based gemini surfactants [16-Im-n-Im-16], 2Br(-) (where n = 2, 3, 4, 5, 6, 8, 10, and 12), exhibit different morphologies and internal packing arrangements by adopting different supramolecular assemblies in aqueous media depending on their number of spacer methylene units (CH(2))(n). Detailed measurements of the small-angle neutron-scattering (SANS) cross sections from different imidazolium-based surfactant micelles in aqueous media (D(2)O) are reported. The SANS data, containing the information of aggregation behavior of such surfactants in the molecular level, have been analyzed on the basis of the Hayter and Penfold model for the macro ion solution to compute the interparticle structure factor S(Q) taking into account the screened Coulomb interactions between the dimeric surfactant micelles. The characteristic changes in the SANS spectra of the dimeric surfactant with n = 4 due to variation of temperature have also been investigated. These data are then compared with the SANS characterization data of the corresponding gemini micelles containing tetrahedral ammonium ion based polar headgroups. The critical micellar concentration of each surfactant micelle (cmc) has been determined using pyrene as an extrinsic fluorescence probe. The variation of cmc as a function of spacer chain length has been explained in terms of conformational variation and progressive looping of the spacer into the micellar interior upon increasing the n values. Small-angle neutron-scattering (SANS) cross sections from different mixed micelles composed of surfactants with ammonium headgroups, 16-A(0), [16-Am-n-Am-16], 2Br(-) (where n = 4), 16-I(0), and [16-Im-n-Im-16], 2Br(-) (where n = 4), in aqueous media (D(2)O) have also been analyzed. The aggregate composition matches with that predicted from the ideal mixing model.
基于咪唑阳离子的双子表面活性剂[16-Im-n-Im-16],2Br(-)(其中 n = 2、3、4、5、6、8、10 和 12),在水溶液中通过采用不同的超分子组装,表现出不同的形态和内部堆积排列,这取决于它们的间隔亚甲基单元(CH(2))(n)的数量。详细测量了不同间隔基甲基单元(CH(2))(n)的基于咪唑的表面活性剂胶束在水介质(D(2)O)中的小角中子散射(SANS)截面。这些 SANS 数据包含了这些表面活性剂在分子水平上的聚集行为信息,已经根据 Hayter 和 Penfold 模型对宏观离子溶液进行了分析,以计算考虑到二聚体表面活性剂胶束之间屏蔽库仑相互作用的粒子间结构因子 S(Q)。还研究了由于温度变化导致 n = 4 的二聚体表面活性剂的 SANS 光谱的特征变化。然后将这些数据与含有四面体铵离子的相应双子胶束的 SANS 表征数据进行比较。使用芘作为外荧光探针确定了每个表面活性剂胶束的临界胶束浓度(cmc)。cmc 随间隔链长度的变化可以用构象变化和间隔链在 n 值增加时逐渐进入胶束内部的环化来解释。由具有铵头基的表面活性剂 16-A(0)、[16-Am-n-Am-16],2Br(-)(n = 4)、16-I(0)和[16-Im-n-Im-16],2Br(-)(n = 4)组成的不同混合胶束在水介质(D(2)O)中的小角中子散射(SANS)截面也进行了分析。聚集组成与理想混合模型预测的一致。