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高分辨率核磁共振扩散测量法揭示了一系列双咪唑鎓双子表面活性剂在水溶液中CAC和CMC之间的明显区别。

Clear distinction between CAC and CMC revealed by high-resolution NMR diffusometry for a series of bis-imidazolium gemini surfactants in aqueous solutions.

作者信息

Szutkowski Kosma, Kołodziejska Żaneta, Pietralik Zuzanna, Zhukov Igor, Skrzypczak Andrzej, Materna Katarzyna, Kozak Maciej

机构信息

NanoBioMedical Centre, Adam Mickiewicz University in Poznań Umultowska 85 PL61614 Poznań Poland

Department of Macromolecular Physics, Faculty of Physics, Adam Mickiewicz University in Poznań Umultowska 85 PL61614 Poznań Poland.

出版信息

RSC Adv. 2018 Nov 22;8(67):38470-38482. doi: 10.1039/c8ra07081d. eCollection 2018 Nov 14.

DOI:10.1039/c8ra07081d
PMID:35559094
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9090568/
Abstract

The aggregation behavior in the transition region was studied for a series of dicationic surfactants 3,3'-[α,ω-(dioxaalkane)]bis(1-dodecylimidazolium)dichlorides with varied spacer length from two to twelve carbon atoms. We employed Nuclear Magnetic Resonance diffusometry and Bayesian DOSY analysis to obtain the aggregate size distribution in the transition region. The critical concentrations CC were independently obtained from surface tension, electric conductivity, UV-Vis and NMR methods. The micelle aggregation numbers were estimated from the self-diffusion coefficients and were independently confirmed using steady-state fluorescence quenching. The morphology of the aggregates was characterized by small-angle scattering of synchrotron radiation and molecular dynamics simulations. The obtained CC values are identified as critical aggregation concentrations CAC. A broad transition region was observed, and stable micelles were obtained at much higher concentrations than CAC. The accurate CMC values could not be identified for the systems in the study. We indicated that the distribution of aggregate size becomes small and the system becomes homogeneous at much larger concentrations than CAC (typically 15-20 mM). The existence of a slow exchange between two environments, an aggregate and aqueous environment, was confirmed by H NMR and 2D HSQC NMR spectroscopy.

摘要

研究了一系列间隔长度从两个到十二个碳原子不等的二价阳离子表面活性剂3,3'-[α,ω-(二氧杂烷)]双(1-十二烷基咪唑鎓)二氯化物在过渡区域的聚集行为。我们采用核磁共振扩散测量法和贝叶斯扩散排序光谱分析来获得过渡区域的聚集体尺寸分布。临界浓度CC通过表面张力、电导率、紫外可见光谱和核磁共振方法独立获得。胶束聚集数由自扩散系数估算,并通过稳态荧光猝灭独立确认。聚集体的形态通过同步辐射小角散射和分子动力学模拟进行表征。所获得的CC值被确定为临界聚集浓度CAC。观察到一个较宽的过渡区域,并且在比CAC高得多的浓度下获得了稳定的胶束。对于本研究中的体系,无法确定准确的临界胶束浓度(CMC)值。我们指出,在比CAC高得多的浓度(通常为15 - 20 mM)下,聚集体尺寸分布变小,体系变得均匀。通过1H NMR和二维异核单量子相干核磁共振光谱证实了聚集体和水性环境这两种环境之间存在缓慢交换。

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