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质子离子液体(PILs)对非离子十二烷基聚(氧化乙烯)表面活性剂自组装结构形成的影响以及这些表面活性剂对 PILs 纳米结构的影响。

Effect of protic ionic liquids (PILs) on the formation of non-ionic dodecyl poly(ethylene oxide) surfactant self-assembly structures and the effect of these surfactants on the nanostructure of PILs.

机构信息

CSIRO Materials Science and Engineering, Bag 10, Clayton, VIC 3169, Australia.

出版信息

Phys Chem Chem Phys. 2011 Dec 7;13(45):20441-52. doi: 10.1039/c1cp21381d. Epub 2011 Oct 12.

Abstract

The ability of a series of non-ionic dodecyl poly(ethylene oxide) surfactants to form micelles in a variety of protic ionic liquids (PILs) was investigated using small and wide angle X-ray scattering (SAXS/WAXS). The C(12)E(n) surfactants with n = 3-8 were examined in PILs which contained either an ethyl, diethyl, triethyl, butyl, pentyl, ethanol or pentanol-ammonium cation in conjunction with either a nitrate or formate anion. The ability of the PILs to support micelles of these surfactants was highly dependent on their liquid nanostructure. The PILs containing hydroxyl groups on the cations were not nanostructured and had very low surfactant solubility (<1 wt%). The highly nanostructured PILs with butylammonium or pentylammonium cations contain large non-polar domains, and had excellent surfactant solubility, but due to the greater hydrocarbon solubility they had insufficient drive from the "solvophobic effect" to enable micelle formation. The PILs of ethylammonium nitrate (EAN), propylammonium nitrate (PAN), diethylammonium formate (DEAF) and triethylammonium formate (TEAF) had smaller non-polar domains, and all supported micelle formation below 20 wt% surfactant. The critical micelle concentration (CMC) of surfactants in EAN were two orders of magnitude greater than in water. The minimum molecular areas of the poly(ethylene oxide) head groups at the air/ionic liquid interface, A(min), were significantly larger in EAN than in water. The SAXS patterns from the micelles present in EAN fitted well to ellipsoids, whereas the micelles present in PAN fitted well to spheres. The nanostructure of select PILs was also influenced by the presence of surfactants.

摘要

一系列非离子型十二烷基聚(环氧乙烷)表面活性剂在各种质子离子液体(PILs)中形成胶束的能力使用小角和广角 X 射线散射(SAXS/WAXS)进行了研究。研究了 C(12)E(n)表面活性剂,其中 n = 3-8,在含有乙基、二乙基、三乙基、丁基、戊基、乙醇或戊醇-铵阳离子的 PILs 中,与硝酸盐或甲酸盐阴离子结合。这些 PILs 支持这些表面活性剂胶束的能力高度依赖于它们的液体纳米结构。阳离子上含有羟基的 PILs 没有纳米结构,表面活性剂溶解度非常低(<1wt%)。具有丁基铵或戊基铵阳离子的高度纳米结构化 PILs 含有大的非极性域,具有极好的表面活性剂溶解度,但由于烃类溶解度较高,它们从“疏溶剂效应”中获得的驱动力不足以形成胶束。硝酸乙基铵(EAN)、硝酸丙基铵(PAN)、甲酸二乙基铵(DEAF)和甲酸三乙基铵(TEAF)的 PILs 具有较小的非极性域,所有这些 PILs在 20wt%以下的表面活性剂浓度下都支持胶束形成。表面活性剂在 EAN 中的临界胶束浓度(CMC)比在水中高两个数量级。在空气/离子液体界面处聚(环氧乙烷)头基的最小分子面积 A(min)在 EAN 中比在水中大得多。存在于 EAN 中的胶束的 SAXS 图谱很好地符合椭球体,而存在于 PAN 中的胶束很好地符合球体。选择的 PILs 的纳米结构也受到表面活性剂的存在的影响。

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