Self-assembly of ionic and non-ionic surfactants in type IV cerium nitrate and urea based deep eutectic solvent.
Self-assembly of ionic and non-ionic surfactants in type IV cerium nitrate and urea based deep eutectic solvent.
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DOI：
10.1063/5.0059238
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发表时间：
2021-08
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通讯作者：
Iva Manasi;M. R. Andalibi;Ria S. Atri;Jake Hooton;S. King;K. Edler
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作者：
Iva Manasi;M. R. Andalibi;Ria S. Atri;Jake Hooton;S. King;K. Edler
理解和操纵胶束形态是在各种应用中开发表面活性剂的关键。最近的研究表明，表面活性剂自组装在各种深铕溶剂（DES），其中表面活性剂的性质和表面活性剂分子与溶剂组分的相互作用影响形成的胶束的大小，形状和形态。到目前为止，胶束形成仅在III型DES中有报道，仅由有机物质组成。本工作研究了阳离子表面活性剂十二烷基三甲基硝酸/溴化铵的自组装（C12 TANO 3/C12 TAB）、阴离子表面活性剂十二烷基硫酸钠（SDS）和非离子表面活性剂六甘醇单十二烷基醚（C12 EO 6）和八甘醇单十六烷基醚（C16 EO 8）在IV型DES中的混合物，所述IV型DES包含金属盐、硝酸铈（III）六水合物和氢键供体脲，摩尔比为1：3.5。C12 TANO 3、C12 TAB、C12 EO 6和C16 EO 8在DES中形成球形胶束，胶束大小取决于表面活性剂烷基链长度和头基，而SDS形成圆柱形胶束。我们推测，胶束形状的差异可以解释由反相稳定的SDS头基的聚阳离子在DES相比，硝酸盐/溴阴离子的相互作用的情况下，阳离子表面活性剂或分子相互作用的尿素和盐析作用的（CeNO 3）3在DES上的烷基链/聚乙氧基头基的非离子表面活性剂。这些研究加深了我们对这种新型离子和氢键溶剂中两亲物自组装的理解，提高了使用这些结构作为液晶模板以在可以使用这些DES合成的金属氧化物（二氧化铈）中产生孔隙的机会。
Understanding and manipulating micelle morphology are key to exploiting surfactants in various applications. Recent studies have shown surfactant self-assembly in a variety of Deep Eutectic Solvents (DESs) where both the nature of surfactants and the interaction of the surfactant molecule with the solvent components influence the size, shape, and morphology of the micelles formed. So far, micelle formation has only been reported in type III DESs, consisting solely of organic species. In this work, we have explored the self-assembly of cationic surfactant dodecyl trimethylammonium nitrate/bromide (C12TANO3/C12TAB), anionic surfactant sodium dodecyl sulfate (SDS), and non-ionic surfactants hexaethylene glycol monododecyl ether (C12EO6) and octaethylene glycol monohexadecyl ether (C16EO8) in a type IV DES comprising metal salt, cerium (III) nitrate hexahydrate, and a hydrogen bond donor, urea, in the molar ratio 1:3.5. C12TANO3, C12TAB, C12EO6, and C16EO8 form spherical micelles in the DES with the micelle size dependent on both the surfactant alkyl chain length and the head group, whereas SDS forms cylindrical micelles. We hypothesize that the difference in the micelle shape can be explained by counterion stabilization of the SDS headgroup by polycations in the DES compared to the nitrate/bromide anion interaction in the case of cationic surfactants or molecular interaction of the urea and the salting out effect of (CeNO3)3 in the DES on the alkyl chains/polyethoxy headgroup for non-ionic surfactants. These studies deepen our understanding of amphiphile self-assembly in this novel, ionic, and hydrogen-bonding solvent, raising the opportunity to use these structures as liquid crystalline templates to generate porosity in metal oxides (ceria) that can be synthesized using these DESs.