Antagonistic mixing in micelles of amphiphilic polyoxometalates and hexaethylene glycol monododecyl ether.
Antagonistic mixing in micelles of amphiphilic polyoxometalates and hexaethylene glycol monododecyl ether.
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两亲性多金属氧酸盐和六乙二醇单十二烷基醚在胶束中的拮抗混合。
DOI：
10.1016/j.jcis.2020.06.007
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发表时间：
2020
影响因子：
9.9
通讯作者：
Di A
中科院分区：
文献类型：
--
作者：
Di A
假设多金属氧酸盐(POMS)是一种金属氧簇，具有一系列有趣的磁性和催化性质。带有碳氢链的POM表现出两亲性，因此我们假设非离子表面活性剂和以多金属氧酸盐簇合物为头基的阴离子表面活性剂的混合物将形成混合胶束，从而控制胶束中的POM密度，并且在大小和形状上与单独的表面活性剂形成的胶束不同。由于POM的高电荷和大尺寸，我们认为由于两种表面活性剂之间的复杂相互作用，这些可能是非理想的混合物。非理想性和胶束组成可以用正则溶液理论来量化。利用小角中子散射(SANS)提供的补充信息，可以建立对这一不寻常的二元表面活性剂体系的理解。实验系统地研究了多金属氧酸盐类两亲化合物(K10[P2W17O61OSi2(CnH2n+1)2]，简写为P2W17-2CN，其中n=12，14或16)与己二醇单十二烷基醚(C12EO6)的混合表面活性剂体系。测量了这些混合物的临界胶束浓度(CMC)，并根据规则溶液理论计算了相互作用参数，从而能够预测胶束组成。将预测结果与SANS获得的胶束结构进行了比较。这些混合物的CMC表明，尽管形成了混合胶束，但两种物种之间的相互作用却异常不利。由SANS得到的胶束组成与用P2W17-2CN/C12EO6(n=12和14)的平均相互作用参数计算的胶束组成一致。我们将不利的相互作用归因于不同现象的组合：反离子介导的P2W17单元之间的相互作用和非离子表面活性剂环氧乙烷头基的展开，但由于表面活性剂尾部之间的疏水相互作用，这些体系中仍形成胶束。
HypothesisPolyoxometalates (POMs) are metal oxygen clusters with a range of interesting magnetic and catalytic properties. POMs with attached hydrocarbon chains show amphiphilic behaviour so we hypothesised that mixtures of a nonionic surfactant and anionic surfactants with a polyoxometalate cluster as headgroup would form mixed micelles, giving control of the POM density in the micelle, and which would differ in size and shape from micelles formed by the individual surfactants. Due to the high charge and large size of the POM, we suggested that these would be nonideal mixtures due to the complex interactions between the two types of surfactants. The nonideality and the micellar composition may be quantified using regular solution theory. With supplementary information provided by small-angle neutron scattering (SANS), an understanding of this unusual binary surfactant system can be established.ExperimentsA systematic study was performed on mixed surfactant systems containing polyoxometalate-headed amphiphiles (K10[P2W17O61OSi2(CnH2n+1)2], abbreviated as P2W17-2Cn, where n = 12, 14 or 16) and hexaethylene glycol monododecyl ether (C12EO6). Critical micelle concentrations (CMCs) of these mixtures were measured and used to calculate the interaction parameters based on regular solution theory, enabling prediction of micellar composition. Predictions were compared to micelle structures obtained from SANS. A phase diagram was also established.FindingsThe CMCs of these mixtures suggest unusual unfavourable interactions between the two species, despite formation of mixed micelles. Micellar compositions obtained from SANS concurred with those calculated using the averaged interaction parameters for P2W17-2Cn/C12EO6(n = 12 and 14). We attribute the unfavourable interactions to a combination of different phenomena: counterion-mediated interactions between P2W17units and the unfolding of the ethylene oxide headgroups of the nonionic surfactant, yet micelles still form in these systems due to the hydrophobic interactions between surfactant tails.
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DOI：
--
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期刊：
影响因子：
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