化学
多金属氧酸盐
层状结构
小泡
超分子化学
溶致性
自组装
溶致液晶
胶束
等温滴定量热法
两亲性
结晶学
膜
小角X射线散射
纳米尺度
化学工程
纳米技术
相(物质)
有机化学
物理化学
散射
晶体结构
材料科学
液晶
生物化学
聚合物
物理
工程类
水溶液
光学
共聚物
催化作用
作者
Clément Falaise,Soumaya Khlifi,Pierre Bauduin,Philipp Schmid,Jéril Degrouard,Amélie Leforestier,William Shepard,Jérôme Marrot,Mohamed Haouas,David Landy,Caroline Mellot‐Draznieks,Emmanuel Cadot
摘要
The self-assembly of organic amphiphilic species into various aggregates such as spherical or elongated micelles and cylinders up to the formation of lyotropic hexagonal or lamellar phases results from cooperative processes orchestrated by the hydrophobic effect, while those involving ionic inorganic polynuclear entities and nonionic organic components are still intriguing. Herein, we report on the supramolecular behavior of giant toroidal molybdenum blue-type polyoxometalate, namely, the {Mo154} species in the presence of n-octyl-β-glucoside (C8G1), widely used as a surfactant in biochemistry. Structural investigations were carried out using a set of complementary multiscale methods including single-crystal X-ray diffraction analysis supported by molecular modeling, small-angle X-ray scattering and cryo-TEM observations. In addition, liquid NMR, viscosimetry, surface tension measurement, and isothermal titration calorimetry provided further information to decipher the complex aggregation pathway. Elucidation of the assembly process reveals a rich scenario where the presence of the large {Mo154} anion disrupts the self-assembly of the C8G1, well-known to produce micelles, and induces striking successive phase transitions from fluid-to-gel and from gel-to-fluid. Herein, intimate organic-inorganic primary interactions arising from the superchaotropic nature of the {Mo154} lead to versatile nanoscopic hybrid C8G1-{Mo154} aggregates including crystalline discrete assemblies, smectic lamellar liquid crystals, and large uni- or multilamellar vesicles where the large torus {Mo154} acts a trans-membrane component.
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