In the field of molecular self‐assembly, the core of an assembly is always made up of hydrophobic moiety like a long alkyl chain, whereas the outer part has always been a hydrophilic moiety such as poly(ethylene glycol) (PEG), or charged species. Hence, reversing the trend to manifest self‐assembled structures with a PEG core and a surface consisting of alkyl chains in aqueous system is incredibly challenging. Herein, we architected a unique class of cationic bolaamphiphiles containing low molecular weight PEG and alkyl chains of different lengths. The bolaamphiphiles spontaneously form vesicles without external stimuli. These vesicles are unprecedented because PEG makes up the vesicle core, while the alkyl chains appear on the vesicles' exterior. Hence, this is the first report on an assembly that reverses the usual trend. The vesicle size increases with the increase in alkyl chain‐length. To our great surprise, we obtained large micelles for longest alkyl‐chain amphiphile, which in turn act as a gemini amphiphile. The shift from a particular bolaamphiphile to gemini amphiphile with the variation of alkyl chain is also unexplored. Therefore, this specific class of self‐assembled structure would compound a new paradigm in the fields of molecular self‐assembly and supramolecular chemistry.

中文翻译：

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扭转趋势：破译具有烷基链和 PEG 的非常规两亲物的自组装

在分子自组装领域，组装体的核心总是由疏水部分组成，如长烷基链，而外部部分始终是亲水部分，如聚乙二醇（PEG）或带电荷的部分。物种。因此，扭转在水性系统中显示具有 PE​​G 核心和由烷基链组成的表面的自组装结构的趋势是非常具有挑战性的。在此，我们构建了一类独特的阳离子双亲物，含有低分子量 PEG 和不同长度的烷基链。博拉两亲物在没有外部刺激的情况下自发形成囊泡。这些囊泡是前所未有的，因为 PEG 构成囊泡核心，而烷基链出现在囊泡外部。因此，这是第一份关于扭转通常趋势的集会的报告。囊泡尺寸随着烷基链长度的增加而增加。令我们大吃一惊的是，我们获得了最长烷基链两亲物的大胶束，这反过来又充当双子两亲物。随着烷基链的变化，从特定的双亲物到双子两亲物的转变也尚未被探索。因此，这种特殊的自组装结构将在分子自组装和超分子化学领域形成新的范式。