Preparation of nanostructures by orthogonal self-assembly of hydrogelators and surfactants
Preparation of nanostructures by orthogonal self-assembly of hydrogelators and surfactants
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DOI：
10.1002/anie.200704609
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
van Esch, Jan
中科院分区：
文献类型：
--
作者：
Brizard, Aurelie;Stuart, Marc;van Esch, Jan
自然界，通过其无处不在的由分子成分（特别是脂质和蛋白质）自组装构建的复杂纳米物体的例子，可以提供拓扑控制的分区结构，这对高端生理功能至关重要自然系统的形成不仅是由互补的分子间相互作用驱动的，而且还来自于导致（微）相分离的成分的固有不相容性，如蛋白质折叠和生物膜。微相分离在嵌段共聚物的自组装中得到了广泛的应用，[2,3]然而，只有少数例子利用不同组分的可控相分离来制造人工纳米结构组件。这些例子包括相分离的聚合物体系，碳氢化合物和全氟磷脂的双层结构，[5]液晶相的低分子水凝胶或表面活性剂胶束[7]以及纳米胶囊[8]尽管超分子化学取得了进展，但人工自组装结构的复杂性和功能水平仍无法与自然系统竞争本文表明，多组分的正交自组装，即在单个系统内独立形成不同的超分子结构，每种超分子结构都有自己的特点，是形成新颖和更复杂结构的一种通用而有力的方法。这些结构包括自组装的互穿网络和与水凝胶纤维共存的囊泡结构（方案1）。表面活性剂是典型的小分子，为通过正交自组装制造结构提供了一个有趣的起点。它们是细胞膜的重要组成部分，有许多技术应用。尽管表面活性剂的结构多样性很大，但它们只能形成有限范围的超分子结构，包括球形或棒状胶束、双层胶束、囊泡和倒胶束另一类有吸引力的自组装单元是低分子量凝胶。虽然它们也会导致类似的超分子结构，但凝胶也可以自组装成高度组织化和反应灵敏的纤维结构这一特性是当前人们对智能材料发展相当感兴趣的原因
Nature, through its ubiquitous examples of complex nanoobjects constructed by the self-assembly of molecular components, in particular lipids and proteins, can deliver the topologically controlled compartmentalized architectures that are essential to high-end physiological functions.[1] The formation of natural systems is driven not only by complementary intermolecular interactions, but also emerges from the inherent incompatibility of components that leads to (micro) phase separation, as manifested in protein folding and biological membranes. Microphase separation has been extensively exploited in the self-assembly of block copolymers,[2, 3] however, there are only a few examples in which the controlled phase separation of distinct components has been utilized to fabricate artificial nanostructured assemblies. These examples include, phase-separated polymer systems,[4] bilayers of hydrocarbon and perfluorinated phospholipids,[5] low-molecular-weight hydrogelators in liquid-crystalline phases [6] or with surfactant micelles [7] as well as nanocapsules [8] Despite the progress in supramolecular chemistry,[9] man-made self-assembled structures can not yet compete with the level of complexity and functionality of natural systems.[10] Herein we show that the orthogonal self-assembly of multiple components, that is, the independent formation within a single system of different supramolecular structures, each with their own characteristics, is a versatile and powerful approach towards the formation of novel and more complex architectures. These architectures include self-assembled interpenetrating networks and vesicle configurations that coexist with hydrogel fibers (Scheme 1).Surfactants are typical small molecules that offer an interesting starting point for the fabrication of architectures through orthogonal self-assembly. They are essential components of cell membranes and have numerous technological applications. Despite their large structural diversity, surfactants lead to a limited range of supramolecular architectures, including spherical or rodlike micelles, bilayers, vesicles, and inverted micelles.[11] Another attractive class of self-assembling units are the low-molecular-weight gelators. Although they too lead to a similar range of supramolecular structures, gelators can also self-assemble into highly organized and responsive fibrillar architectures.[12] This property is the source of the considerable current interest in the development of smart materials.[13]