Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel.
Chemistry. 2011 May 23;17(22):6068-75. doi: 10.1002/chem.201003419. Epub 2011 May 3.
Most molecular self-assembly strategies involve equilibrium systems, leading to a single thermodynamic product as a result of weak, reversible non-covalent interactions. Yet, strong non-covalent interactions may result in non-equilibrium self-assembly, in which structural diversity is achieved by forming several kinetic products based on a single covalent building block. We demonstrate that well-defined amphiphilic molecular systems based on perylene diimide/peptide conjugates exhibit kinetically controlled self-assembly in aqueous medium, enabling pathway-dependent assembly sequences, in which different organic nanostructures are evolved in a stepwise manner. The self-assembly process was characterized using UV/Vis circular dichroism (CD) spectroscopy, and cryogenic transmission electron microscopy (cryo-TEM). Our findings show that pathway-controlled self-assembly may significantly broaden the methodology of non-covalent synthesis.
大多数分子自组装策略涉及平衡体系，由于弱的、可逆的非共价相互作用，导致只有单一的热力学产物。然而，强非共价相互作用可能导致非平衡自组装，其中通过基于单个共价构筑块形成几种动力学产物来实现结构多样性。我们证明，基于苝二酰亚胺/肽缀合物的具有良好定义的两亲性分子系统在水介质中表现出动力学控制的自组装，从而能够实现基于途径的组装序列，其中不同的有机纳米结构以逐步的方式演变。使用紫外/可见圆二色性（CD）光谱和低温透射电子显微镜（cryo-TEM）对自组装过程进行了表征。我们的研究结果表明，途径控制的自组装可能会极大地拓宽非共价合成的方法学。
