State Key Lab of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200230, P. R. China.
Angew Chem Int Ed Engl. 2022 Nov 14;61(46):e202211812. doi: 10.1002/anie.202211812. Epub 2022 Oct 18.
Kinetic co-assembly pathway induced chirality inversion along with morphology transition is of importance to understand biological processes, but still remains a challenge to realize in artificial systems. Herein, helical nanofibers consisting of phenylalanine-based enantiomers (L/DPF) successfully transform into kinetically trapped architectures with opposite helicity through a kinetic co-assembly pathway. By contrast, the co-assemblies obtained by a thermodynamic pathway exhibit non-helical structures. The formation sequence of non-covalent interactions plays a crucial role in structural chirality of co-assemblies. For the kinetic pathway, the hydrogen bonding between D/LPF and naphthylamide derivatives forms before π-π stacking to facilitate the formation of helical structures with inverse handedness. This study may provide an approach to explore chirality inversion accompanied by morphology transition by manipulating the kinetic co-assembly pathway.
动力学共组装途径诱导手性反转以及形态转变对于理解生物过程非常重要,但在人工系统中实现仍然是一个挑战。在此,由苯丙氨酸对映异构体(L/DPF)组成的螺旋纳米纤维通过动力学共组装途径成功转化为具有相反手性的动力学捕获结构。相比之下,通过热力学途径获得的共组装体表现出非螺旋结构。非共价相互作用的形成顺序在手性共组装体的结构中起着关键作用。对于动力学途径,D/LPF 与萘酰胺衍生物之间的氢键在 π-π 堆积之前形成,以促进具有相反手性的螺旋结构的形成。这项研究可能为通过操纵动力学共组装途径探索伴随形态转变的手性反转提供一种方法。