Chiral superstructures in confined spaces are subtly affected by the complex interplay among various noncovalent interactions, details of which are still inadequately understood. Herein, we report the three-dimensional confined assembly of the chiral block co-polymers of polystyrene-block-poly(d-lactide) and its enantiomer in emulsion droplets and demonstrate unprecedented successive microphase transformations from single helices to double helices with inverted helicity, and then to twisted cylinders in the constructed colloidal particles. The above hierarchical structural transformations of chiral microphases are kinetically dependent and can further transform into thermodynamically stable achiral cylinders with saddle-shaped topology upon solvent annealing. The formation and subsequent structural transformations as well as the final degeneration of chiral architectures provide guidance to understand the chiral evolution at different length scales within spherical confined space and to fabricate biomimetic systems.

密闭空间中的手性上层结构受到各种非共价相互作用之间复杂相互作用的微妙影响，其细节仍未得到充分了解。在此，我们报告了聚苯乙烯-嵌段-聚( d-丙交酯）及其在乳液液滴中的对映异构体，并展示了前所未有的连续微相转变，从单螺旋到具有倒螺旋度的双螺旋，然后到构建的胶体颗粒中的扭曲圆柱体。上述手性微相的分级结构转变是动力学相关的，并且可以在溶剂退火后进一步转变为具有马鞍形拓扑结构的热力学稳定的非手性圆柱体。手性结构的形成和随后的结构转变以及最终的退化为理解球形受限空间内不同长度尺度的手性演化和制造仿生系统提供了指导。