Structural self-sorting of pseudopeptide homo and heterodimeric disulfide cages in water: mechanistic insights and cation sensing

Abstract

The molecular components of biological systems self-sortviadifferent mechanisms to act in a cooperative manner and to avoid interfering with each other. Herein we describe mechanistic insights and a versatile strategy for the synthesis of water-soluble, pseudopeptide molecular cages based on disulfide bonds. The use of trifunctional thiols led to a dynamic combinatorial library (DCL) of readily isolable, multi-component homo and hetero cage-like architectures showing a degree of self-sorting related to the symmetry and size of the trithiol. The work provided detailed kinetic studies and DFT molecular modeling giving original insights into the disulfide cages' properties. We also applied the selected cage system in the fluorometric detection of La3+cations, which led to the generation of a strongly luminescent metal-organic assembly.