Expanding structural diversity in a library of disulfide macrocycles through in-situ imide hydrolysis

We describe here an unorthodox approach to dynamic covalent chemistry in which the initially-unexpected in-situ hydrolysis of a bis-imide is employed to control the composition of a library of structurally diverse macrocycles. A single building block is used to generate a library of numerous disulfide-based architectures in a one-pot single-step process. The dual-stimuli method is based on simultaneous changes in pH and DMSO concentration to expand the structural diversity of the macrocyclic products. Mechanistic details of this complex process are investigated by the kinetics analysis. We delivered a facile strategy for the synthesis of water-soluble, multicomponent and dynamic macrocycles equipped with number of different functional groups, thus giving a prospect of their application in guest-driven phase transfer.

Impact of dynamic covalent chemistry and precise linker length on crystallization kinetics and morphology in ethylene vitrimers

Vitrimers, dynamic polymer networks with topology conserving exchange reactions, can lead to unusual evolution of the melting temperature and crystal structure of ethylene networks.

Profiling single-molecule reaction kinetics under nanopore confinement

The development of single-molecule reaction inside nanoconfinement is benefit to study the intrinsic molecular mechanism of a complex chemical reaction. However, the reaction kinetics model of single-molecule reaction inside confinement remains elusive. Herein we engineered the Aerolysin nanopore reactor to elaborate the single-molecule reaction kinetics inside nanoconfinement. By identifying bond forming and non-forming events directly, a four-state kinetics model is proposed for the first time. Our results demonstrated that the single-molecule reaction kinetics inside a nanopore depends on the voltage-dependent frequency of captured individual reactant and the fraction of effective collision inside nanopore confined space. This new insight will guide the design of nanoconfinement for resolving the single-molecule chemistry, and shed light on the mechanistic understanding of dynamic covalent chemistry in-side a nanopore