Programming of Dissipative Networks and Transient Vesicles Using Intrinsic Kinetic Discrimination of Thiol Oxidation
Year: 2026
Type: preprint
Abstract: Programmable dissipative systems that mimic life’s ability to execute timed functions—such as apoptosis triggered by inherent reactivity contrasts—remain a fundamental challenge, as most synthetic designs lack the kinetic complexity to orchestrate multi-step, autonomous sequences. Here, we introduce a synthetic dissipative network in which the intrinsic oxidation kinetics of mono- and dithiols serve as an embedded reaction window to program a cascade of thiol-thioester exchange reactions. This autonomous mechanism dictates reaction timing and sequence, translating molecular-scale kinetic differences into a programmed, system-level response. By extending this principle to the material scale, we further construct fuel-driven, self-assembled vesicles that undergo a life-like cycle of formation, functional execution (as catalytic microreactors), and dissipation. This work establishes intrinsic kinetic hierarchies as a general design paradigm for programming temporal order in non-equilibrium systems, inspiring the development of time-evolving functional materials.
Source: ChemRxiv
Authors: Yingjie Huang, Yulu Wang, Hui Zhao
Institution: Sichuan University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Award: G4416038674
OpenAlex ID: W7223182345