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PreprintCC BYChemRxiv

Programming of Dissipative Networks and Transient Vesicles Using Intrinsic Kinetic Discrimination of Thiol Oxidation

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.

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BibTeX
@misc{huang2026programming,
  title = {{Programming of Dissipative Networks and Transient Vesicles Using Intrinsic Kinetic Discrimination of Thiol Oxidation}},
  author = {Yingjie Huang and Yulu Wang and Hui Zhao},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010879/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010879/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Programming of Dissipative Networks and Transient Vesicles Using Intrinsic Kinetic Discrimination of Thiol Oxidation
AU  - Yingjie Huang
AU  - Yulu Wang
AU  - Hui Zhao
PY  - 2026
DA  - 2026/10/22
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010879/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010879/v1
AB  - 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.
ER  -