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February 8, 2026Journal of Chemical Theory and Computation0 citations

Transition State Theory for Dissociation of Dynamic Bonding Networks

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EAEric V. AnslynDMDmitrii E. Makarov

Key Points

  • The aim is to estimate the time required to dissociate multiple chemical bonds in dynamic bonding networks using a new approach.
  • Used transition-state theory analogously to assess bond dynamics.
  • Analyzed the mean first passage time for forming or breaking N bonds.
  • Connected single-bond properties and thermodynamic characteristics for predictions.
  • The new estimation method aligns closely with kinetic details of individual bond dynamics.
  • The prediction is supported by statistical-mechanical models, such as the Ising model.
  • Demonstrated that network dynamics can be effectively linked to thermodynamic properties.

Abstract

Cell adhesion, molecular recognition, biomolecular folding and unfolding, dynamic cross-linking in soft materials, and many other phenomena involve formation or dissociation of multiple chemical bonds. Here, we study the overall time scale required to break or form N bonds. Strictly speaking, this time scale depends on the initial conditions, e.g., the number and which bonds are formed/broken, and its estimation requires kinetic details about forming and breaking of each individual bond influenced by the larger network of other bonds. We show, however, that a simple estimate, analogous to transition-state theory in chemical kinetics, accurately predicts the mean first passage time to form or break all the bonds in terms of single-bond properties and thermodynamic properties of the network. As the thermodynamics of bond networks can often be described by well-studied statistical-mechanical models, such as the Ising model and its extensions, our theory provides a link between the global dynamics and thermodynamics of multibond arrays and networks.

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Cite This Study

Anslyn et al. (2026) studied this question.

synapsesocial.com/papers/698827b40fc35cd7a8846a38https://doi.org/10.1021/acs.jctc.5c01797
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