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<p>Catch bonds—dynamic molecular interactions whose lifetimes increase under mechanical load—are central to biological mechanotransduction but remain challenging to replicate synthetically. Here, we report a covalent catch-bonding mechanism in a low-molecular-weight motif based on hydroxyethyl phosphate (HEP) triesters. Our design uses force-mediated inhibition of a neighboring group participation (NGP) pathway: mechanical tension suppresses intramolecular assistance, thereby increasing the reaction barrier and prolonging bond lifetimes. Density Functional Theory calculations confirm that tensile force hinders the geometric contraction required for NGP, providing a mechanistic basis for catch-bond behaviour. Single-molecule force spectroscopy reveals that HEP triester lifetimes increase over threefold at 400 pN. This work establishes a molecular mechanism for engineering covalent catch bonds, offering opportunities to design force-responsive polymer networks. By translating a biological concept into a synthetic framework, our findings open new avenues for adaptive materials and mechanochemical sensing.</p>

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Neighbouring group participation hindered by force as a molecular design for covalent catch bonds

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月22日

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  • Soumabrata Majumdar,
  • Diederik van Luijk,
  • Martijn M. van Galen,
  • Pascal Vermeeren,
  • Trevor A. Hamlin,
  • F. Matthias Bickelhaupt,
  • Joris H. B. Sprakel,
  • Rolf A. T. M. van Benthem,
  • Johan P. A. Heuts,
  • Rint P. Sijbesma

摘要

Catch bonds—dynamic molecular interactions whose lifetimes increase under mechanical load—are central to biological mechanotransduction but remain challenging to replicate synthetically. Here, we report a covalent catch-bonding mechanism in a low-molecular-weight motif based on hydroxyethyl phosphate (HEP) triesters. Our design uses force-mediated inhibition of a neighboring group participation (NGP) pathway: mechanical tension suppresses intramolecular assistance, thereby increasing the reaction barrier and prolonging bond lifetimes. Density Functional Theory calculations confirm that tensile force hinders the geometric contraction required for NGP, providing a mechanistic basis for catch-bond behaviour. Single-molecule force spectroscopy reveals that HEP triester lifetimes increase over threefold at 400 pN. This work establishes a molecular mechanism for engineering covalent catch bonds, offering opportunities to design force-responsive polymer networks. By translating a biological concept into a synthetic framework, our findings open new avenues for adaptive materials and mechanochemical sensing.