Enzymatic Reaction-Coupled, Cooperative Supramolecular Polymerization

J Am Chem Soc. 2024 May 29;146(21):14844-14855. doi: 10.1021/jacs.4c03588. Epub 2024 May 15.

Abstract

Nature employs sophisticated mechanisms to precisely regulate self-assembly and functions within biological systems, exemplified by the formation of cytoskeletal filaments. Various enzymatic reactions and auxiliary proteins couple with the self-assembly process, meticulously regulating the length and functions of resulting macromolecular structures. In this context, we present a bioinspired, reaction-coupled approach for the controlled supramolecular polymerization in synthetic systems. To achieve this, we employ an enzymatic reaction that interfaces with the adenosine triphosphate (ATP)-templated supramolecular polymerization of naphthalene diimide monomers (NSG). Notably, the enzymatic production of ATP (template) plays a pivotal role in facilitating reaction-controlled, cooperative growth of the NSG monomers. This growth process, in turn, provides positive feedback to the enzymatic production of ATP, creating an ideal reaction-coupled assembly process. The success of this approach is further evident in the living-growth characteristic observed during seeding experiments, marking this method as the pioneering instance where reaction-coupled self-assembly precisely controls the growth kinetics and structural aspects of supramolecular polymers in a predictive manner, akin to biological systems.

MeSH terms

  • Adenosine Triphosphate* / chemistry
  • Adenosine Triphosphate* / metabolism
  • Imides* / chemistry
  • Kinetics
  • Macromolecular Substances / chemical synthesis
  • Macromolecular Substances / chemistry
  • Macromolecular Substances / metabolism
  • Molecular Structure
  • Naphthalenes* / chemical synthesis
  • Naphthalenes* / chemistry
  • Naphthalenes* / metabolism
  • Polymerization*
  • Polymers / chemistry

Substances

  • Naphthalenes
  • Adenosine Triphosphate
  • naphthalenediimide
  • Imides
  • Macromolecular Substances
  • Polymers