In Situ Biocatalytic ATP Regulated, Transient Supramolecular Polymerization

Abstract

Temporal control over the self-assembly process is a highly desirable attribute that is efficiently exhibited by biological systems, such as actin filaments. In Nature, various proteins undergo enzymatically catalysed chemical reactions that kinetically govern their structural and functional properties. Consequently, any stimuli that can alter their reaction kinetics can lead to a change in their growth or decay profiles. This underscores the urgent need to investigate bioinspired, adaptable and controllable synthetic materials. Herein we intend to develop a general strategy for controlling the growth and decay of self-assembled systems via enzymatically coupled reactions. We achieve this by the coupling of enzymes phosphokinase/phosphatase with a bolaamphiphilic cationic chromophore (PDI) which selectively self-assembles with ATP and disassembles upon its enzymatic hydrolysis. The aggregation process is efficiently regulated by the controlled in-situ generation of ATP, through enzymatic reactions. By carefully managing the ATP generating components, we realize a precise control over the self-assembly process. Moreover, we also show self-assembled structures with programmed temporal decay profiles through coupled enzymatic reactions of ATP generation and hydrolysis, essentially rendering the process dissipative. This work introduces a novel strategy to generate reaction-coupled one-dimensional nanostructure with controlled dimensions inspired by biological systems.