Harnessing autocatalytic reactions in polymerization and depolymerization

Abstract

Autocatalysis and its relevance to various polymeric systems are discussed by taking inspiration from biology. A number of research directions related to synthesis, characterization, and multi-scale modeling are discussed in order to harness autocatalytic reactions in a useful manner for different applications ranging from chemical upcycling of polymers (depolymerization and reconstruction after depolymerization), self-generating micelles and vesicles, and polymer membranes. Overall, a concerted effort involving in situ experiments, multi-scale modeling, and machine learning algorithms is proposed to understand the mechanisms of physical and chemical autocatalysis. It is argued that a control of the autocatalytic behavior in polymeric systems can revolutionize areas such as kinetic control of the self-assembly of polymeric materials, synthesis of self-healing and self-immolative polymers, as next generation of materials for a sustainable circular economy. Graphic Abstract

Size-Dependent Sigmoidal Reaction Kinetics for Pyruvic Acid Condensation at the Air–Water Interface in Aqueous Microdroplets

“…For product formation, similar kinetics was observed (Figure S8). For bulk solutions, these kinetic profiles of reactant and products represent an autocatalytic reaction. − …”

Bringing Quantum Mechanics to Coarse-Grained Soft Materials Modeling

“…60 More recently, researchers are trying to understand how to manipulate autocatalytic processes to induce biology-inspired self-assembly pathways in synthetic materials. 61 As time goes on, it becomes clear that biology has effectively integrated QM phenomena over many length scales of intrinsically heterogeneous and disordered morphologies of soft materials, making biological materials fascinating grounds for integrating both QM and classical mechanical modeling. Significant previous method development efforts have gone into addressing many of these challenging biological design problems.…”

“…Understanding QM transport in photosynthetic and light-harvesting complexes has occupied an enormous fraction of modern chemical research agendas. − Biological energy transduction in active materials is typically derived from multielectron state changes in ATP, for which QM effects are fundamental . More recently, researchers are trying to understand how to manipulate autocatalytic processes to induce biology-inspired self-assembly pathways in synthetic materials . As time goes on, it becomes clear that biology has effectively integrated QM phenomena over many length scales of intrinsically heterogeneous and disordered morphologies of soft materials, making biological materials fascinating grounds for integrating both QM and classical mechanical modeling.…”

Chemical Amplification of Subthreshold Base Triggers To Drive Sol–Gel Transitions in Polymers

“…Thus, for practical purposes, we define the apparent gelation point as when G ′ first reached 100 Pa. When a more dilute BPD solution was used as the trigger, the induction period increased correspondingly, which is characteristic of an autocatalytic reaction. , As BPD concentration was decreased to 5 mM (BA/BPD = 120, mol/mol), gelation was not observed until several days later. Nonetheless, all three samples reached very similar plateaus, and the plateau G ′ was on the order of several MPa, which is 2 orders of magnitude higher than the maximum theoretical value from rubber elasticity theory (27.60 kPa; see the Supporting Information (SI) for calculation).…”