Autocatalysis: Kinetics, Mechanisms and Design

Abstract

The importance of autocatalysis spans from practical applications such as in chemically amplified photoresists, to autocatalysis playing a fundamental role in evolution as well as a plausible key role in the origin of life. The phenomenon of autocatalysis is characterized by its kinetic signature rather than by its mechanistic aspects. The molecules that form autocatalytic systems and the mechanisms underlying autocatalytic reactions are very diverse. This chemical diversity, combined with the strong involvement of chemical kinetics, creates a formidable barrier for entrance to the field. Understanding these challenges, we wrote this Review with three main goals in mind: (i) To provide a basic introduction to the kinetics of autocatalytic systems and its relation to the role of autocatalysis in evolution, (ii) To provide a comprehensive overview, including tables, of synthetic chemical autocatalytic systems, and (iii) To provide an in‐depth analysis of the concept of autocatalytic reaction networks, their design, and perspectives for their development.

On the use of catalysis to bias reaction pathways in out-of-equilibrium systems

“…7,32 A classic example of a bistable system and the basis of some oscillatory systems is an autocatalytic reaction in a CSTR. 33,34 Due to the inherent non-linearity the system shows hysteresis in the reactant efflux vs. feed rate. 35 Illustrative examples of oscillatory CRNs with integrated feedback elements come from the hands of Semenov, Huck and Whitesides.…”

Robust Dynamics of Synthetic Molecular Systems as a Consequence of Broken Symmetry

“…The flaws of the hypothesis will be discussed below and in [6]. An autocatalytic reaction, in which the A → B reaction is accelerated by B, is introduced as a symmetry-broken reaction [7]. The reaction with the co-existence of a non-autocatalytic process, the kinetics equation of which is described in Appendix A, is shown in Figure 2a [6].…”

“…Considering the intrinsic feature of cell amplification, the concept of autocatalysis is fundamental [56,57], and all self-replications occur in an autocatalytic manner [7,[58][59][60][61][62][63][64][65][66][67][68][69][70][71]. In the vesicular self-reproduction system without autocatalysis, the generated vesicles were different from the original ones-the catalytic ratio decreased proportionally in each generation, and the system tended to reach equilibrium, even if the precursor for the membrane molecule was continuously supplied (Figure 4a) [49,50,52].…”

Robust Dynamics of Synthetic Molecular Systems as A Consequence of Broken Symmetry

“…An autocatalytic reaction, in which the A → B reaction is accelerated by B, is introduced as a symmetry-broken reaction. [6] The reaction with the co-existence of a non-autocatalytic process, the kinetics equation of which termed as a logistic equation. An example is shown in Figure 2a.…”

“…Considering the intrinsic feature of cell amplification, the concept of autocatalysis is fundamental, [54,55] and all self-replications occur in an autocatalytic manner. [6,[56][57][58][59][60][61][62][63][64][65][66][67][68][69] In the vesicular self-reproduction system without autocatalysis, the generated vesicles were different from the original ones -the catalytic ratio decreased proportionally in each generation, and the system tended to equilibrium, even if the precursor for the membrane molecule was continuously supplied (Figure 4a). [47,48,50] This behavior is the same as inanimate systems.…”