Law of Mass Action Type Chemical Mechanisms for Modeling Autocatalysis and Hypercycles: Their Role in the Evolutionary Race

Abstract

One of our most appealing challenge is to unravel the role of a presumably autocatalytic system in controlling the origin and spreading of Life on our entire planet. Here we show that in the simplest autocatalytic loop involving reactions capable of self‐replication and obeying law of mass action kinetics, concentration growth of the autocatalyst may be characterized by parametrization of direct and autocatalytic pathways rather than by kinetic orders of the autocatalyst. Extending this model by feasible elementary steps allows us to outline super‐exponential growth where kinetic order of the autocatalyst is higher than unity. Furthermore, it is shown in case of the simplest hypercycle that such a situation might appear where the otherwise more sluggish autocatalytic route receives a decisive support from the crosscatalytic pathway to become an apparently stronger autocatalytic loop even if the other route contains a more efficient autocatalysis. If the hypercycle is performed under flow conditions selection of autocatalyst depends on kinetic and flow parameters influenced by external factors mimicking that the most adaptive loop of hypercycle eventually finds its wining way in the evolutionary race.

Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

“…Such a situation is often encountered in the framework of autocatalyzed reactions. 35 However, in this specific case, such autocatalysis-like evolution is not due to a simple molecular mechanism, but more likely to a complex combination of rheological and physicochemical phenomena. From this point of view, the silica acceleration effect is instructive, because it was assumed to originate from a preassociation mechanism resulting from a rigid anchoring of the reaction partners within a critical bonding distance.…”

Thermodynamic Analysis of the Landolt-Type Autocatalytic System

“…This work, in fact, was motivated by a model analysis published recently by Horváth [14]. He analyzed several typical autocatalytic reaction schemes from the kinetic viewpoint, focusing particularly on the time evolution of the concentration of a product with the autocatalytic action.…”

“…He analyzed several typical autocatalytic reaction schemes from the kinetic viewpoint, focusing particularly on the time evolution of the concentration of a product with the autocatalytic action. Among the schemes was a three-step reaction sequence called the Landolt-type autocatalytic system [14]. Horváth stressed the importance of parametrization in autocatalytic routes.…”

“…The thermodynamic viewpoint was not presented in ref. [14]. Recently, the method of applying a methodology of non-equilibrium thermodynamics to the analysis of autocatalytic processes and their kinetics was shown [15].…”

“…This work extends both Horváth's and the previous [15] works by thermodynamic analysis of the Landolt-type system studied kinetically in ref. [14]. First, the consistency with non-equilibrium thermodynamics is demonstrated, then the description using independent reactions is discussed; a brief comment on thermodynamic driving force follows.…”