Autocatalytic Cores in Reaction Networks with Explicit Catalysis

Abstract

Autocatalytic cores are minimal units in reaction networks (RNs) responsible for the emergence of autocatalysis. In the absence of explicit catalysis, i.e., when an entity appears both as reactant and product in the same reaction, they are known to be encoded by square submatrices of the stoichiometric matrix whose columns can be reordered as an irreducible child-selection (CS) matrix with negative diagonal and nonnegative off-diagonal (Metzler matrix). In the bipartite Koenig graph representing the RN, these CS matrices can be identified by fluffles, i.e., strong blocks with an identical number of entity and reaction vertices that have out- and in-degree 1, respectively. Here, we adapt the concepts derived for autocatalytic cores to RNs with explicitly catalyzed reactions, which emerge as digons, i.e., elementary circuits in the Koenig graph of length 2. In this setting, we confirm that an inspection of the stoichiometric matrix alone is inconclusive concerning the presence and number of autocatalytic cores, requiring a more delicate algebraic analysis. Nevertheless, this generalization preserves both the graph and the matrix representation as fluffles and irreducible Metzler CS matrices, respectively, although the diagonal is no longer necessarily strictly negative. We introduce the notion of hard autocatalytic cores, i.e. those that do not yield other autocatalytic cores upon inclusion of all reverse reactions. Finally, we consider the case of unit stoichiometries and show that each autocatalytic core can be constructed as the superposition of at most 2 elementary circuits. In particular, autocatalytic cores involving explicitly catalyzed reactions always contain a spanning subgraph consisting of a single elementary circuit together with a simple entity-to-reaction chord. Moreover, we identify the essentially unique example for which at least two circuits are required.