Inferring Chemical Reaction Patterns Using Rule Composition in Graph Grammars

Modeling molecules as undirected graphs and chemical reactions as graph rewriting operations is a natural and convenient approach tom odeling chemistry. Graph grammar rules are most naturally employed to model elementary reactions like merging, splitting, and isomerisation of molecules. It is often convenient, in particular in the analysis of larger systems, to summarize several subsequent reactions into a single composite chemical reaction. We use a generic approach for composing graph grammar rules to define a chemically useful rule compositions. We iteratively apply these rule compositions to elementary transformations in order to automatically infer complex transformation patterns. This is useful for instance to understand the net effect of complex catalytic cycles such as the Formose reaction. The automatically inferred graph grammar rule is a generic representative that also covers the overall reaction pattern of the Formose cycle, namely two carbonyl groups that can react with a bound glycolaldehyde to a second glycolaldehyde. Rule composition also can be used to study polymerization reactions as well as more complicated iterative reaction schemes. Terpenes and the polyketides, for instance, form two naturally occurring classes of compounds of utmost pharmaceutical interest that can be understood as "generalized polymers" consisting of five-carbon (isoprene) and two-carbon units, respectively

Model validation of simple-graph representations of metabolism

The large-scale properties of chemical reaction systems, such as the metabolism, can be studied with graph-based methods. To do this, one needs to reduce the information -- lists of chemical reactions -- available in databases. Even for the simplest type of graph representation, this reduction can be done in several ways. We investigate different simple network representations by testing how well they encode information about one biologically important network structure -- network modularity (the propensity for edges to be cluster into dense groups that are sparsely connected between each other). To reach this goal, we design a model of reaction-systems where network modularity can be controlled and measure how well the reduction to simple graphs capture the modular structure of the model reaction system. We find that the network types that best capture the modular structure of the reaction system are substrate-product networks (where substrates are linked to products of a reaction) and substance networks (with edges between all substances participating in a reaction). Furthermore, we argue that the proposed model for reaction systems with tunable clustering is a general framework for studies of how reaction-systems are affected by modularity. To this end, we investigate statistical properties of the model and find, among other things, that it recreate correlations between degree and mass of the molecules.Comment: to appear in J. Roy. Soc. Intefac

Bulvallene Reaction Graph

The Monster Graph describing a rapidly reversible degenerate Cope rearrangement of bullvalene molecule is considered. Some global properties of this 1209600-vertex reaction graph, such as shell counts, properties of geodesics connection enantiomers etc., are discussed

Reaction Spreading on Graphs

We study reaction-diffusion processes on graphs through an extension of the standard reaction-diffusion equation starting from first principles. We focus on reaction spreading, i.e. on the time evolution of the reaction product, M(t). At variance with pure diffusive processes, characterized by the spectral dimension, d_s, for reaction spreading the important quantity is found to be the connectivity dimension, d_l. Numerical data, in agreement with analytical estimates based on the features of n independent random walkers on the graph, show that M(t) ~ t^{d_l}. In the case of Erdos-Renyi random graphs, the reaction-product is characterized by an exponential growth M(t) ~ e^{a t} with a proportional to ln, where is the average degree of the graph.Comment: 4 pages, 3 figure

On the Complexity of Reconstructing Chemical Reaction Networks

The analysis of the structure of chemical reaction networks is crucial for a better understanding of chemical processes. Such networks are well described as hypergraphs. However, due to the available methods, analyses regarding network properties are typically made on standard graphs derived from the full hypergraph description, e.g.\ on the so-called species and reaction graphs. However, a reconstruction of the underlying hypergraph from these graphs is not necessarily unique. In this paper, we address the problem of reconstructing a hypergraph from its species and reaction graph and show NP-completeness of the problem in its Boolean formulation. Furthermore we study the problem empirically on random and real world instances in order to investigate its computational limits in practice