Searcharxiv⌕ Search
Home/Archive/arXiv

arXiv · 2201.04515

Representing catalytic mechanisms with rule composition

Jakob L. Andersen·Rolf Fagerberg·Christoph Flamm·Walter Fontana·Juri Kolčák·Christophe V. F. P. Laurent·Daniel Merkle·Nikolai Nøjgaard
View original source ↗Read source document ↗Export metadata ↓

Abstract

Reaction mechanisms are often presented as sequences of elementary steps, such as codified by arrow pushing. We propose an approach for representing such mechanisms using graph transformation. In this framework, each elementary step is a rule for modifying a molecular graph and a mechanism is a sequence of such rules. To generate a compact representation of a multi-step reaction, we compose the rules of individual steps into a composite rule, providing a rigorous and fully automated approach to coarse-graining. While the composite rule retains the graphical conditions necessary for the execution of a mechanism, it also records information about transient changes not visible by comparing educts and products. By projecting the rule onto a single "overlay graph", we generalize Fujita's idea of an Imaginary Transition Structure from elementary reactions to composite reactions. The utility of the overlay graph construct is exemplified in the context of enzyme-catalyzed reactions. In a first application, we exploit mechanistic information in the Mechanism and Catalytic Site Atlas to construct overlay graphs of hydrolase reactions listed in the database. These graphs point at a spectrum of catalytic entanglement of enzyme and substrate, de-emphasizing the notion of a singular catalyst in favor of a collection of catalytic sites that can be distributed across enzyme and substrate. In a second application, we deploy composite rules to search the Rhea database for reactions of known or unknown mechanism that are, in principle, compatible with the mechanisms implied by the composite rules. We believe this work adds to the utility of graph-transformation formalisms in representing and reasoning about chemistry in an automated yet insightful fashion.

Explore related subjects

cs.DMphysics.chem-phq-bio.MN

Keep this discovery

BibTeXRIS

Jakob L. Andersen, Rolf Fagerberg, Christoph Flamm, Walter Fontana, Juri Kolčák, Christophe V. F. P. Laurent, Daniel Merkle, Nikolai Nøjgaard. 2022-01-12. Representing catalytic mechanisms with rule composition. https://arxiv.org/abs/2201.04515

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

arXiv2026

An FPTAS for Two-Machine Open-Shop Scheduling with a Single Unavailability Interval

We consider the two-machine open-shop scheduling problem in which one machine is unavailable during a fixed interval. We study the resumable setting: an operation interrupted by the unavailability interval may resume, without penalty, when the machine becomes available. The objective is to minimize the makespan. Although the problem is NP-hard and several approximation algorithms are known, whether it admits a fully polynomial-time approximation scheme (FPTAS) has remained open for two decades. We resolve this question affirmatively by giving the first FPTAS, thereby strengthening the previously known polynomial-time approximation scheme (PTAS). As an intermediate result, we develop a new pseudo-polynomial dynamic program with seven state dimensions, improving on the ten-dimensional formulation in the literature.

cs.DM↗
arXiv2026

Generalized Graph Search Trees

Graph search algorithms and their corresponding graph search trees are commonly used in algorithmic graph theory. In recent years, the recognition problem of these graph search trees has received significant attention. So far, the research has focused on two types of search trees: first-in trees that behave like BFS-trees and last-in trees that behave like DFS-trees. The search tree paradigms differ from each other by the parent a vertex is connected to. In first-in trees, it is the first visited neighbor, while in last-in trees it is the last neighbor visited before that vertex. Here, we will generalize these concepts of graph search trees by allowing every preceding neighbor of a vertex to be the parent. We study the complexity of the recognition problem of these generalized graph search trees. We present NP-completeness proofs for most searches. We also show that the problem is trivial for Generic Search and polynomial-time solvable for several searches on bipartite graphs and chordal graphs. We also study the question how fixing the start vertex influences the complexity of the problem.

cs.DM↗
arXiv2026

The exact asymptotic constant in the metric dimension of Jaccard space

Let $X$ be a finite set with $|X|=n$ and let $\mathrm{Jac}(a,b)=|a\,\triangle\, b|/|a\cup b|$ be the Jaccard distance on the power set $2^X$. Lladser and Paradise recently proved that the metric dimension of $(2^X,\mathrm{Jac})$ is $\Theta(n/\ln n)$, with the constant left open; their bounds are $(\ln 2)\,n/\ln n\lesssim \beta(2^X,\mathrm{Jac})\lesssim 2\ln(2e)\,n/\ln n$. We determine the constant: \[ \beta(2^X,\mathrm{Jac})=\frac{2n}{\log_2 n}\,(1+o(1))=(2\ln 2)\,\frac{n}{\ln n}\,(1+o(1)). \] The proof identifies the problem, on each ``slice'' of subsets of fixed cardinality, with the Erd\H{o}s--R\'enyi coin-weighing problem for a spring scale (the problem of \emph{detecting matrices}). The lower bound is the Erd\H{o}s--R\'enyi entropy argument applied to the middle slice; the upper bound follows from the explicit detecting families of Lindstr\"om and of Cantor and Mills, augmented by a single extra landmark that reveals cardinality.

cs.DM↗