Generating system-level responses from a network of simple synthetic replicators
Abstract
The creation of reaction networks capable of exhibiting responses that are properties of entire systems represents a significant challenge for the chemical sciences. The system- level behavior of a reaction network is linked intrinsically to its topology and the functional connections between its nodes. A simple network of chemical reactions constructed from four reagents, in which each reagent reacts with exactly two others, can exhibit up-regulation of two products even when only a single chemical reaction is addressed catalytically. We implement a system with this topology using two maleimides and two nitrones of different sizes—either short or long and each bearing complementary recognition sites—that react pairwise through 1,3-dipolar cycloaddition reactions to create a network of four length-segregated replicating templates. Comprehensive 1H NMR spectroscopy experiments unravel the network topology, confirming that, in isolation, three out of four templates self-replicate, with the shortest template exhibiting the highest efficiency. The strongest template effects within the network are the mutually cross-catalytic relationships between the two templates of intermediate size. The network topology is such that the addition of different preformed templates as instructions to a mixture of all starting materials elicits system-level behavior. Instruction with a single template up-regulates the formation of two templates in a predictable manner. These results demonstrate that the rules governing system-level behavior can be unraveled through the application of wholly synthetic networks with well-defined chemistries and interactions.
Citation
Sadownik , J W , Kosikova , T & Philp , D 2017 , ' Generating system-level responses from a network of simple synthetic replicators ' , Journal of the American Chemical Society , vol. 139 , no. 48 , pp. 17565-17573 . https://doi.org/10.1021/jacs.7b09735
Publication
Journal of the American Chemical Society
Status
Peer reviewed
ISSN
0002-7863Type
Journal article
Description
The financial support for this work was provided by EaStCHEM and the Engineering and Physical Sciences Research Council (Grant EP/K503162/1).Collections
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.