Probing Crosscatalysis, Autocatalysis and Amplification Effects in Hypercyclic Replication Networks

Lead Research Organisation: University of St Andrews
Department Name: Chemistry

Abstract

Replication is the cornerstone of the success of biological systems. The behaviour of replicating systems has many attractive features that are of interest to synthetic chemists. If we can learn to design and exploit replication in a purely synthetic, i.e. non-biological context, the development of cleaner and more efficient synthetic routes to important compounds becomes possible. The cooperation and interaction between replication systems in biology is key to evolving more complex behaviour. This behaviour is termed hypercyclic and encompasses features such as feedback loops and amplification of specific products. This project aims to investigate, develop and exploit this hypercyclic behaviour in synthetic systems. The outcome of this research programme is very hard to predict a priori. It is possible, though unlikely based on our preliminary simulations, that placing different replicating systems in competition or cooperation might simply lead to each system inhibiting the operation of the others. If this scenario emerges, that this result in itself is important in that it places certain constraints on the emergence and the identity of early replicators on the prebiotic earth. If, however, we can evolve complex hypercyclic cooperative behaviour, such as feedback loops and amplification, then we will have demonstrated that complex behaviour is ubiquitous and by careful design can be harnessed to whatever synthetic end is demanded by the chemist. This proposal aims to address these issues through a programme of fundamental and systematic studies of minimal and reciprocal replication and their interactions with the goals of both exposing the basic physical organic chemistry of replication and developing an integrated design framework for replicating systems with which to move forward.

Publications

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Bottero I (2016) A Synthetic Replicator Drives a Propagating Reaction-Diffusion Front. in Journal of the American Chemical Society

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Del Amo V (2010) Integrating replication-based selection strategies in dynamic covalent systems. in Chemistry (Weinheim an der Bergstrasse, Germany)

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Hassan NI (2011) Low temperature capture of pseudorotaxanes. in Organic letters

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Huck J (2019) Compositional Persistence in a Multicyclic Network of Synthetic Replicators. in Journal of the American Chemical Society

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Kassianidis E (2010) Designing instructable networks using synthetic replicators in Faraday Discuss.

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Kosikova T (2015) Orthogonal Recognition Processes Drive the Assembly and Replication of a [2]Rotaxane. in Journal of the American Chemical Society

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Turega SM (2008) Target-driven selection in a dynamic nitrone library. in Chemical communications (Cambridge, England)

 
Description o Developed first truly synthetic reciprocal replicator
o Demonstrated that amplification is inherently limited in closed systems
o Demonstrated that a simple replicator can process an pool of reagents autonomously
o Developed a series of reaction networks that exhibit system level behaviour
Exploitation Route Our findings have inspired a number of groups to utilise target amplification strategies developed as part of this work in the development of new materials.
Sectors Chemicals

URL http://chemistry.st-andrews.ac.uk/staff/dp/group/
 
Description An obvious question was "Is the structural complexity of nucleic acids necessary to store and transmit information at a molecular level?" In addition, the concept of a chemical template that is capable of making billions of exact copies of itself, given appropriate starting materials, is a highly attractive one for the synthetic chemist. It was therefore clear that the development of a detailed understanding of the behaviour of minimal self- replicating systems has important perspectives for both biology and chemistry.
First Year Of Impact 2011
Sector Chemicals