Developing complexity using networks of synthetic replicators

Molecular recognition;

Kosikova, Tamara ; Philp, Douglas ; Philp, Douglas

University:University of St Andrews

Department:Chemistry (School of)

关键词: Molecular recognition;   

Others  :  https://research-repository.st-andrews.ac.uk/bitstream/handle/10023/10835/TamaraKosikovaPhDThesis.pdf?sequence=2&isAllowed=y

来源: DR-NTU

【 摘 要 】

Molecular recognition plays an essential role in the self-assembly and self-organisationof biological and chemical systems alike—allowing individual components to formcomplex interconnected networks. Within these systems, the nature of the recognitionand reactive processes determines their functional and structural properties, and evensmall changes in their identity or orientation can exert a dramatic effect on the observedproperties. The rapidly developing field of systems chemistry aims to move awayfrom the established paradigm in which molecules are studied in isolation, towardsthe study of networks of molecules that interact and react with each other. Takinginspiration from complex natural systems, where recognition processes never operatein isolation, systems chemistry aims to study chemical networks with the view toexamining the system-level properties that arise from the interactions and reactionsbetween the components within these systems.The work presented in this thesis aims to advance the nascent field of systemschemistry by bringing together small organic molecules that can react and interacttogether to form interconnected networks, exhibiting complex behaviour, such as self-replication, as a result. Three simple building blocks are used to construct a networkof two structurally similar replicators and their kinetic behaviour is probed through acomprehensive kinetic analysis. The selectivity for one of the recognition-mediatedreactive processes over another is examined within the network in isolation as well asin a scenario where the network is embedded within a pool of exchanging components.The interconnected, two-replicator network is examined under far-from-equilibriumreaction-diffusion conditions, showing that chemical replicating networks can exhibitsigns of selective replication—a complex phenomenon normally associated with biologicalsystems. Finally, a design of a well-characterised replicator is exploited forthe construction of a network integrating self-replication with a another recognition-directedprocess, leading to the formation of a mechanically-interlocked architecture—a[2]rotaxane.