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dc.contributor.authorKosikova, Tamara
dc.contributor.authorPhilp, Douglas
dc.date.accessioned2018-08-03T23:34:32Z
dc.date.available2018-08-03T23:34:32Z
dc.date.issued2019-09-13
dc.identifier.citationKosikova , T & Philp , D 2019 , ' A critical cross-catalytic relationship determines the outcome of competition in a replicator network ' , Journal of the American Chemical Society , vol. 139 , no. 36 , pp. 12579-12590 . https://doi.org/10.1021/jacs.7b06270en
dc.identifier.issn0002-7863
dc.identifier.otherPURE: 250656295
dc.identifier.otherPURE UUID: a2cbcc2b-583a-442d-8dcb-6d4369ddaf3d
dc.identifier.otherScopus: 85029507425
dc.identifier.otherORCID: /0000-0002-9198-4302/work/56639244
dc.identifier.otherWOS: 000411043900044
dc.identifier.urihttp://hdl.handle.net/10023/15767
dc.descriptionThe financial support for this work was provided by the University of St Andrews and the Engineering and Physical Sciences Research Council (Grant EP/K503162/1).en
dc.description.abstractA network of two synthetic replicators exhibits a critical unidirectional cross-catalytic relationship that directs competing replication processes. In this network, nitrone N bearing a 6-methylamidopyridine recognition site can participate in 1,3-dipolar cycloaddition reactions with two maleimides that differ in the relative position of their carboxylic acid recognition site: either para (Mp) or meta (Mm) relative to the maleimide ring. These cycloaddition reactions create replicators trans-Tp and trans-Tm. In isolation, trans-Tp templates its own formation with an efficiency that is markedly greater than that of trans-Tm. Kinetic fitting and simulations reveal that this efficiency arises from a higher template-mediated rate constant for the cycloaddition and lower stability of the trans-Tp template duplex, compared to trans-Tm. By contrast, in a situation where Mp and Mm compete for a limited quantity of N, the normally less efficient trans-Tm outcompetes trans-Tp. Through a series of comprehensive kinetic 19F{1H} NMR spectroscopy experiments, this system-level outcome is traced to a critical cross-catalytic pathway, whereby the presence of trans-Tp templates the formation of trans-Tm, but not vice versa. Replicator trans-Tm also reduces the efficiency of its competitor trans-Tp by sequestering trans-Tp in a heteroduplex that is more stable than homoduplex [Tp•Tp]. The addition of different templates as instructions reveals that, while the outcome of competition between replicators can be altered selectively, it is limited by the reaction environment employed. These results represent a conceptual and practical framework for the examination of selectivity in replication networks operating outside well-stirred batch reactor conditions.
dc.format.extent12
dc.language.isoeng
dc.relation.ispartofJournal of the American Chemical Societyen
dc.rightsCopyright © 2017 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1021/jacs.7b06270en
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subjectBDCen
dc.subject.lccQDen
dc.titleA critical cross-catalytic relationship determines the outcome of competition in a replicator networken
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews.Biomedical Sciences Research Complexen
dc.identifier.doihttps://doi.org/10.1021/jacs.7b06270
dc.description.statusPeer revieweden
dc.date.embargoedUntil2018-08-04


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