Orthogonal recognition processes drive the assembly and replication of a rotaxane
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Within a small interconnected reaction network, orthogonal recognition processes drive the assembly and replication of a rotaxane. Rotaxane formation is governed by a central, hydrogen bonding-mediated binding equilibrium between a macrocycle and a linear component, which associate to give a reactive pseudorotaxane. Both the pseudorotaxane and the linear component undergo irreversible, recognition-mediated 1,3-dipolar cycloaddition reactions with a stoppering maleimide group, forming rotaxane and thread, respectively. As a result of these orthogonal recognition-mediated processes, the rotaxane and thread can act as autocatalytic templates for their own formation and also operate as crosscatalytic templates for each other. However, the interplay between the recognition and reaction processes in this reaction network results in the formation of undesirable pseudorotaxane complexes, causing thread formation to exceed rotaxane formation in the current experimental system. Nevertheless, in the absence of competitive macrocycle-binding sites, realization of a replicating network favoring formation of rotaxane is possible.
Kosikova , T , Hassan , N I B , Cordes , D B , Slawin , A M Z & Philp , D 2015 , ' Orthogonal recognition processes drive the assembly and replication of a rotaxane ' Journal of the American Chemical Society , vol 137 , no. 51 , pp. 16074–16083 . DOI: 10.1021/jacs.5b09738
Journal of the American Chemical Society
Copyright © 2015 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://dx.doi.org/10.1021/jacs.5b09738
The financial support for this work was provided by EPSRC (Grant EP/K503162/1 and EP/E017851/1) and the Ministry for Higher Education Malaysia.
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