Orthogonal Recognition Processes Drive the Assembly and Replication of a [2]Rotaxane

Tamara Kosikova, Nurul Izzaty Hassan, David B. Cordes, Alexandra M Z Slawin, Douglas Philp

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

Within a small, interconnected reaction network, orthogonal recognition processes drive the assembly and replication of a [2]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 auto-catalytic templates for their own formation and also operate as cross-catalytic 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.

Original languageEnglish
Pages (from-to)16074-16083
Number of pages10
JournalJournal of the American Chemical Society
Volume137
Issue number51
DOIs
Publication statusPublished - 30 Dec 2015

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Rotaxanes
Cycloaddition
Binding sites
Hydrogen bonds
Competitive Binding
Cycloaddition Reaction
Hydrogen Bonding
Binding Sites

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Orthogonal Recognition Processes Drive the Assembly and Replication of a [2]Rotaxane. / Kosikova, Tamara; Hassan, Nurul Izzaty; Cordes, David B.; Slawin, Alexandra M Z; Philp, Douglas.

In: Journal of the American Chemical Society, Vol. 137, No. 51, 30.12.2015, p. 16074-16083.

Research output: Contribution to journalArticle

Kosikova, Tamara ; Hassan, Nurul Izzaty ; Cordes, David B. ; Slawin, Alexandra M Z ; Philp, Douglas. / Orthogonal Recognition Processes Drive the Assembly and Replication of a [2]Rotaxane. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 51. pp. 16074-16083.
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