Aromatic stacking interactions in flavin model systems

Vikas Nandwana, Ifor David William Samuel, Graeme Cooke*, Vincent M. Rotello

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

31 Citations (Scopus)

Abstract

Flavins feature multiple attributes that explain their widespread occurrence in nature, including photostability, reversible electrochemistry, and especially the tunability of their optical, electronic, and redox properties by supramolecular interactions and modification of their chemical structure. Flavins are important redox cofactors for enzymatic catalysis and are central to a wide variety of processes, including biosynthesis, electron transport, photosynthesis, and DNA repair. The wide range of processes catalyzed by flavins makes them promising leads for synthetic catalysts. Their properties are also relevant to organic electronic and optoelectronic devices, where they have the potential to serve as photoactive electron carriers, a very uncommon property in current photovoltaic systems.

In flavoenzymes, the flavin cofactor binds to the active site of the apoenzyme through noncovalent interactions. These interactions regulate cofactor recognition and tune the redox behavior of the flavin cofactor. In this Account, we describe the creation of host guest systems based on small molecule, polymer, and nanoparticle scaffolds that explore the role of aromatic stacking on the redox properties of the flavin and provide insight into flavoenzyme function. We also describe the creation of synthetic flavin-based interlocked structures featuring aromatic stacking interactions, along with the use of aromatic stacking to direct self-assembly of flavin-based materials.

The interplay between redox events and aromatic stacking interactions seen in these synthetic models is important for fundamental understanding of biological systems including the flavoenzymes. The precise control of aromatic interactions and binding of flavins not only underpins their biological activity but gives them the potential to be developed into novel organic optoelectronic materials based on tuned synthetic flavin receptor assemblies. In a broader context, the redox properties of the flavin provide a very concise tool for looking at the role of electronics in aromatic stacking, an issue of general importance in biological and supramolecular chemistry.

Original languageEnglish
Pages (from-to)1000-1009
Number of pages10
JournalAccounts of Chemical Research
Volume46
Issue number4
Early online date19 Nov 2012
DOIs
Publication statusPublished - 16 Apr 2013

Keywords

  • REDOX POTENTIAL MODULATION
  • SITE-DIRECTED MUTAGENESIS
  • GOLD CLUSTER COMPOUNDS
  • FLAVOENZYME ACTIVITY
  • MOLECULAR RECOGNITION
  • ELECTROSTATIC INTERACTIONS
  • PI INTERACTIONS
  • SOL-GEL
  • FLAVODOXIN
  • COFACTOR

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