Chemoenzymatic synthesis of fluorinated cellodextrins identifies a new allomorph for cellulose‐like materials

Peterson de Andrade, Juan C. Muñoz-García, Giulia Pergolizzi, Valeria Gabrielli, Sergey Nepogodiev, Dinu Iuga, Laszlo Fabian, Rinat Nigmatullin, Marcus A. Johns, Robert Harniman, Stephen J. Eichhorn, Jesus Angulo Alvarez, Yaroslav Khimyak, Robert A. Field

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Abstract

Understanding the fine details of the self-assembly of building blocks into complex hierarchical structures represents a major challenge en route to the design and preparation of soft-matter materials with specific properties. Enzymatically synthesised cellodextrins are known to have limited water solubility beyond DP9, a point at which they self-assemble into particles resembling the antiparallel cellulose II crystalline packing. We have prepared and characterised a series of site-selectively fluorinated cellodextrins with different degrees of fluorination and substitution patterns by chemoenzymatic synthesis. Bearing in mind the potential disruption of the hydrogen-bond network of cellulose II, we have prepared and characterised a multiply 6-fluorinated cellodextrin. In addition, a series of single site-selectively fluorinated cellodextrins was synthesised to assess the structural impact upon the addition of one fluorine atom per chain. The structural characterisation of these materials at different length scales, combining advanced NMR spectroscopy and microscopy methods, showed that a 6-fluorinated donor substrate yielded multiply 6-fluorinated cellodextrin chains that assembled into particles presenting morphological and crystallinity features, and intermolecular interactions, that are unprecedented for cellulose-like materials.

Original languageEnglish
Pages (from-to)1374-1382
Number of pages9
JournalChemistry - A European Journal
Volume27
Issue number4
Early online date29 Sep 2020
DOIs
Publication statusPublished - 18 Jan 2021

Keywords

  • allomorphs
  • cellodextrins
  • chemoenzymatic synthesis
  • fluorine
  • soft-matter materials

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