Enzymically attaching oligosaccharide-linked ‘cargoes’ to cellulose and other commercial polysaccharides via stable covalent bonds

Klaus Herburger, Lenka Frankova, Dayan Sanhueza, Soledad Roig-Sanchez, Frank Meulewaeter, Andrew D. Hudson, Axel Thomson, Anna Laromaine, Tatiana Budtova, Stephen C. Fry

Research output: Contribution to journalArticlepeer-review


The Equisetum enzyme hetero-trans-β-glucanase (HTG) covalently grafts native plant cellulose (donor-substrate) to xyloglucan (acceptor-substrates), potentially offering a novel ‘green’ method of cellulose functionalisation. However, the range of cellulosic and non-cellulosic donor substrates that can be utilised by HTG is unknown, limiting our insight into its biotechnological potential. Here we show that HTG binds all celluloses tested (papers, tissues, hydrogels, bacterial cellulose) to radioactively- or fluorescently-labelled xyloglucan-heptasaccharide (XXXGol; acceptor-substrate). Glycol-chitin, glycol-chitosan and chitosan also acted as donor substrates but less effectively than cellulose. Cellulose-XXXGol conjugates were formed throughout the volume of a block of hydrogel, demonstrating penetration. Plant-derived celluloses (cellulose Iβ) became more effective donor-substrates after ‘mercerisation’ in ≥3 M NaOH; the opposite was true for bacterial cellulose Iα. Cellulose-XXXGol bonds resisted boiling 6 M NaOH, demonstrating strong glycosidic bonding. In conclusion, HTG stably grafts native and processed celluloses to xyloglucan-oligosaccharides, which may carry valuable ‘cargoes’, exemplified by sulphorhodamine. We thus demonstrate HTG's biotechnological potential to modify various cellulose-based substrates such as textiles, pulps, papers, packaging, sanitary products and hydrogels.
Original languageEnglish
JournalInternational Journal of Biological Macromolecules
Early online date10 Sep 2020
Publication statusE-pub ahead of print - 10 Sep 2020


  • cellulose modification
  • hetero-transglycosylation
  • xyloglucan

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