The electronic nature of the 1,4-β-glycosidic bond and its chemical environment: DFT insights into cellulose chemistry.

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  • Author(s): Loerbroks C;Loerbroks C; Rinaldi R; Thiel W
  • Source:
    Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2013 Nov 25; Vol. 19 (48), pp. 16282-94. Date of Electronic Publication: 2013 Oct 18.
  • Publication Type:
    Journal Article
  • Language:
    English
  • Additional Information
    • Source:
      Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 9513783 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3765 (Electronic) Linking ISSN: 09476539 NLM ISO Abbreviation: Chemistry Subsets: MEDLINE
    • Publication Information:
      Original Publication: Weinheim, Germany : Wiley-VCH
    • Subject Terms:
      Cellobiose/*chemistry ; Cellulose/*chemistry; Hydrogen Bonding ; Hydrolysis ; Molecular Structure ; Thermodynamics
    • Abstract:
      The molecular understanding of the chemistry of 1,4-β-glucans is essential for designing new approaches to the conversion of cellulose into platform chemicals and biofuels. In this endeavor, much attention has been paid to the role of hydrogen bonding occurring in the cellulose structure. So far, however, there has been little discussion about the implications of the electronic nature of the 1,4-β-glycosidic bond and its chemical environment for the activation of 1,4-β-glucans toward acid-catalyzed hydrolysis. This report sheds light on these central issues and addresses their influence on the acid hydrolysis of cellobiose and, by analogy, cellulose. The electronic structure of cellobiose was explored by DFT at the BB1 K/6-31++G(d,p) level. Natural bond orbital (NBO) analysis was performed to grasp the key bonding concepts. Conformations, protonation sites, and hydrolysis mechanisms were examined. The results for cellobiose indicate that cellulose is protected against hydrolysis not only by its supramolecular structure, as currently accepted, but also by its electronic structure, in which the anomeric effect plays a key role.
      (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
    • Contributed Indexing:
      Keywords: NBO analysis; cellobiose; cellulose hydrolysis; computational chemistry; density functional calculations
    • Accession Number:
      16462-44-5 (Cellobiose)
      9004-34-6 (Cellulose)
    • Publication Date:
      Date Created: 20131019 Date Completed: 20140612 Latest Revision: 20131119
    • Publication Date:
      20231215
    • Accession Number:
      10.1002/chem.201301366
    • Accession Number:
      24136817