Cellulose

, Volume 21, Issue 6, pp 3979–3991 | Cite as

Constraints on \({\rm I}\beta\) cellulose twist from DFT calculations of \(^{13}\hbox {C}\) NMR chemical shifts

  • Oleg E. Shklyaev
  • James D. Kubicki
  • Heath D. Watts
  • Vincent H. Crespi
Original Paper

Abstract

We investigate theoretically the NMR response of twisted configurations of \({\rm I}\beta\) cellulose in the tg conformation. These finite helical angle structures were constructed by a mathematical deformation of zero-angle configurations obtained via the periodic density functional energy minimizations with dispersion corrections (DFT-D2). Subsequent calculations of the \({^{13}\hbox {C}}\) nuclear magnetic resonance chemical shifts \(({\delta}^{13} \hbox {C})\) were compared with experimental findings by Erata et al. (Cellul Commun 4:128–131, 1997) and Kono et al. (Macromolecules 36:5131–5138, 2003). We determine the sensitivity of the NMR chemical shifts to helical deformation of the microfibril and find that a substantial range of helical angle, ±2 degrees/nm, is consistent with current experimental observations, with a most probable angle of ∼0.2 degree/nm. Through exhaustive combinatorial provisional assignments, we also demonstrate that there are different choices of the chemical shift \(({\delta}^{13} \hbox {C})\) assignments which are consistent with the experiments, including ones with lower deviations than existing identifications.

Keywords

Cellulose Structure Twist DFT NMR 

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Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • Oleg E. Shklyaev
    • 1
  • James D. Kubicki
    • 2
  • Heath D. Watts
    • 2
  • Vincent H. Crespi
    • 1
  1. 1.Department of PhysicsThe Pennsylvania State UniversityUniversity ParkUSA
  2. 2.Department of Geosciences, Earth and Environmental Systems InstituteThe Pennsylvania State UniversityUniversity ParkUSA

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