, Volume 26, Issue 1, pp 329–339 | Cite as

Atomic resolution of cotton cellulose structure enabled by dynamic nuclear polarization solid-state NMR

  • Alex Kirui
  • Zhe Ling
  • Xue Kang
  • Malitha C. Dickwella Widanage
  • Frederic Mentink-Vigier
  • Alfred D. FrenchEmail author
  • Tuo WangEmail author
Original Paper


The insufficient resolution of conventional methods has long limited the structural elucidation of cellulose and its derivatives, especially for those with relatively low crystallinities or in native cell walls. Recent 2D/3D solid-state NMR studies of 13C uniformly labeled plant biomaterials have initiated a re-investigation of our existing knowledge in cellulose structure and its interactions with matrix polymers but for unlabeled materials, this spectroscopic method becomes impractical due to limitations in sensitivity. Here, we investigate the molecular structure of unlabeled cotton cellulose by combining natural abundance 13C–13C 2D correlation solid-state NMR spectroscopy, as enabled by the sensitivity-enhancing technique of dynamic nuclear polarization, with statistical analysis of the observed and literature-reported chemical shifts. The atomic resolution allows us to monitor the loss of Iα and Iβ allomorphs and the generation of a novel structure during ball-milling, which reveals the importance of large crystallite size for maintaining the Iα and Iβ model structures. Partial order has been identified in the “disordered” domains, as evidenced by a discrete distribution of well-resolved peaks. This study not only provides heretofore unavailable high-resolution insights into cotton cellulose but also presents a widely applicable strategy for analyzing the structure of cellulose-rich materials without isotope-labeling. This work was part of a multi-technique study of ball-milled cotton described in the previous article in the same issue.

Graphical abstract


Cotton Cellulose Solid-state NMR Dynamic nuclear polarization Natural abundance 



This work is supported by the National Science Foundation through NSF OIA-1833040. The National High Magnetic Field Laboratory is supported by the National Science Foundation through NSF/DMR-1644779 and the State of Florida. The MAS-DNP system at NHMFL is funded in part by NIH S10 OD018519 and NSF CHE-1229170.

Supplementary material

10570_2018_2095_MOESM1_ESM.docx (275 kb)
Supplementary material 1 (DOCX 274 kb)


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Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Department of ChemistryLouisiana State UniversityBaton RougeUSA
  2. 2.Southern Regional Research Center USDANew OrleansUSA
  3. 3.Beijing Forestry UniversityBeijingPeople’s Republic of China
  4. 4.National High Magnetic Field LaboratoryTallahasseeUSA

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