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Title: Structural factors affecting 13C NMR chemical shifts of cellulose: a computational study

Journal Article · · Cellulose
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Here, the doublet C4 peaks at ~ 85 and ~ 89 ppm in solid-state 13C NMR spectra of native cellulose have been attributed to signals of C4 atoms on the surface (solvent-exposed) and in the interior of microfibrils, designated as sC4 and iC4, respectively. The relative intensity ratios of sC4 and iC4 observed in NMR spectra of cellulose have been used to estimate the degree of crystallinity of cellulose and the number of glucan chains in cellulose microfibrils. However, the molecular structures of cellulose responsible for the specific surface and interior C4 peaks have not been positively confirmed. Using density functional theory (DFT) methods and structures produced from classical molecular dynamics simulations, we investigated how the following four factors affect 13C NMR chemical shifts in cellulose: conformations of exocyclic groups at C6 (tg, gt and gg), H2O molecules H-bonded on the surface of the microfibril, glycosidic bond angles (Φ, Ψ) and the distances between H4 and HO3 atoms. We focus on changes in the δ13C4 value because it is the most significant observable for the same C atom within the cellulose structure. DFT results indicate that different conformations of the exocyclic groups at C6 have the greatest influence on δ13C4 peak separation, while the other three factors have secondary effects that increase the spread of the calculated C4 interior and surface peaks.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Lignocellulose Structure and Formation (CLSF)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001090; AC05-00OR22725
OSTI ID:
1406658
Alternate ID(s):
OSTI ID: 1407765
Journal Information:
Cellulose, Journal Name: Cellulose Vol. 25 Journal Issue: 1; ISSN 0969-0239
Publisher:
Springer Science + Business MediaCopyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 39 works
Citation information provided by
Web of Science

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Cited By (9)

Molecular architecture of softwood revealed by solid-state NMR journal October 2019
Solid state nuclear magnetic resonance studies of hydroxypropylmethylcellulose acetyl succinate polymer, a useful carrier in pharmaceutical solid dispersions journal February 2020
Effects of ball milling on the structure of cotton cellulose journal January 2019
An evaluation of the structures of cellulose generated by the CHARMM force field: comparisons to in planta cellulose journal April 2018
Atomic resolution of cotton cellulose structure enabled by dynamic nuclear polarization solid-state NMR journal November 2018
A revised solid-state NMR method to assess the crystallinity of cellulose journal September 2019
A density functional theory study on the shape of the primary cellulose microfibril in plants: effects of C6 exocyclic group conformation and H-bonding journal January 2020
Investigation of the internal structure and dynamics of cellulose by 13C-NMR relaxometry and 2DPASS-MAS-NMR measurements journal August 2019
The Shape of Native Plant Cellulose Microfibrils journal September 2018

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Related Subjects

60 APPLIED LIFE SCIENCES
59 BASIC BIOLOGICAL SCIENCES
Cellulose
NMR
DFT
MD simulation
Microfibril