Solid-state 13C-NMR study of conformations of oligosaccharides and cellulose

Horii, Fumitaka; Hirai, Asako; Kitamaru, Ryozo

doi:10.1007/bf00281948

Cited by 148 publications

(154 citation statements)

References 26 publications

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“…Additionally, the differing C-2 epimers of cellulose and mannan may contribute to these chemical shift differences. Assuming that -the C-2 epimer difference does not have an influence on the correlation data of Horii et al (13), the observed chemical shift for C-6 in Fig. 1 corresponds to the 0 -6 oxygen in the gt arrangement (i.e., 016 is gauche with respect to 0-5 and trans with respect to C-4), supporting the diffractionbased modeling for mannan I.…”

Section: Discussionsupporting

confidence: 75%

¹³C CP/MAS NMR spectra of poly-β-D(1 → 4) mannose: mannan

Marchessault¹,

Taylor²,

Winter³

1990

Can. J. Chem.

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I3c solid-state NMR spectra (CP/MAS) were recorded for rnannan polyrnorphs: rnannan I ("ivory nut") and rnannan I1 (Codiumfragile). These pure mannans, poly-P-(1-4) rnannopyranose, show a single resonance for each carbon of the chemical repeat unit. This is the expected result based on the crystalline P2,212' and1222 symmetries. The TI values were also recorded and the results are compared to those for cellulose obtained from the literature. The much lower mobility of C-6, even in noncrystalline rnannan, compared to native cellulose is attributed to the epirneric difference at C-2 between cellulose and rnannan allowing intramolecular hydrogen bonding in the former but not the latter.

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Section: Discussionsupporting

confidence: 75%

¹³C CP/MAS NMR spectra of poly-β-D(1 → 4) mannose: mannan

Marchessault¹,

Taylor²,

Winter³

1990

Can. J. Chem.

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“…The calculated results are in good agreement with the observed C6 peaks (centered at * 62 and * 65 ppm) in solid-state NMR spectra. This confirmed that the percentage of residues with gt and gg conformations can be estimated by calculating the size of the upfield C6 peak, whereas the percentage of residues with tg conformations can be estimated by the size of the downfield C6 peak (Horii et al 1983;Oehme et al 2015). In addition, microfibril bundling and intermolecular interactions with matrix polysaccharides, two factors crucial to wall mechanics, may also perturb the NMR chemical shifts of cellulose, thus are of high interest for future studies (Cosgrove 2016a, b …”

Section: Effect Of Adjacent Ho3 Groupmentioning

confidence: 73%

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

et al. 2017

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The doublet C4 peaks at * 85 and * 89 ppm in solid-state 13 C 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 13 C NMR chemical shifts in cellulose: conformations of exocyclic groups at C6 (tg, gt and gg), H 2 O molecules H-bonded on the surface of the microfibril, glycosidic bond angles (U, W) and the distances between H4 and HO3 atoms. We focus on changes in the d 13 C4 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 d 13 C4 peak separation, while the other three factors have secondary effects that increase the spread of the calculated C4 interior and surface peaks.

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“…The 13 C CP/MAS spectrum of an 81.7 mg sample of raw stock of G. barbadense (Pima) cotton is shown in Figure 1A, along with a vertical expansion ( Figure 1B) to show the smaller peaks in the spectrum arising from various minor components. As per Attala and VanderHart [7,19], the cellulose resonances are assigned as follows: C-1, the anomeric carbon, ranges from 102 to 108 ppm; C-4 has a relatively large resonance at ~89 ppm with a smaller one upfield at ~84 ppm; C-2,3,5, the remaining ring carbons, appear at ~75 ppm and ~72 ppm; and finally C-6, the primary alcohol, has a relatively large resonance at ~65 ppm (tg orientation of O-6 according to Horii [9], in agreement with the diffraction studies) with a smaller resonance upfield at ~63 ppm (gt orientation). C-1 and C-4 provide the linkages in the cellulose chains.…”

Section: Resultsmentioning

confidence: 99%

“…Diffraction studies have provided structures for a number of polymorphs, designated I α , I β , II, III I , and IV I [2][3][4][5][6]. Many spectroscopic studies of the chemical and physical properties of cellulose [1,[7][8][9][10][11][12], not only from plants but also from algae and bacteria, have examined the structure, morphology, and interactions with water. Often these studies have focused on processed samples of exceptional crystallinity, rather than on cellulose in its native form.…”

Section: Introductionmentioning

confidence: 99%

1H and 13C solid-state NMR of Gossypium barbadense (Pima) cotton

Taylor

French

Gamble

et al. 2008

Journal of Molecular Structure

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Abstract:The interaction of water with cellulose and its influence on the nuclear spin dynamics in Gossypium barbadense (Pima) C resonances from only the crystalline or the amorphous domains or from only the surface of the cellulose). However, spatial localization of the combined Goldman-Shen-13 C CP/MAS experiment using both short mixing and contact times yields a spectrum consistent with predominantly the I β polymorph of cellulose. Longer mixing times and the same, short contact time yield a spectrum that is indicative of an increased I α polymorph content in the crystallite interiors relative to the smaller values found with short mixing times.

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Solid-state 13C-NMR study of conformations of oligosaccharides and cellulose

Cited by 148 publications

References 26 publications

¹³C CP/MAS NMR spectra of poly-β-D(1 → 4) mannose: mannan

¹³C CP/MAS NMR spectra of poly-β-D(1 → 4) mannose: mannan

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

1H and 13C solid-state NMR of Gossypium barbadense (Pima) cotton

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Solid-state 13C-NMR study of conformations of oligosaccharides and cellulose

Cited by 148 publications

References 26 publications

13C CP/MAS NMR spectra of poly-β-D(1 → 4) mannose: mannan

13C CP/MAS NMR spectra of poly-β-D(1 → 4) mannose: mannan

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

1H and 13C solid-state NMR of Gossypium barbadense (Pima) cotton

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Product

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¹³C CP/MAS NMR spectra of poly-β-D(1 → 4) mannose: mannan

¹³C CP/MAS NMR spectra of poly-β-D(1 → 4) mannose: mannan