Abstract
A survey of the literature reporting solid-state 13C NMR spectra of native celluloses reveals inconsistencies in the reported 13C chemical shifts for cellulose Iα and Iβ allomorphs. With reported chemical shifts varying by up to 2 ppm, it is not clear what the correct chemical shifts actually are. Since reliable experimental data are important to future work, such as quantum chemical calculations of NMR parameters or identification of cellulose phases in complex cellulosic materials, it is important that the correct experimental chemical shifts be established with confidence. Through a process of digitization of previously reported spectra and careful consideration of how chemical shifts were referenced in the past, it has been possible to correct previously reported spectra of cellulose Iα and Iβ, putting them on the same chemical shift scale and establishing a definitive set of correctly referenced 13C chemical shifts for cellulose Iα and Iβ allomorphs. In addition, 1D and 2D 13C NMR experiments were carried out on a cellulose Iα-rich bacterial cellulose sample (with 25% 13C enrichment), providing additional evidence for these 13C chemical shifts and a new peak assignment of the 13C signals to the glucose units in cellulose Iα. This work resolves many of inconsistencies in the cellulose solid-state NMR literature and provides a definitive set of 13C chemical shifts that will be important for future work.
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Data availability
The raw data (Bruker format) for the 1D and 2D spectra in Fig. 5 is available as Supporting Information.
References
Atalla RH, VanderHart DL (1999) The role of solid state 13C NMR spectroscopy in studies of the nature of native celluloses. Solid State Nucl Magn Reson 15:1–19. https://doi.org/10.1016/S0926-2040(99)00042-9
Atalla RH, Gast JC, Sindorf DW et al (1980) 13C NMR spectra of cellulose polymorphs. J Am Chem Soc 102:3249–3251. https://doi.org/10.1021/ja00529a063
Atalla RH, VanderHart DL (1984) Native cellulose: a composite of two distinct crystalline forms. Science 223:283–285. https://doi.org/10.1126/science.223.4633.283
Belton PS, Tanner SF, Cartier N, Chanzy H (1989) High-resolution solid-state 13C nuclear magnetic resonance spectroscopy of tunicin, an animal cellulose. Macromolecules 22:1615–1617. https://doi.org/10.1021/ma00194a019
Brinkmann A, Chen M, Couillard M et al (2016) Correlating cellulose nanocrystal particle size and surface area. Langmuir 32:6105–6114. https://doi.org/10.1021/acs.langmuir.6b01376
Brouwer DH, White AL (2022) A comprehensive collection of solid-state 31P NMR spectra of aluminophosphate zeolites. Microporous Mesoporous Mater 337:111934. https://doi.org/10.1016/j.micromeso.2022.111934
Brouwer DH, Brouwer CC, Mesa S et al (2020) Solid-state 29Si NMR spectra of pure silica zeolites for the International Zeolite Association Database of Zeolite Structures. Microporous Mesoporous Mater 297:110000. https://doi.org/10.1016/j.micromeso.2020.110000
Bryce DL (2017) NMR crystallography: structure and properties of materials from solid-state nuclear magnetic resonance observables. IUCrJ 4:350–359. https://doi.org/10.1107/S2052252517006042
Carravetta M, Edén M, Zhao X et al (2000) Symmetry principles for the design of radiofrequency pulse sequences in the nuclear magnetic resonance of rotating solids. Chem Phys Lett 321:205–215. https://doi.org/10.1016/S0009-2614(00)00340-7
Debzi EM, Chanzy H, Sugiyama J et al (1991) The Iα → Iß transformation of highly crystalline cellulose by annealing in various mediums. Macromolecules 24:6816–6822. https://doi.org/10.1021/ma00026a002
Earl WL, VanderHart DL (1980) High resolution magic angle sample spinning 13C NMR of solid cellulose I. J Am Chem Soc 102:3251–3252. https://doi.org/10.1021/ja00529a064
Earl WL, VanderHart DL (1981) Observations by high-resolution carbon-13 nuclear magnetic resonance of cellulose I related to morphology and crystal structure. Macromolecules 14:570–574. https://doi.org/10.1021/ma50004a023
Erata T, Shikano T, Yunoki S, Takai M (1997) The complete assignment of the 13C CP/MAS NMR spectrum of native cellulose by using 13C labeled glucose. Cellul Commun 4:128–131
Fung BM, Khitrin AK, Ermolaev K (2000) An improved broadband decoupling sequence for liquid crystals and solids. J Magn Reson 142:97–101. https://doi.org/10.1006/jmre.1999.1896
Harris RK, Becker ED, Cabral De Menezes SM et al (2008) Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008). Pure Appl Chem 80:59–84. https://doi.org/10.1351/pac200880010059
Harris RK, Wasylishen RE, Duer MJ (2009) NMR crystallography. Wiley, New York
Hestrin S, Schramm M (1954) Synthesis of cellulose by Acetobacter xylinum. II. Preparation of freeze-dried cells capable of polymerizing glucose to cellulose. Biochem J 58:345–352. https://doi.org/10.1042/bj0580345
Hirai A, Horii F, Kitamaru R (1987) Transformation of native cellulose crystals from cellulose Ib to Ia through solid-state chemical reactions. Macromolecules 20:1440–1442. https://doi.org/10.1021/ma00172a057
Hodgkinson P (2020) NMR crystallography of molecular organics. Prog Nucl Magn Reson Spectrosc 118–119:10–53. https://doi.org/10.1016/j.pnmrs.2020.03.001
Hoffman R (2022) Solid-state chemical-shift referencing with adamantane. J Magn Reson 340:107231. https://doi.org/10.1016/j.jmr.2022.107231
Horii F, Hirai A, Kitamaru R (1982) Solid-state high-resolution 13C-NMR studies of regenerated cellulose samples with different crystallinities. Polym Bull 8:163–170. https://doi.org/10.1007/BF00263023
Horii F, Hirai A, Kitamaru R (1984) CP/MAS carbon-13 NMR study of spin relaxation phenomena of cellulose containing crystalline and noncrystalline components. J Carbohydr Chem 3:641–662. https://doi.org/10.1080/07328308408057922
Horii F, Hirai A, Kitamaru R (1987) CP/MAS 13C NMR spectra of the crystalline components of native celluloses. Macromolecules 20:2117–2120. https://doi.org/10.1021/ma00175a012
Hult EL, Larsson PT, Iversen T (2000) Comparative CP/MAS 13C-NMR study of cellulose structure in spruce wood and kraft pulp. Cellulose 7:35–55. https://doi.org/10.1023/A:1009236932134
Kirui A, Ling Z, Kang X et al (2019) Atomic resolution of cotton cellulose structure enabled by dynamic nuclear polarization solid-state NMR. Cellulose 26:329–339. https://doi.org/10.1007/s10570-018-2095-6
Kono H, Numata Y (2006) Structural investigation of cellulose Iαand Iβ by 2D RFDR NMR spectroscopy: determination of sequence of magnetically inequivalent D-glucose units along cellulose chain. Cellulose 13:317–326. https://doi.org/10.1007/s10570-005-9025-0
Kono H, Yunoki S, Shikano T et al (2002) CP/MAS C-13 NMR study of cellulose and cellulose derivatives. 1. Complete assignment of the CP/MAS C-13 NMR spectrum of the native cellulose. J Am Chem Soc 124:7506–7511. https://doi.org/10.1021/Ja010704o
Kono H, Erata T, Takai M (2003) Determination of the through-bond carbon-carbon and carbon-proton connectivities of the native celluloses in the solid state. Macromolecules 36:5131–5138. https://doi.org/10.1021/ma021769u
Larsson PT, Westermark U, Iversen T (1995) Determination of the cellulose Iα allomorph content in a tunicate cellulose by CP/MAS 13C-NMR spectroscopy. Carbohydr Res 278:339–343. https://doi.org/10.1016/0008-6215(95)00248-0
Larsson PT, Wickholm K, Iversen T (1997) A CP/MAS 13C NMR investigation of molecular ordering in celluloses. Carbohydr Res 302:19–25. https://doi.org/10.1016/S0008-6215(97)00130-4
Larsson PT, Hult EL, Wickholm K et al (1999) CP/MAS 13C-NMR spectroscopy applied to structure and interaction studies on cellulose I. Solid State Nucl Magn Reson 15:31–40. https://doi.org/10.1016/S0926-2040(99)00044-2
Lennholm H, Larsson T, Iversen T (1994) Determination of cellulose Iα and Iβ in lignocellulosic materials. Carbohydr Res 261:119–131. https://doi.org/10.1016/0008-6215(94)80011-1
Maciel GE, Kolodziejski WL, Bertran MS et al (1982) 13C NMR and order in cellulose. Macromolecules 15:686–687. https://doi.org/10.1021/ma00230a097
Malm E, Bulone V, Wickholm K et al (2010) The surface structure of well-ordered native cellulose fibrils in contact with water. Carbohydr Res 345:97–100. https://doi.org/10.1016/j.carres.2009.10.020
Morcombe CR, Zilm KW (2003) Chemical shift referencing in MAS solid state NMR. J Magn Reson 162:479–486. https://doi.org/10.1016/S1090-7807(03)00082-X
Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082. https://doi.org/10.1021/ja0257319
Nishiyama Y, Sugiyama J, Chanzy H, Langan P (2003) Crystal structure and hydrogen bonding system in cellulose Iα from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 125:14300–14306. https://doi.org/10.1021/ja037055w
Phyo P, Wang T, Yang Y et al (2018) Direct determination of hydroxymethyl conformations of plant cell wall cellulose using 1 H polarization transfer solid-state NMR. Biomacromol 19:1485–1497. https://doi.org/10.1021/acs.biomac.8b00039
Potrzebowski MJ, Tekely P, Dusausoy Y (1998) Comment to 13C-NMR studies of α and γ polymorphs of glycine. Solid State Nucl Magn Reson 11:253–257. https://doi.org/10.1016/S0926-2040(98)00028-9
Rohatgi A (2019) WebPlotDigitizer, version 4.2. https://automeris.io/WebPlotDigitizer
Simmons TJ, Mortimer JC, Bernardinelli OD et al (2016) Folding of xylan onto cellulose fibrils in plant cell walls revealed by solid-state NMR. Nat Commun 7:13902. https://doi.org/10.1038/ncomms13902
States DJ, Haberkorn RA, Ruben DJ (1982) A two-dimensional nuclear overhauser experiment with pure absorption phase in four quadrants. J Magn Reson 48:286–292. https://doi.org/10.1016/0022-2364(82)90279-7
Sternberg U, Koch F-T, Priess W, Witter R (2003) Crystal structure refinements of cellulose polymorphs using solid state 13C chemical shifts. Cellulose 10:189–199. https://doi.org/10.1023/A:1025185416154
Taylor RE, Dybowski C (2008) Variable temperature NMR characterization of α-glycine. J Mol Struct 889:376–382. https://doi.org/10.1016/j.molstruc.2008.02.023
VanderHart DL (1986) Field-dependent C-13 chemical shifts in solids: a second-order dipolar perturbation. J Chem Phys 84:1196–1205. https://doi.org/10.1063/1.450511
VanderHart DL, Atalla RH (1984) Studies of microstructure in native celluloses using solid-state 13C NMR. Macromolecules 17:1465–1472. https://doi.org/10.1021/ma00138a009
VanderHart D, Atalla R (1987) Further carbon-13 NMR evidence for the coexistence of two crystalline forms in native celluloses. ACS Symp Ser 340:88–118. https://doi.org/10.1021/bk-1987-0340.ch005
Wang T, Yang H, Kubicki JD, Hong M (2016) Cellulose structural polymorphism in plant primary cell walls investigated by high-field 2D solid-state NMR spectroscopy and density functional theory calculations. Biomacromol 17:2210–2222. https://doi.org/10.1021/acs.biomac.6b00441
Wickholm K, Larsson PT, Iversen T (1998) Assignment of non-crystalline forms in cellulose I by CP/MAS 13C NMR spectroscopy. Carbohydr Res 312:123–129. https://doi.org/10.1016/S0008-6215(98)00236-5
Wolfram Research Inc (2019) Mathematica, version 12.0
Yamamoto H, Horii F (1993) CP/MAS 13C NMR analysis of the crystal transformation induced for Valonia cellulose by annealing at high temperatures. Macromolecules 26:1313–1317. https://doi.org/10.1021/ma00058a020
Acknowledgments
The authors thank the Department of Chemistry and Chemical Biology at McMaster University for access to the 850 MHz NMR spectrometer.
Funding
This work was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada in the form of a Discovery Grant (funding reference number 03836) and an Undergraduate Student Research Award.
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Material preparation was carried out by JM. Data collection, analysis, and writing of the manuscript were carried out by DB. Both authors have read and approved the final manuscript.
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Brouwer, D.H., Mikolajewski, J.G. Resolving the discrepancies in reported 13C solid state NMR chemical shifts for native celluloses. Cellulose 30, 4827–4839 (2023). https://doi.org/10.1007/s10570-023-05186-9
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DOI: https://doi.org/10.1007/s10570-023-05186-9