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Licensed Unlicensed Requires Authentication Published by De Gruyter November 1, 2006

Spatial relationships between polymers in Sitka spruce: Proton spin-diffusion studies

  • Clemens Altaner , David C. Apperley and Michael C. Jarvis
From the journal


The spatial arrangement of polymers in Sitka spruce (Picea sitchensis) was investigated by NMR proton spin-diffusion studies, supplemented by deuterium-exchange experiments monitored by FTIR spectroscopy. The FTIR spectra of earlywood sections after vapour-phase exchange with deuterium oxide showed that 43% of the hydroxyl groups were accessible to deuteration. This value is lower than predicted in the absence of aggregation of cellulose microfibrils into larger units, but greater than the predicted level of deuteration if 3.5-nm microfibrils surrounded by hemicellulose sheaths were aggregated into 4×4 arrays without space for deuterium oxide to penetrate between the microfibrils. The rate of proton spin diffusion between lignin and cellulose was consistent with the presence of microfibril arrays with approximately these dimensions and with lignin located outside them, in both earlywood and latewood. Proton spin-diffusion data for hemicelluloses were complicated by difficulties in assigning signals to glucomannans and xylans, but there was evidence for the spatial association of one group of hemicelluloses, including acetylated glucomannans, with cellulose surfaces, while another group of hemicelluloses was in spatial proximity to lignin. These data are consistent with a number of nanoscale models for the Sitka spruce cell wall, including a model in which glucomannans are associated with microfibril surfaces within the aggregate and water can penetrate partially between these surfaces, and one in which all non-cellulosic polymers and water are excluded from the interior of each microfibril aggregate.


Corresponding author. Chemistry Department, Glasgow University, Glasgow G12 8QQ, UK


Ahvazi, B.C., Argyropoulos, D.S. (1999) Proton spin-lattice relaxation time measurements of solid wood and its constituents as a function of pH: Part II. Solid State Nucl. Magn. Reson.15:49–57.10.1016/S0926-2040(99)00046-6Search in Google Scholar

Akerholm, M., Salmén, L. (2004) Softening of wood polymers induced by moisture studied by dynamic FTIR spectroscopy. J. Appl. Polym. Sci.94:2032–2040.10.1002/app.21133Search in Google Scholar

Bardet, M., Gagnaire, D., Nardin, R., Robert, D., Vincendon, M. (1986) Use of C-13 enriched wood for structural NMR investigation of wood and wood components, cellulose and lignin, in solid and in solution. Holzforschung40:17–24.Search in Google Scholar

Bertaud, F., Holmbom, B. (2004) Chemical composition of earlywood and latewood in Norway spruce heartwood, sapwood and transition zone wood. Wood Sci. Technol.38:245–256.10.1007/s00226-004-0241-9Search in Google Scholar

Fahlén, J., Salmén, L. (2005) Pore and matrix distribution in the fiber wall revealed by atomic force microscopy and image analysis. Biomacromolecules6:433–438.10.1021/bm040068xSearch in Google Scholar

Ha, M.A., Evans, B.W., Jarvis, M.C., Apperley, D.C., Kenwright, A.M. (1996) CP-MAS NMR of highly mobile hydrated biopolymers: polysaccharides of Allium cell walls. Carbohydr. Res.288:15–23.10.1016/0008-6215(96)00095-XSearch in Google Scholar

Ha, M.A., Apperley, D.C., Evans, B.W., Huxham, I.M., Jardine, W.G., Viëtor, R.J., Reis, D., Vian, B., Jarvis, M.C. (1998) Fine structure in cellulose microfibrils: NMR evidence from onion and quince. Plant J.16:183–190.10.1046/j.1365-313x.1998.00291.xSearch in Google Scholar

Hafren, J., Fujino, T., Itoh, T. (1999) Changes in cell wall architecture of differentiating tracheids of Pinus thunbergii during lignification. Plant Cell Physiol.40:532–541.10.1093/oxfordjournals.pcp.a029574Search in Google Scholar

Haw, J.F., Maciel, G.E., Schroeder, H.A. (1984) Carbon-13 nuclear magnetic resonance spectrometric study of wood and wood pulping with cross polarization and magic-angle spinning. Anal. Chem.56:1323–1329.10.1021/ac00272a028Search in Google Scholar

Hult, E.L., Larsson, P.T., Iversen, T. (2000) A comparative CP/MAS C-13-NMR study of cellulose structure in spruce wood and kraft pulp. Cellulose7:35–55.10.1023/A:1009236932134Search in Google Scholar

Jarvis, M.C. (1994) Relationship of chemical shift to glycosidic conformation in the solid-state 13C NMR spectra of (1→4)-linked glucose polymers and oligomers: Anomeric and related effects. Carbohydr. Res.259:311–318.10.1016/0008-6215(94)84067-9Search in Google Scholar

Kenwright, A.M., Packer, K.J. (1990) On T1 cancellation schemes in Goldman-Shen-type experiments. Chem. Phys. Lett.173:471–475.10.1016/0009-2614(90)87237-LSearch in Google Scholar

Kim, Y.S., Newman, R.H. (1995) Solid-state C-13 NMR study of wood degraded by the brown-rot fungus Gloeophyllum trabeum.Holzforschung49:109–114.10.1515/hfsg.1995.49.2.109Search in Google Scholar

Larsson, P.T., Wickholm, K., Iversen, T. (1997) A CP/MAS C-13 NMR investigation of molecular ordering in celluloses. Carbohydr. Res.302:19–25.10.1016/S0008-6215(97)00130-4Search in Google Scholar

Larsson, P.T., Hult, E.L., Wickholm, K., Pettersson, E., Iversen, T. (1999) CP/MAS C-13-NMR spectroscopy applied to structure and interaction studies on cellulose I. Solid State Nucl. Magn. Reson.15:31–40.10.1016/S0926-2040(99)00044-2Search in Google Scholar

Liitia, T., Maunu, S.L., Hortling, B. (2000) Solid-state NMR studies of residual lignin and its association with carbohydrates. J. Pulp Paper Sci.26:323–330.Search in Google Scholar

Maunu, S.L. (2002) NMR studies of wood and wood products. Prog. Nucl. Magn. Reson. Spectrosc.40:151–174.10.1016/S0079-6565(01)00041-3Search in Google Scholar

Newman, R.H. (1992) Nuclear magnetic resonance study of spatial relationships between chemical components in wood cell walls. Holzforschung46:205–210.10.1515/hfsg.1992.46.3.205Search in Google Scholar

Newman, R.H. (1999) Estimation of the lateral dimensions of cellulose crystallites using C-13 NMR signal strengths. Solid State Nucl. Magn. Reson.15:21–29.10.1016/S0926-2040(99)00043-0Search in Google Scholar

Newman, R.H., Davidson, T.C. (2004) Molecular conformations at the cellulose-water interface. Cellulose11:23–32.10.1023/B:CELL.0000014778.49291.c6Search in Google Scholar

Newman, R.H., Hemmingson, J.A. (1990) Determination of the degree of cellulose crystallinity in wood by C-13 nuclear magnetic resonance spectroscopy. Holzforschung44:351–355.10.1515/hfsg.1990.44.5.351Search in Google Scholar

Newman, R.H., Hemmingson, J.A. (1995) C-13 NMR distinction between categories of molecular order and disorder in cellulose. Cellulose2:95–110.10.1007/BF00816383Search in Google Scholar

Singh, A., Daniel, G., Nilsson, T. (2002) Ultrastructure of the S-2 layer in relation to lignin distribution in Pinus radiata tracheids. J. Wood Sci.48:95–98.10.1007/BF00767284Search in Google Scholar

Sivonen, H., Nuopponen, M., Maunu, S.L., Sundholm, F., Vuorinen, T. (2003) Carbon-13 cross-polarization magic angle spinning nuclear magnetic resonance and Fourier transform infrared studies of thermally modified wood exposed to brown and soft rot fungi. Appl. Spectrosc.57:266–273.10.1366/000370203321558164Search in Google Scholar

Tekely, P., Vignon, M.R. (1987a) Cross polarization magic angle spinning C-13 NMR characterization of steam exploded poplar wood. J. Wood Chem. Technol.7:215–228.10.1080/02773818708085263Search in Google Scholar

Tekely, P., Vignon, M.R. (1987b) Proton T1 and T2 relaxation times of wood components using C-13 CP MAS NMR. J. Polym. Sci. C-Polym. Lett.25:257–261.10.1002/pol.1987.140250604Search in Google Scholar

Teleman, A., Larsson, P.T., Iversen, T. (2001) On the accessibility and structure of xylan in birch kraft pulp. Cellulose8:209–215.10.1023/A:1013195030404Search in Google Scholar

Terashima, N., Awano, T., Takabe, K., Yoshida, M. (2004) Formation of macromolecular lignin in ginkgo xylem cell walls as observed by field emission scanning electron microscopy. C. R. Biol.327:903–910.10.1016/j.crvi.2004.08.001Search in Google Scholar

Viëtor, R.J., Newman, R.H., Ha, M.A., Apperley, D.C., Jarvis, M.C. (2002) Conformational features of crystal-surface cellulose from higher plants. Plant J.30:721–731.10.1046/j.1365-313X.2002.01327.xSearch in Google Scholar

Wickholm, K., Larsson P.T., Iversen, T. (1998) Assignment of non-crystalline forms in cellulose I by CP/MAS C-13 NMR spectroscopy. Carbohydr. Res.312:123–129.10.1016/S0008-6215(98)00236-5Search in Google Scholar

Wickholm, K., Hult, E.L., Larsson, P.T., Iversen, T., Lennholm, H. (2001) Quantification of cellulose forms in complex cellulose materials: A chemometric model. Cellulose8:139–148.10.1023/A:1016700325434Search in Google Scholar

Wikberg, H., Maunu, S.L. (2004) Characterisation of thermally modified hard- and softwoods by C-13 CPMAS NMR. Carbohydr. Polym.58:461–466.10.1016/j.carbpol.2004.08.008Search in Google Scholar

Zhang, S., Mehring, M. (1989) A modified Goldman-Shen NMR pulse sequence. Chem. Phys. Lett.160:644.10.1016/0009-2614(89)80079-XSearch in Google Scholar

Published Online: 2006-11-01
Published in Print: 2006-11-01

©2006 by Walter de Gruyter Berlin New York

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