Abstract
The hydrophilicity of wood cell walls derives from the presence of hydroxyls, but their accessibility is restricted by physical confinement from the stiff, solid cell walls. This study examines how this confinement affects water uptake of the accessible hydroxyls by tuning their amount through replacement with various non-hydrophilic functional groups. Results from gravimetrically determined hydroxyl accessibility by deuterium exchange are shown not to correlate with moisture uptake in cell walls under vapour conditions or at water-saturation. Instead, spatial availability for water inside solid cell walls is suggested as the dominant factor in controlling cell wall moisture uptake at given climatic conditions.
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References
Agarwal UP (1999) An overview of Raman spectroscopy as applied to lignocellulosic materials. In: Argyropoulos DS (ed) Advances in lignocellulosics characterization. Tappi Press, Atlanta, pp 201–225
Altgen M, Willems W, Hosseinpourpia R, Rautkari L (2018) Hydroxyl accessibility and dimensional changes of Scots pine sapwood affected by alterations in the cell wall ultrastructure during heat-treatment. Polym Degrad Stabil 152:244–252. https://doi.org/10.1016/j.polymdegradstab.2018.05.005
Berthold J, Desbrieres J, Rinaudo M, Salmén L (1994) Types of adsorbed water in relation to the ionic groups and their counterions for some cellulose derivatives. Polymer 35:5729–5736. https://doi.org/10.1016/S0032-3861(05)80048-5
Berthold J, Rinaudo M, Salmén L (1996) Association of water to polar groups; estimations by an adsorption model for ligno-cellulosic materials. Colloid Surface A 112:117–129. https://doi.org/10.1016/0927-7757(95)03419-6
Berthold J, Olsson RJO, Salmén L (1998) Water sorption to hydroxyl and carboxylic acid groups in carboxymethylcellulose (CMC) studied with NIR-spectroscopy. Cellulose 5:281–298. https://doi.org/10.1023/A:1009298907734
Bertinetti L, Fischer FD, Fratzl P (2013) Physicochemical basis for water-actuated movement and stress generation in nonliving plant tissues. Phys Rev Lett 111:238001. https://doi.org/10.1103/PhysRevLett.111.238001
Bertinetti L, Fratzl P, Zemb T (2016) Chemical, colloidal and mechanical contributions to the state of water in wood cell walls. New J Phys 18:083048. https://doi.org/10.1088/1367-2630/18/8/083048
Bro R, De Jong S (1997) A fast non-negativity-constrained least squares algorithm. J Chemometr 11:393–401. https://doi.org/10.1002/(sici)1099-128x(199709/10)11:5%3c393:aid-cem483%3e3.0.co;2-l
Cabane E, Keplinger T, Künniger T, Merk V, Burgert I (2016) Functional lignocellulosic materials prepared by ATRP from a wood scaffold. Sci Rep 6:31287. https://doi.org/10.1038/srep31287
Cabane E, Keplinger T, Merk V, Hass P, Burgert I (2014) Renewable and functional wood materials by grafting polymerization within cell walls. Chemsuschem 7:1020–1025. https://doi.org/10.1002/cssc.201301107
Eilers PHC (2004) Parametric time warping. Anal Chem 76:404–411. https://doi.org/10.1021/ac034800e
Ermeydan MA, Cabane E, Gierlinger N, Koetz J, Burgert I (2014a) Improvement of wood material properties via in situ polymerization of styrene into tosylated cell walls. RSC Adv 4:12981–12988. https://doi.org/10.1039/C4RA00741G
Ermeydan MA, Cabane E, Hass P, Koetz J, Burgert I (2014b) Fully biodegradable modification of wood for improvement of dimensional stability and water absorption properties by poly([varepsilon]-caprolactone) grafting into the cell walls. Green Chem 16:3313–3321. https://doi.org/10.1039/C4GC00194J
Ermeydan MA, Cabane E, Masic A, Koetz J, Burgert I (2012) Flavonoid insertion into cell walls improves wood properties. ACS Appl Mater Inter 4:5782–5789. https://doi.org/10.1021/am301266k
Fredriksson M, Thybring EE (2019) On sorption hysteresis in wood: separating hysteresis in cell wall water and capillary water in the full moisture range. PLoS ONE 14:e0225111. https://doi.org/10.1371/journal.pone.0225111
Frey M, Widner D, Segmehl JS, Casdorff K, Keplinger T, Burgert I (2018) Delignified and densified cellulose bulk materials with excellent tensile properties for sustainable engineering. ACS Appl Mater Inter 10:5030–5037. https://doi.org/10.1021/acsami.7b18646
Gibbons GC (1953) The moisture regain of methylcellulose and cellulose acetate. J Text I T 44:T201–T208. https://doi.org/10.1080/19447025308659739
Gierlinger N, Keplinger T, Harrington M (2012) Imaging of plant cell walls by confocal Raman microscopy. Nat protoc 7:1694–1708. https://doi.org/10.1038/nprot.2012.092
Glass SV, Boardman CR, Thybring EE, Zelinka SL (2018) Quantifying and reducing errors in equilibrium moisture content measurements with dynamic vapor sorption (DVS) experiments. Wood Sci Technol 52:909–927. https://doi.org/10.1007/s00226-018-1007-0
Gold V, Satchell DPN (1955) The principles of hydrogen isotope exchange reactions in solution. Q Rev Chem Soc 9:51–72. https://doi.org/10.1039/qr9550900051
Guthrie JD, Heinzelman DC (1974) Deuterium-hydrogen-exchange accessibility of cellulose by use of D2O–18 and mass-spectroscopy. Text Res J 44:981–985. https://doi.org/10.1177/004051757404401214
Hill CAS, Jones D (1996) The dimensional stabilisation of Corsican pine sapwood by reaction with carboxylic acid anhydrides: the effect of chain length. Holzforschung 50:457–462. https://doi.org/10.1515/hfsg.1996.50.5.457
Hill CAS, Curling SF, Kwon JH, Marty V (2009) Decay resistance of acetylated and hexanoylated hardwood and softwood species exposed to Coniophora puteana. Holzforschung 63:619–625. https://doi.org/10.1515/HF.2009.124
Hofstetter K, Hinterstoisser B, Salmén L (2006) Moisture uptake in native cellulose—the roles of different hydrogen bonds: a dynamic FT-IR study using deuterium exchange. Cellulose 13:131–145. https://doi.org/10.1007/s10570-006-9055-2
Howsmon JA (1949) Water sorption and the poly-phase structure of cellulose fibers. Text Res J 19:152–163. https://doi.org/10.1177/004051754901900303
Jaumot J, Gargallo R, de Juan A, Tauler R (2005) A graphical user-friendly interface for MCR-ALS: a new tool for multivariate curve resolution in MATLAB. Chemometr Intell Lab 76:101–110. https://doi.org/10.1016/j.chemolab.2004.12.007
Keplinger T, Cabane E, Chanana M, Hass P, Merk V, Gierlinger N, Burgert I (2015) A versatile strategy for grafting polymers to wood cell walls. Acta Biomater 11:256–263. https://doi.org/10.1016/j.actbio.2014.09.016
Larkin P (2011) Illustrated IR and Raman spectra demonstrating important functional groups. In: Larkin P (ed) Infrared and Raman spectroscopy. Elsevier, Oxford, pp 135–176. https://doi.org/10.1016/B978-0-12-386984-5.10008-4
Lide DR (2013) Enthalpy of fusion. In: Haynes WM (ed) CRC handbook of chemistry and physics, 94th edition (internet version) edn. CRC Press/Taylor and Francis, Boca Raton, pp 146–155
Lindh EL, Bergenstråhle-Wohlert M, Terenzi C, Salmén L, Furó I (2016) Non-exchanging hydroxyl groups on the surface of cellulose fibrils: the role of interaction with water. Carbohydr Res 434:136–142. https://doi.org/10.1016/j.carres.2016.09.006
Mann J, Marrinan HJ (1956) The reaction between cellulose and heavy water 1. A qualitative study by infra-red spectroscopy. Trans Faraday Soc 52:481–487. https://doi.org/10.1039/TF9565200481
Olaniran SO, Etienne C, Keplinger T, Olufemi B, Rüggeberg M (2019) Mechanical behaviour of acetylated rubber wood subjected to artificial weathering. Holzforschung 73:1005. https://doi.org/10.1515/hf-2018-0274
Papadopouls AN (2001) Swelling, cell wall porosity and chemical modification of wood. Ph.D. Thesis, University of Wales Bangor, pp 285
Papadopoulos AN, Hill CAS (2003) The sorption of water vapour by anhydride modified softwood. Wood Sci Technol 37:221–231. https://doi.org/10.1007/s00226-003-0192-6
Papadopoulos AN, Hill CAS, Gkaraveli A (2004) Analysis of the swelling behaviour of chemically modified softwood: a novel approach. Holz Roh Werkst 62:107–112. https://doi.org/10.1007/s00107-003-0448-8
Piqueras S, Duponchel L, Tauler R, de Juan A (2011) Resolution and segmentation of hyperspectral biomedical images by Multivariate Curve Resolution-Alternating Least Squares. Anal Chim Acta 705:182–192. https://doi.org/10.1016/j.aca.2011.05.020
Popescu CM, Hill CAS, Curling S, Ormondroyd GA, Xie Y (2014) The water vapour sorption behaviour of acetylated birch wood: how acetylation affects the sorption isotherm and accessible hydroxyl content. J Mater Sci 49:2362–2371. https://doi.org/10.1007/s10853-013-7937-x
Rautkari L, Hill CAS, Curling S, Jalaludin Z, Ormondroyd GA (2013) What is the role of the accessibility of wood hydroxyl groups in controlling moisture content? J Mater Sci 48:6352–6356. https://doi.org/10.1007/s10853-013-7434-2
Rousselle MA, Nelson ML (1971) Accessibility of cotton cellulose by deuterium exchange. Text Res J 41:599–604. https://doi.org/10.1177/004051757104100708
Schmidt M, Gierlinger N, Schade U, Rogge T, Grunze M (2006) Polarized infrared microspectroscopy of single spruce fibers: hydrogen bonding in wood polymers. Biopolymers 83:546–555. https://doi.org/10.1002/bip.20585
Sepall O, Mason SG (1961) Hydrogen exchange between cellulose and water 1. Measurement of accessibility. Can J Chem 39:1934–1943. https://doi.org/10.1139/v61-260
Slonimskii GL, Askadskii AA, Kitaigorodskii AI (1970) The packing of polymer molecules. Polym Sci USSR 12:556–577. https://doi.org/10.1016/0032-3950(70)90345-X
Stevens CV, Smith BF (1970) Crosslinking cotton cellulose with ethyleneurea derivatives having varying hydrogen-bonding capabilities. II Accessibility determinations. J Appl Polym Sci 14:1691–1700. https://doi.org/10.1002/app.1970.070140704
Taniguchi T, Harada H, Nakato K (1966) Accessibility of hydroxyl groups in wood. Mokuzai Gakkaishi 10:215–220
Tarkow H, Turner HD (1958) The swelling pressure of wood. Forest Prod J 8:193–197
Tarmian A, Burgert I, Thybring EE (2017) Hydroxyl accessibility in wood by deuterium exchange and ATR-FTIR spectroscopy: methodological uncertainties. Wood Sci Technol 51:845–853. https://doi.org/10.1007/s00226-017-0922-9
Thybring EE (2013) The decay resistance of modified wood influenced by moisture exclusion and swelling reduction. Int Biodeter Biodegr 82:87–95. https://doi.org/10.1016/j.ibiod.2013.02.004
Thybring EE, Thygesen LG, Burgert I (2017) Hydroxyl accessibility in wood cell walls as affected by drying and re-wetting procedures. Cellulose 24:2375–2384. https://doi.org/10.1007/s10570-017-1278-x
Tjeerdsma BF, Boonstra M, Pizzi A, Tekely P, Militz H (1998) Characterisation of thermally modified wood: molecular reasons for wood performance improvement. Holz Roh Werkst 56:149–153. https://doi.org/10.1007/s001070050287
Wadehra IL, Manley RS (1966) Accessibility of hydrocelluloses and oligosaccharides by hydrogen exchange. Makromolekul Chem 94:42–51. https://doi.org/10.1002/macp.1966.020940105
Watanabe A, Morita S, Kokot S, Matsubara M, Fukai K, Ozaki Y (2006) Drying process of microcrystalline cellulose studied by attenuated total reflection IR spectroscopy with two-dimensional correlation spectroscopy and principal component analysis. J Mol Struct 799:102–110. https://doi.org/10.1016/j.molstruc.2006.03.018
Zauer M, Kretzschmar J, Großmann L, Pfriem A, Wagenführ A (2014) Analysis of the pore-size distribution and fiber saturation point of native and thermally modified wood using differential scanning calorimetry. Wood Sci Technol 48:177–193. https://doi.org/10.1007/s00226-013-0597-9
Acknowledgments
The PCL grafting was performed by Benjamin Michen, Empa.
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EET gratefully acknowledges financial support from FP7: People Marie-Curie action COFUND (EMPA POSTDOCS, Project No. 267161).
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Dedicated to the loving memory of the amazing colleague Hervé Bellanger (1985–2017).
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Thybring, E.E., Piqueras, S., Tarmian, A. et al. Water accessibility to hydroxyls confined in solid wood cell walls. Cellulose 27, 5617–5627 (2020). https://doi.org/10.1007/s10570-020-03182-x
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DOI: https://doi.org/10.1007/s10570-020-03182-x