Surface accessibility of cellulose fibrils studied by hydrogen–deuterium exchange with water
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A problem with cellulose-based materials is that they are highly influenced by moisture, leading to reduced strength properties with increasing moisture content. By achieving a more detailed understanding of the water–cellulose interactions, the usage of cellulose-based materials could be better optimized. Two different exchange processes of cellulose hydroxyl/deuteroxyl groups have been monitored by transmission FT-IR spectroscopy. By using line-shape-assisted deconvolution of the changing intensities, we have been able to follow the exchange kinetics in a very detailed and controlled manner. The findings reveal a hydrogen exchange that mainly is located at two different kinds of fibril surfaces, where the differences arise from the water accessibility of that specific surface. The slowly accessible regions are proposed to be located between the fibrils inside of the aggregates, and the readily accessible regions are suggested to be at the surfaces of the fibril aggregates. It was also possible to identify the ratio of slowly and readily accessible surfaces, which indicated that the average aggregate of cotton cellulose is built up by approximately three fibrils with an assumed average size of 12 × 12 cellulose chains. Additionally, the experimental setup enabled visualizing and discussing the implications of some of the deviating spectral features that are pronounced when recording FT-IR spectra of deuterium-exchanging cellulose: the insufficient red shift of the stretching vibrations and the vastly decreasing line widths.
KeywordsCellulose Deuterium FT-IR Hydrogen bond Exchange Morphology
We thank Leif Falk for the creation of the special-made box suitable for infrared measurements and Malin Bergenstråhle-Wohlert for all the helpful comments and discussions. Wallenberg Wood Science Center is gratefully acknowledged for the financial support.
Funding was provided by Knut och Alice Wallenbergs Stiftelse.
- Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, Weder C, Thielemans W, Roman M, Renneckar S, Gindl W, Veigel S, Keckes J, Yano H, Abe K, Nogi M, Nakagaito AN, Mangalam A, Simonsen J, Benight AS, Bismarck A, Berglund LA, Peijs T (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45:1–33CrossRefGoogle Scholar
- Langan P, Petridis L, O’Neill HM, Pingali SV, Foston M, Nishiyama Y, Schulz R, Lindner B, Hanson BL, Harton S, Heller WT, Urban V, Evans BR, Gnanakaran S, Ragauskas AJ, Smith JC, Davison BH (2014) Common processes drive the thermochemical pretreatment of lignocellulosic biomass. Green Chem 16:63–68CrossRefGoogle Scholar
- Pimentel CG, McClellan LA (1960) The hydrogen bond. Reinhold Publishing Corporation, New YorkGoogle Scholar
- Reishofer D, Spirk S (2016) Deuterium and cellulose: a comprehensive review. Adv Polym Sci 271:93–114Google Scholar
- Salmén L, Fahlén J (2006) Reflections on the ultrastructure of softwood fibers. Cellul Chem Technol 40:181–185Google Scholar