Polarized infrared microspectroscopy of single spruce fibers: Hydrogen bonding in wood polymers

Schmidt, Martin; Gierlinger, Notburga; Schade, U.; Rogge, Tilmann; Grunze, M.

doi:10.1002/bip.20585

Cited by 31 publications

(24 citation statements)

References 41 publications

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“…5). In particular, there was little sign of the sharp, longitudinally oriented bands at 3,240 and 3;270 cm −1 , characteristic of the dominant hydrogen-bonding systems between O2 and O6 of successive glucosyl units in the same chain of, respectively, cellulose Iα and cellulose Iβ (28,62). These two bands were dispersed within a broad, longitudinally polarized shoulder.…”

Section: Resultsmentioning

confidence: 97%

Nanostructure of cellulose microfibrils in spruce wood

Fernandes

Thomas

Altaner

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

636

693

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The structure of cellulose microfibrils in wood is not known in detail, despite the abundance of cellulose in woody biomass and its importance for biology, energy, and engineering. The structure of the microfibrils of spruce wood cellulose was investigated using a range of spectroscopic methods coupled to small-angle neutron and wide-angle X-ray scattering. The scattering data were consistent with 24-chain microfibrils and favored a "rectangular" model with both hydrophobic and hydrophilic surfaces exposed. Disorder in chain packing and hydrogen bonding was shown to increase outwards from the microfibril center. The extent of disorder blurred the distinction between the I alpha and I beta allomorphs. Chains at the surface were distinct in conformation, with high levels of conformational disorder at C-6, less intramolecular hydrogen bonding and more outward-directed hydrogen bonding. Axial disorder could be explained in terms of twisting of the microfibrils, with implications for their biosynthesis.crystallinity | infrared | deuterium exchange | nuclear magnetic resonance | spin diffusion

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Section: Resultsmentioning

confidence: 97%

Nanostructure of cellulose microfibrils in spruce wood

Fernandes

Thomas

Altaner

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

636

693

View full text Add to dashboard Cite

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“…From vibrational spectroscopic studies, it can be seen that wood-water interactions are dominated by interactions with O-H groups (hydroxyls), since deuteration only affects O-H vibrations, while C-H stretching vibrations remain unchanged and no C-D stretching vibrations are observed (Hofstetter et al 2006;Mann and Marrinan 1956a;Schmidt et al 2006;Taniguchi et al 1966;Watanabe et al 2006). After deuteration and drying, the relative accessibility of hydroxyls to water can be determined as the ratio of integrated areas of O-D to the sum of O-H and O-D vibrations (Suchy et al 2010b;Taniguchi et al 1966) or alternatively as the ratio of weighted intensities of O-D to the sum of O-H and O-D vibrations (Mann and Marrinan 1956b;Sepall and Mason 1961).…”

Section: Vibrational Spectroscopymentioning

confidence: 99%

Experimental techniques for characterising water in wood covering the range from dry to fully water-saturated

2017

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Water plays a central role in wood research, since it affects all material properties relevant to the performance of wood materials. Therefore, experimental techniques for characterising water within wood are an essential part of nearly all scientific investigations of wood materials. This review focuses on selected experimental techniques that can give deeper insights into various aspects of water in wood in the entire moisture domain from dry to fully water-saturated. These techniques fall into three broad categories: (1) gravimetric techniques that determine how much water is absorbed, (2) fibre saturation techniques that determine the amount of water within cell walls, and (3) spectroscopic techniques that provide insights into chemical wood-water interactions as well as yield information on water distribution in the macro-void wood structure. For all techniques, the general measurement concept is explained, its history in wood science as well as advantages and limitations.

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“…For instance, stretching vibrations of O-H, N-H, and C-H are shifted to lower wavenumbers by roughly 1000, 900, and 800 cm -1 , respectively, compared to the same vibrations without deuterium. For wood and its constituent polymers, the interactions with water is dominated by hydroxyl-water bonds as seen by the absence of a C-D stretching peak and the unchanged nature of the C-H stretching peak after deuteration (Hofstetter et al 2006;Mann and Marrinan 1956a;Schmidt et al 2006;Taniguchi et al 1966;Watanabe et al 2006). Therefore, focusing on OD and OH stretching peaks and assuming that Beer's law holds, the relative hydroxyl accessibility can be determined by the ratio of areas of OD to OD ?…”

Section: Introductionmentioning

confidence: 99%

Hydroxyl accessibility in wood cell walls as affected by drying and re-wetting procedures

2017

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The first drying of wood cell walls from the native state has sometimes been described as producing irreversible structural changes which reduce the accessibility to water, a phenomenon often referred to as hornification. This study demonstrates that while changes do seem to take place, these are more complex than what has hitherto been described. The accessibility of wood cell wall hydroxyls to deuteration in the form of liquid water was not found to be affected by drying, since vacuum impregnation with liquid water restores the native cell wall accessibility. Contrary to this, hydroxyl accessibility to deuteration by water vapour was found to decrease to different levels depending on the drying conditions. Vacuum drying at 60°C for 3 days reduced the accessibility more than drying for 1 day at 103°C without vacuum. Drying for 3 days at 103°C increased the hydroxyl accessibility compared to 1 day. Moreover, the decrease in hydroxyl accessibility to deuteration by water vapour induced by the first drying could be at least partially erased by subsequent vacuum impregnation with liquid water, indicating reversibility. For the drying of solid, non-degraded wood cell walls the results challenge the often supposed process of hornification, understood as a permanent decrease in hydroxyl accessibility to water.

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Polarized infrared microspectroscopy of single spruce fibers: Hydrogen bonding in wood polymers

Cited by 31 publications

References 41 publications

Nanostructure of cellulose microfibrils in spruce wood

Nanostructure of cellulose microfibrils in spruce wood

Experimental techniques for characterising water in wood covering the range from dry to fully water-saturated

Hydroxyl accessibility in wood cell walls as affected by drying and re-wetting procedures

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