The states of water in Norway spruce (<i>Picea abies</i> (L.) Karst.) studied by low-field nuclear magnetic resonance (LFNMR) relaxometry:assignment of free-water populations based on quantitative wood anatomy

Low-field nuclear magnetic resonance (LFNMR) relaxometry was applied to determine the spin-spin relaxation time (T2) of water-saturated Norway spruce (Picea abies (L.) Karst.) specimens cut from mature sapwood (sW) and mature and juvenile heartwood (hW), where earlywood (EW) and latewood (LW) were separated. In combination with quantitative wood anatomy data focusing on the void volumes in various morphological regions, the NMR data served for a more reliable assignment of free-water populations found in water-saturated solid wood. Two free-water populations were identified within most sample types. One was assigned to water in the tracheid lumen and the other to water inside bordered pits. Whether water in the ray cell lumina was included in one or the other of these two populations depends on the curve-fit method applied (continuous or discrete). In addition, T2 differences between the different tissue types were studied and, for comparison, sorption isotherms were measured by means of a sorption balance. There was a significant difference between EW and LW as well as between juvenile wood and mature wood in terms of T2 related to the cell wall water. However, no differences were seen between the sorption isotherms, which indicates that the observed T2 differences were not due to differences in cell wall moisture content (MC)

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

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.ISSN:1572-882XISSN:0969-023

The Mechanisms of Plant Cell Wall Deconstruction during Enzymatic Hydrolysis

Mechanical agitation during enzymatic hydrolysis of insoluble plant biomass at high dry matter contents is indispensable for the initial liquefaction step in biorefining. It is known that particle size reduction is an important part of liquefaction, but the mechanisms involved are poorly understood. Here we put forward a simple model based on mechanical principles capable of capturing the result of the interaction between mechanical forces and cell wall weakening via hydrolysis of glucosidic bonds. This study illustrates that basic material science insights are relevant also within biochemistry, particularly when it comes to up-scaling of processes based on insoluble feed stocks

Bacterial and abiotic decay in waterlogged archaeological Picea abies (L.) Karst studied by confocal Raman imaging and ATR-FTIR spectroscopy

Waterlogged archaeological Norway spruce [Picea abies (L.) Karst] poles were studied by means of confocal Raman imaging (CRI) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) analysis to determine lignin and polysaccharide composition and distribution in the cell wall. The waterlogged archaeological wood (WAW) was submerged under anoxic conditions for approximately 400 years and solely decayed by erosion bacteria (EB). CRI showed that decayed tracheids contain a residual material (RM) with heterogeneous lignin distribution; within the same tracheid RM often contained regions with intensities lower than sound S2 layers up to intensity values as high as the compound middle lamella (CML). CRI revealed strong depletion of carbohydrates in RM which indicated that EB are able to utilise the carbohydrate fraction of the cell wall effectively. Raman bands assigned to lignin did not show any difference between RM and sound S2. This is a hint that EB do not modify the lignin structure. Sound WAW free from EB decay showed evidence of loss of acetyl groups in glucomannan, loss of un-conjugated ester linkages in the lignin-carbohydrate complexes between xylan and lignin, and minor oxidation of the lignin polymer compared to recent reference material. This is evidence for abiotic decay in the course of waterlogging

Structure and enzymatic accessibility of leaf and stem from wheat straw before and after hydrothermal pretreatment

BACKGROUND: Biomass recalcitrance is affected by a number of chemical, physical and biological factors. In this study we looked into the differences in recalcitrance between two major anatomical fractions of wheat straw biomass, leaf and stem. A set of twenty-one wheat cultivars was fractionated and illustrated the substantial variation in leaf-to-stem ratio between cultivars. The two fractions were compared in terms of chemical composition, enzymatic convertibility, cellulose crystallinity and glucan accessibility. The use of water as a probe for assessing glucan accessibility was explored using low field nuclear magnetic resonance and infrared spectroscopy in combination with hydrogen-deuterium exchange. RESULTS: Leaves were clearly more degradable by lignocellulolytic enzymes than stems, and it was demonstrated that xylose removal was more linked to glucose yield for stems than for leaves. Comparing the locations of water in leaf and stem by low field NMR and FT-IR revealed that the glucan hydroxyl groups in leaves were more accessible to water than glucan hydroxyl groups in stems. No difference in crystallinity between leaf and stem was observed using wide angle x-ray diffraction. Hydrothermal pretreatment increased the accessibility towards water in stems but not in leaves. The results in this study indicate a correlation between the accessibility of glucan to water and to enzymes. CONCLUSIONS: Enzymatic degradability of wheat straw anatomical fractions can be indicated by the accessibility of the hydroxyl groups to water. This suggests that water may be used to assess glucan accessibility in biomass samples