•A solvent blending approach for evenly mixing two polymers was proposed.•Hotmelt extrusion of composites of wood polysaccharides and polylactic acid was demonstrated.•3D scaffold prototypes of wood ...hemicellulose composites were successfully printed.•Mechanical and morphological properties of composite filament and scaffolds were measured and the results compared.
Hemicelluloses, the second most abundant polysaccharide right after cellulose, are in practice still treated as a side-stream in biomass processing industries. In the present study, we report an approach to use a wood-derived and side-stream biopolymer, spruce wood hemicellulose (galactoglucomannan, GGM) to partially replace the synthetic PLA as feedstock material in 3D printing. A solvent blending approach was developed to ensure the even distribution of the formed binary biocomposites. The blends of hemicellulose and PLA with varied ratio up to 25% of hemicellulose were extruded into filaments by hot melt extrusion. 3D scaffold prototypes were successfully printed from the composite filaments by fused deposition modeling 3D printing. Combining with 3D printing technique, the biocompatible and biodegradable feature of spruce wood hemicellulose into the composite scaffolds would potentially boost this new composite material in various biomedical applications such as tissue engineering and drug-eluting scaffolds.
Main conclusion Phloem production and structural development were interlinked with seasonal variation in the primary and secondary metabolites of phloem. Novel microtechniques provided new ...perspectives on understanding phloem structure and chemistry. To gain new insights into phloem formation in Norway spruce (Picea abies), we monitored phloem cell production and seasonal variation in the primary and secondary metabolites of inner bark (non-structural carbohydrates and phenolic stilbene glucosides) during the 2012 growing season in southern and northern Finland. The structure of developing phloem was visualised in 3D by synchrotron X-ray microtomography. The chemical features of developing phloem tissues isolated by laser microdissection were analysed by chemical microanalysis. Within-year phloem formation was associated with seasonal changes in non-structural carbohydrates and phenolic extractive contents of inner bark. The onset of phloem cell production occurred in early and mid-May in southern and northern Finland, respectively. The maximal rate of phloem production and formation of a tangential band of axial phloem parenchyma occurred in mid-June, when total non-structural carbohydrates peaked (due to the high amount of starch). In contrast, soluble sugar content dropped during the most active growth period and increased in late summer and winter. The 3D visualisation showed that the new axial parenchyma clearly enlarged from June to August. Subcellular changes appeared to be associated with accumulation of stilbene glucosides and soluble sugars in the newest phloem. Stilbene glucosides also increased in inner bark during late summer and winter. Our findings may indicate that stilbene biosynthesis in older phloem predominantly occurs after the formation of the new band(s) of axial parenchyma. The complementary use of novel microtechniques provides new perspectives on the formation, structure, and chemistry of phloem.
Modified natural rosins were evaluated as binders in the production of thermoplastic road marking paints (TRMPs). Pine rosin (GR), wood rosin (WR), and tall oil rosin (TOR) were used. Fourier ...transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), matrix-assisted laser desorption/ionization (MALDI-ToF-MS), and gel permeation chromatography-high pressure liquid chromatography (GPC-HPLC) were performed on natural and modified rosins. Acid number (mg KOH/g) ASTM D 465 – 05 and softening point, (°C) ASTM E 28 – 99 standard tests were applied to the samples. For the optimum synthesis condition, the pentaerythritol/rosin mol/mol ratio is 1/1, with the levels of Irganox 1425/rosin w/w, 0.5%, and TBM-6/rosin w/w, 1.0%. Gel permeation chromatography-high pressure analysis revealed that the esterification reaction yield was over 90% for each of the three natural rosins. Moreover, chromaticity coordinates (x,y), gloss factor (β), softening point (°C), and UVB aging test were applied to TRMPs. Modified natural rosins showed better results in the production of TRMPs. This is an important development and crucial step for sustainable TRMP production.
To understand the positional and temporal defense mechanisms of coniferous tree bark at the tissue and cellular levels, the phloem topochemistry and structural properties were examined after ...artificially induced bark defense reactions. Wounding and fungal inoculation with
of spruce bark were carried out, and phloem tissues were frequently collected to follow the temporal and spatial progress of chemical and structural responses. The changes in (+)-catechin, (-)-epicatechin, stilbene glucoside, and resin acid distribution, and accumulation patterns within the phloem, were mapped using time-of-flight secondary ion mass spectrometry (cryo-ToF-SIMS), alongside detailed structural (LM, TEM, SEM) and quantitative chemical microanalyses of the tissues. Our results show that axial phloem parenchyma cells of Norway spruce contain (+)-catechins, the amount of which locally increases in response to fungal inoculation. The preformed, constitutive distribution and accumulation patterns of (+)-catechins closely follow those of stilbene glucosides. Phloem phenolics are not translocated but form a layered defense barrier with oleoresin compounds in response to pathogen attack. Our results suggest that axial phloem parenchyma cells are the primary location for (+)-catechin storage and synthesis in Norway spruce phloem. Chemical mapping of bark defensive metabolites by cryo-ToF-SIMS, in addition to structural and chemical microanalyses of the defense reactions, can provide novel information on the local amplitudes and localizations of chemical and structural defense mechanisms and pathogen-host interactions of trees.
Phenolic stilbene glucosides (astringin, isorhapontin, and piceid) and their aglycons commonly accumulate in the phloem of Norway spruce (Picea abies). However, current knowledge about the ...localization and accumulation of stilbenes within plant tissues and cells remains limited. Here, we used an innovative combination of novel microanalytical techniques to evaluate stilbenes in a frozen-hydrated condition (i.e. in planta) and a freeze-dried condition across phloem tissues. Semiquantitative time-of-flight secondary ion-mass spectrometry imaging in planta revealed that stilbenes were localized in axial parenchyma cells. Quantitative gas chromatography analysis showed the highest stilbene content in the middle of collapsed phloem with decreases toward the outer phloem. The same trend was detected for soluble sugar and water contents. The specimen water content may affect stilbene composition; the glucoside-to-aglycon ratio decreased slightly with decreases in water content. Phloem chemistry was correlated with three-dimensional structures of phloem as analyzed by microtomography. The outer phloem was characterized by a high volume of empty parenchyma, reduced ray volume, and a large number of axial parenchyma with porous vacuolar contents. Increasing porosity from the inner to the outer phloem was related to decreasing compactness of stilbenes and possible secondary oxidation or polymerization. Our results indicate that aging-dependent changes in phloem may reduce cell functioning, which affects the capacity of the phloem to store water and sugar, and may reduce the defense potential of stilbenes in the axial parenchyma. Our results highlight the power of using a combination of techniques to evaluate tissue- and cell-level mechanisms involved in plant secondary metabolite formation and metabolism.
In this work we have analyzed the pine and spruce softwood lignin fraction recovered from a novel pressurized hot water extraction pilot process. The lignin structure was characterized using multiple ...NMR techniques and the thermal properties were analyzed using thermal gravimetric analysis. Acetylated and selectively methylated derivatives were prepared, and their structure and properties were analyzed and compared to the unmodified lignin. The lignin had relatively high molar weight and low PDI values and even less polydisperse fractions could be obtained by fractionation based on solubility in
-PrOH. Condensation, especially at the 5-position, was detected in this sulphur-free technical lignin, which had been enriched with carbon compared to the milled wood lignin (MWL) sample of the same wood chips. An increase in phenolic and carboxylic groups was also detected, which makes the lignin accessible to chemical modification. The lignin was determined to be thermally stable up to (273⁻302 °C) based on its T
value. Due to the thermal stability, low polydispersity, and possibility to tailor its chemical properties by modification of its hydroxyl groups, possible application areas for the lignin could be in polymeric blends, composites or in resins.
Hot-water extraction of hemicelluloses, especially galactoglucomannans, from fractions of ground spruce wood with different particle sizes was studied at 170°C with extraction times up to 60 min. ...Extraction of spruce sapwood, heartwood, and thermomechanical pulp (TMP) was also compared at 160 to 180°C. Static batch extractions were carried out in an accelerated solvent extractor (ASE). The extracted hemicelluloses were characterized by sugar unit analysis and determination of acetyl groups and molar masses. The particle size significantly affected the extraction of ground wood. The total extraction yield, as well as the yields of hemicelluloses and monosaccharides, was the highest from the finest ground wood fraction (< 0.1 mm). The release of acetic acid, average molar mass of extracted hemicelluloses, and end-pH of the extracts were also dependent of the particle size, although to a lower extent. Irrespectively of the ground wood particle size, the yield of hemicelluloses reached a plateau after 40 min extraction at 170°C. The results indicate that extraction of hemicelluloses is limited mainly by the diffusion in the fiber wall, and for coarse wood shives also by the mass transfer in the wood matrix. There were only small differences in the hot-water extraction yields of hemicelluloses from spruce sapwood, heartwood, and TMP, considering both poly- and monosaccharides.
Lignans are bioactive compounds that are especially abundant in the Norway spruce (
L. Karst.) knotwood. By combining a variety of chromatographic, spectroscopic and imaging techniques, we were able ...to quantify, qualify and localise the easily extractable lignans in the xylem tissue. The knotwood samples contained 15 different lignans according to the gas chromatography-mass spectrometry analysis. They comprised 16% of the knotwood dry weight and 82% of the acetone extract. The main lignans were found to be hydroxymatairesinols HMR1 and HMR2. Cryosectioned and resin-embedded ultrathin sections of the knotwood were analysed with scanning transmission X-ray microscopy (STXM). Cryosectioning was found to retain only lignan residues inside the cell lumina. In the resin-embedded samples, lignan was interpreted to be unevenly distributed inside the cell lumina, and partially confined in deposits which were either readily present in the lumina or formed when OsO
used in staining reacted with the lignans. Furthermore, the multi-technique characterisation enabled us to obtain information on the chemical composition of the structural components of knotwood. A simple spectral analysis of the STXM data gave consistent results with the gas chromatographic methods about the relative amounts of cell wall components (lignin and polysaccharides). The STXM analysis also indicated that a torus of a bordered pit contained aromatic compounds, possibly lignin.
The ecophysiology of the Norway spruce (Picea abies (L.) Karst.) trees that were used by three-toed woodpeckers (TTW) (Picoides tridactylus) for their sap-feeding activities were investigated. The ...pilot study was conducted in southern Finland (61°15′ N, 25°00′ E). During April–June 2015, three different tree categories of Norway spruce were selected for monitoring: trees that were frequently used by the TTWs for phloem sap-feeding for several previous years; trees that were only recently used by TTWs for sap-feeding; and control trees that were not used at all for sap-feeding. Phloem sap and phloem tissue samples were frequently extracted from tree trunks and analyzed for the content and composition of nonstructural carbohydrates, phloem sap osmolality, solute, and water content, as well as for the content and composition of secondary metabolites typical for defense reactions in the phloem. Simple crown characteristics were also measured, including tree height, diameter at breast height, and their ratio (slenderness index). According to our results, the TTWs preferred Norway spruce trees that showed advanced spring phenology to feed on, as evidenced especially by the lower ratio of raffinose (typically high during the winter months) to total soluble sugars of phloem tissues as compared to non-used control trees. The lower slenderness index of the trees chosen by the TTWs indicates low canopy competition pressure with good access to light (i.e., the sun heats the trunks well in spring). There were no differences in the phloem osmolality or solute content between the used or unused control trees. The trees used by the TTWs had significantly higher concentrations of antioxidant phenolic (+)-catechins and stilbene glycosides in phloem tissue, and the stilbene content was also higher in the extracted sap. The phenolics content of the phloem tissue had a clear seasonal trend, being the highest in the early spring and lower towards the onset of the cambial growth processes. The phloem sap is rich in antioxidants and soluble sugars that are potentially beneficial for the TTWs, but more quantitative research is needed to explore the importance of the sap properties to TTWs.
The physical, mechanical, and chemical properties of both stem wood and knot wood were investigated from two subfossil Scots pine (Pinus sylvestris L.) trunks retrieved from a lake in Finnish ...Lapland, dated to 404–486 CE and to 1318–1444 CE. Both the stem wood and the knot wood of the younger trunk had higher moisture content, lower density, and lower strength properties in comparison to the older trunk. The ash content of the stem wood of the younger trunk was lower, but the ash content of the knot wood was higher than that of the older trunk. Due to the degradation that occurred over time, all the values of physical and mechanical properties were lower compared to typical values of recently grown Scots pine wood. The chemical composition of both stem wood samples was close to the composition of the recently grown wood, and the only exception was the small decrease of the cellulose and hemicellulose in the subfossil samples. The bulk extractives were well-preserved, but terpenes and fatty acids underwent transformation, resulting in more stable compounds. The SWOT analysis (strengths, weaknesses, opportunities, and threats) showed pros and cons for the productization of subfossil wood, with the branding value of an ancient material being the potential enabler in developing commercial niche uses.
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