Lipophilic extractives in different tree fractions and forestry assortments of Pinus sylvestris due for thinning or final cutting

The objectives were to determine the content and composition of lipophilic extractives, particularly fatty and resin acids, in three Scots pine trees from each of two stands in northern Sweden, one that was due for thinning and one due for final cutting. Extractives content of branches, needles, barks, stem discs from branch whorls, and sapwood and heartwood samples from various heights was measured. Fractions had very different concentrations and distributions of extractives due to differences in the composition of tissues. The needles had the highest total extractive concentration (around 150?kg/ton d.w.), followed by the branches, bark, timber from the final cut stand, and then the pulpwood and timber from the thinning stand. The final cut stand generally provided higher yields of extractives in assortments per hectare than the thinning stand; the difference was five-fold for timber, three-fold for whole trees, two-fold for branches, needles and bark and similar for pulpwood. This information on the content and composition of extractives in different tissues, and the dependence of these quantities on tree age could be used together with information on conventional stand data such as tree numbers and dimensions to guide the selection and management of feedstocks for biorefineries.     

Acceleration of the cure of phenolic resin adhesives VII: Influence of extractives of merbau wood on bonding

The influence of merbau wood extractives on the gelation rate of a phenolic adhesive and the effects of some cure accelerators on the bond performance of merbau plywood were investigated. The addition of merbau wood extractives slightly increased the gelation rate of the phenolic resin. This increase in the gelation rate was revealed to be due to a fall in the resin pH caused by addition of the extractives. The addition of cure accelerators, sodium carbonate and propylene carbonate, caused a considerable reduction in the hot-pressing time required for the merbau plywood to achieve sufficient bond qualities. Brushing veneer surfaces caused an increase in bond qualities. The combination of the cure acceleration and the surface brushing greatly improved the bondability of merbau wood. The main factor of gluing difficulty is considered to be the poor wettability of the veneer surfaces resulted from the accumulation of migrating extractives.Part of this work was presented at the 47th annual meeting of The Japan Wood Research Society, Kochi, April 3–5, 1997     

Degradation of lipophilic wood extractive constituents in Pinus sylvestris by the white-rot fungi Bjerkandera sp. and Trametes versicolor

The white-rot fungi Trametes versicolor and Bjerkandera spp. are among the most frequent decomposers of angiosperm wood in forest ecosystems and in wood products in service. Wood extractives have a major impact on wood properties and wood utilization. This work evaluated the ability of two white-rot fungal strains (Bjerkandera sp. strain BOS55 and T. versicolor strain LaVec94-6) to degrade the main lipophilic extractive constituents in Scots pine (Pinus sylvestris L.). The time course of wood decay and wood extractive degradation was monitored in stationary batch assays incubated for eight weeks. The strains tested eliminated high levels of total resin, 34 to 51% in two weeks. Wood triglycerides were the most readily degraded extractive components (over 93% elimination in only two weeks). Free fatty acids and resin acids, which are potential fungal inhibitors, were also rapidly decomposed by the fungal strains. Sterols were used more slowly, nonetheless, the fungal degradation of this extractive fraction ranged from 50 to 88% after four weeks. Received 19 March 1999     

Comparative study of organic solvent-soluble and water-soluble lipophilic extractives from wheat straw 2: spectroscopic and thermal analysis

As a continuing study of six organic solventsoluble lipophilic extractives and one water-soluble lipophilic extract from wheat straw, seven extracts were further compared using Fourier transform-infrared (FT-IR) analysis,¹H and¹³C nuclear magnetic resonance (NMR) spectroscopy, and thermal analysis. In the FT-IR spectra of two-thirds chloroform/one-third methanol, methyltertbutyl ether (MTBE), hexane, petroleum ether, and dichloromethane extracts, a strong band at 1746cm^–1 is indicative of the ester carbonyl of triglycerides or steryl esters or waxes, whereas the occurrence of carboxylic carbonyl of free fatty acids or resin acids at 1712–1719 cm^–1 is verified in the spectra of two-thirds toluene/one-third ethanol and hot water extracts. Signals at 187.9,178.4, and 173.3 ppm in the¹³C NMR spectrum of MTBE extract correspond to carbonyl groups of resin acids, fatty acids, and fatty acid/steryl esters, respectively. All the extractives were to varying degrees thermally unstable at a temperature of about 200°C, and the melting temperature occurred at about 54°C.     

Chemical characterization of wood and extractives of fast-growing Schizolobium parahyba and Pinus taeda

This study aims to evaluate the chemical composition of wood and extractives of Pinus taeda and Schizolobium parahyba (guapuruvu) as potential feedstock for new applications in the biorefinery industry. For this purpose, their content of α-cellulose, hemicellulose, insoluble lignin, hot water solubility, NaOH_1% solubility, inorganic materials (ash), and monomeric sugars by high-performance liquid chromatography was quantified. Attenuated total reflectance infrared spectroscopy and thermogravimetric analysis were also used to complete the physicochemical characterization of the studied woods. The extractives were obtained by soxhlet extraction with ethanol:toluene and dichloromethane and identified with pyrolysis-gas chromatography/mass spectroscopy technique. The results showed that guapuruvu wood has the higher amount of hemicellulose (16%) when compared to pine wood (10%), which resulted in higher solubility in alkali solution. Furthermore, in relation to other biomasses, the two woods presented more percentage of lignin and minor content of hemicelluloses. The P. taeda wood presented the highest percentage of extractives mainly composed of fatty acids and aromatic hydrocarbons, while guapuruvu wood had a higher percentage of phenolic compounds and also fatty acids. Both the materials have low content of extractives with dichloromethane and were mainly composed of lipophilic compounds.     

Residual extractives in aspen kraft pulps and their impact on kappa number and Klason lignin determination

We investigated the impact of residual extractives on lignin determination by lignin content difference between unextracted and extracted pulps, residual extractives analysis, and lignin content contribution from model extractive compounds. There were two different kinds of extractives in aspen kraft pulp. The extractives impacting on kappa number determination were well removed in oxygen delignification; these were mainly unsaturated fatty acids. However, the extractives impacting on Klason lignin determination were largely resistant to oxygen delignification; these were mainly saturated fatty acids, sterols, and hydrocarbons. Oxidation of unsaturated fatty acids was the main reaction in oxygen delignification. These trends were confirmed by simulation of lignin content determination with three model extractive compounds (β-sitosterol, linoleic acid, and palmitic acid). The publication of this article was made possible by an Emachu Research Fund. The authors are grateful for the fund.     

Enhanced seed production and metabolic alterations in Larix leptolepis by girdling

The demand for Japanese larch (Larix leptolepis) seeds has increased in Korea but their supply has been limited due to sporadic natural seed production. Among the various flower induction techniques, girdling woody stems has been recognized as a simple and efficient method to enhance seed production in a number of conifers. In this study, stem girdling was applied to 42-year-old Japanese larches, resulting in remarkable enhancement of seed cone production with no morphological changes in the seed characteristics. Metabolic alterations in needles of the girdled and the control trees were interrogated by using 23 individual metabolites including soluble sugars, polyamines and amino acids. In the girdled trees, the contents of both soluble sugars and polyamines were higher from June to July and then became similar to those in the control. The levels of amino acids were significantly increased only in August by girdling compared to the non-girdled trees. In control larch trees, the dominant amino acids were changed from Glu and Ala until July to Asp and Tyr in August. Interestingly, the concentrations of Asp-derived amino acids such as Lys, Met and Thr, were increased by girdling and they also showed significant correlations with the number of seed cones per trees, suggesting that the enhanced levels of three amino acids might positively influence on the development of seed cones in girdled larch trees. Although the role of Asp-derived amino acids on enhanced seed cone production remains unclear, the approach presented in this study might provide useful information in elucidating metabolic network modulation induced by girdling and will be further applied for enhanced seed cone production in Japanese larch trees.     

Improvement mechanism of bondability in UF-bonded reed and wheat straw boards by silane coupling agent and extraction treatments

The effects of silane coupling agents and extractives on the wettability of reed and wheat straws were investigated. The inherent wettability of these materials was low but could be significantly improved by treating with silane coupling agents. The degree of improvement achieved by each silane coupling agent was different: Vinyl silane had almost no effect on wettability, epoxide silane was found to be more effective for reed straw, and amino silane was better for wheat straw. The wettability of these materials could also be improved by ethanol-benzene extraction, which resulted in more improvement in wheat straw than reed straw. The analyses of untreated reed and wheat straws by electron spectroscopy for chemical analysis (ESCA) revealed that there was much silicon on both the outer and inner surfaces of the former but only on the outer surface of the latter. The influence of hot-water extractives and silane coupling agents on the gelation time and pH of urea formaldehyde (UF) resin was also examined. The addition of extractives was found to increase the gelation time. Amino silane greatly retarded the gelation of OF resin, whereas epoxide and vinyl silanes had no influence on resin gelation. This retardation was found to be due to an increase in the pH of the resin.     

连续树脂法分离林可霉素的新工艺研究

指出了采用新型XAD-2010极性大孔树脂和LX脱色树脂对林可霉素进行连续分离的方法,中间杂质可以得到有效分离。对新型XAD-2010极性大孔树脂和LX脱色树脂柱的吸附参数、解析参数进行了考察,进一步对树脂的再生方法和参数进行了优化,确定了连续树脂法分离林可霉素各项工艺参数。结果表明:极性大孔树脂XAD-2010的理论最大吸附量92~79.6 g/L,上柱吸附近饱容量在53~43 g/L,平均洗脱率98.5%。LX3#脱色树脂在酸性条件下,对酸解液的最大处理能力达到40BV以上,对浓缩液的处理能力更高。该工艺大孔树脂洗脱收率95%,脱色后收率92%,一次结晶总收率87.4%。新工艺采用活性炭、新型极性大孔树脂XAD-2010、LX弱碱性阴离子脱色树脂连续分离法可以有效分离林可霉素,有望完全替代生产上的正丁醇萃取法。     

Stem respiration is influenced by pruning and girdling in Pinus sylvestris

Abstract

Stem respiration was measured in the growing season (June to July) and in the dormant season (October) to detect cambial activity induced by pruning live branches or girdling stems in Scots pine trees (Pinus sylvestris L.) growing in northern Sweden. Immediately after the treatments, the treatment:control ratio of stem respiration increased to between 1.38 and 1.44 in the pruning treatment and between 1.17 and 1.20 in the girdling treatment. The treatment:control ratio of stem respiration then decreased by the end of July, to 0.65 in the pruning treatment and 0.55 in the girdling treatment. In October, the treatment:control ratios were higher: between 0.87 and 0.97 in the pruning treatment and between 0.85 and 0.97 in the girdling treatment. In both pruning and girdling treatments, the time trends of stem respiration rates largely followed those of stem temperatures: the stem respiration rate increased exponentially with an increase in stem temperature. The Q ₁₀ values were 2.83–4.05 and 2.57–2.89 in the pruning treatment and control, and 2.10–2.60 and 1.99–3.19 in the girdling treatment and control, respectively. In most cases, the values of Q ₁₀ in both treatments did not differ significantly from those in the controls.     

Effects of stem girdling on cone yield and endogenous phytohormones and metabolites in developing long shoots of Douglas-fir (Pseudotsuga menziesii)

Stem-girdling treatments were applied in early spring to stimulate cone formation in two genotypes of interior Douglas-fir (Pseudotsuga menziesii var. glauca (Beissn.) Franco). After girdling treatments, male cone yield increased significantly in the next growing season. The increase was 14-fold in genotype 9137. In genotype 9550, more than 8,700 male cones were induced from each tree whereas no male cones were found in controls. Female cone yield was zero in controls and low for girdled trees in both genotypes. Multiple phytohormone-related compounds, including gibberellins (GAs), cytokinins, indole-3-acetic acid (IAA), abscisic acid (ABA) and their selected metabolites, were analyzed in developing long shoots after girdling treatments by high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC?CESI?CMS/MS) in multiple reaction monitoring mode. Concentrations of GA₄ were slightly higher at week 2 following girdling treatment, whereas at week 8 lower GA₄ concentrations were found in girdled samples. Stem girdling did not affect concentrations of IAA and major cytokinins, such as zeatin riboside and isopentenyl adenosine. Concentrations of ABA differed two-fold between the genotypes. Although girdling treatment did not cause differences in ABA concentrations, it generally resulted in higher concentrations of ABA glucose ester. Concentration increase of 7??-hydroxy ABA by girdling was only found in genotype 9550 at week 8. Girdling caused little change in concentrations of phaseic acid in both genotypes.     

Recovery of bioactive compounds from Pinus pinaster wood by consecutive extraction stages

Pinus pinaster wood samples, obtained at different positions of three healthy trees, were subjected to two sequential extractions using an Accelerated Solvent Extraction instrument. The first extraction was carried out with hexane (to remove lipophilic extractives) and the second one with acetone/water (95:5 v/v) to recover bioactive phenolic compounds, the target compounds of this study. The extracted fractions were assayed for total yield and composition. The extracts contained a spectrum of phenolic compounds (simple phenolics, phenolic stilbenes, flavonoids and lignans) and non-phenolic components (juvabiones, resin and fatty acids, steryl esters and triglycerides). The fractionation effects achieved by consecutive extractions and the recovery of bioactive phenolics are discussed.     

The effect of brown-rot decay on water adsorption and chemical composition of Scots pine heartwood

? The effect of brown-rot (Coniophora puteana) decay on the water adsorption capacity and concentration of extractives of Scots pine (Pinus sylvestris L.) heartwood were studied by comparing corresponding properties of decayed and undecayed wood samples.

? The samples derived from 39 felled trees having a large between-tree variation in the extractive concentrations, and subsequently in the mass loss in the decay test. The water adsorption capacity, expressed as equilibrium moisture content (EMC), was measured at a high relative humidity (RH ～100%, 21 °C).

? In contrast to the widely held belief, the water adsorption capacity of brow-rotted heartwood appeared to be significantly higher than that of undecayed heartwood.

? The chemical composition of heartwood was changed radically by the fungus: the concentration of stilbenes, resin acids and free fatty acids decreased, while the concentration of soluble sugars increased as a result of decay. In addition, fungal sugars were found in the decayed samples. The concentration of total phenolics increased, which obviously reflected chemical changes in cell wall constituents other than extractives.

? As a conclusion, the information concerning the hygroscopicity of brown-rotted wood might be valuable e.g. when carrying out repairs on buildings damaged by advanced decay.

     

Quantitative comparisons of antitermite extractives in heartwood from the same clones of <Emphasis Type="Italic">Cryptomeria japonica</Emphasis> planted at two different sites

The quantities of some extractives in the heartwood of 25 plus tree clones of Japanese cedar (Cryptomeria japonica) from two different sites were investigated to clarify the differences in antitermite properties in relation to clones and environmental factors. The measured compounds were cubebol, epicubebol, sandaracopimarinol, and ferruginol. The total amounts of extractives were calculated from gas chromatogram peak areas. The heartwoods from Tano (Tano Forest Research Station, Miyazaki University; 31° N, 131° E, 130 m asl) tended to contain more of the individual extractives and total extractives than those from Komenono (Komenono Forest Research Station, Ehime University; 33° N, 132° E, 700 m asl). There was a significant difference (calculated by analysis of variance) at the 1% level among clones at both sites in quantities of total and individual extractives. This result suggests that the qualities and quantities of heartwood extractives are largely affected by genetic factors. Spearman’s rank correlation with the average of the extractive quantities at the sites was investigated. The correlation coefficients of total extractives, cubebol, epicubebol, sandaracopimarinol, and ferruginol were 0.61, 0.85, 0.76, 0.67, and 0.74, respectively. This result means that the order of the amounts of these compounds among the cultivars could be maintained at different sites. It is apparent that both environmental and genetic factors affected the quantities of these extractives in the heartwoods of Japanese cedar.     

Comparative study of organic solvent and water-soluble lipophilic extractives from wheat straw I: yield and chemical composition

 The chemical composition of six lipophilic extractives from wheat straw by extraction with toluene-ethanol (2 : 1, v/v), chloroform-methanol (2 : 1, v/v), methyl tert-butyl ether, hexane, petroleum ether, and dichloromethane, respectively, in a Soxhlet extractor, and one water-soluble lipophilic extract has been examined. Five main lipid classes (free fatty/resin acids, sterols, waxes, steryl esters, triglycerides) were identified and their individual components quantified by gas chromatography as their trimethylsilyl (TMS) esters (free fatty/resin acids) and TMS ethers (sterols). The abundant saturated fatty acids were palmitic acid (C16:0), myristic acid (C14:0), and pentadecanoic acid (C15:0). Palmitoleic acid (C16:1), linoleic acid (C18:2), and oleic acid (C18:1) were the major unsaturated free fatty acids. Abietic acid was detected as the only single component in the resin acids. Of the sterols identified, β-sitosterol was found to be the major compound together with minor amounts of cholesterol, ergosterol, stigmasterol, and stigmastanol. Palmityl palmitate and oleyl palmitate were identified as the major components in waxes. The steryl esters analyzed were composed of steryl laurate, steryl myristate, steryl palmitate, steryl heptadecanoate, and steryl oleate. Tripalmitin, dipalmitoyl-oleoylglycerol, and triolein were the major components of the triglycerides. Received: January 29, 2001 / Accepted: January 30, 2001 Acknowledgments We are grateful for the financial support of this research from the LINK program (fractionation of wheat straw) of the U.K. Ministry of Agriculture, Fisheries, and Food, and the prominent young scientist program of National Natural Science Foundation of China (no. 30025036). We also thank Mrs. Jianmin Fang for her help with extraction of the samples. Correspondence to:R.C. Sun     

Selection of feeding trees by capercaillie Tetrao urogallus in winter

Selection of winter feeding trees by capercaillie Tetrao urogallus was studied by sampling of needles of Scots pine Pinus sylvestris trees browsed by capercaillie and closely situated unbrowsed trees in 5 localities situated in the southern half of Norway. Browsed trees contained higher concentrations of N than unbrowsed trees but no differences in P were found among browsed and unbrowsed samples. Needles eaten by capercaillie were significantly lower in resin content than needles from unbrowsed trees. For tannin, no differences between browsed and unbrowsed trees were found. Results give evidence that capercaillie select needles richest in N when the resin content is low, but when high, the birds select needles low in resin. Thus, both N and resin play an important role in selection of winter browse by capercaillie.     

Wood properties of juvenile and mature heartwood in Robinia pseudoacacia L.

The aim of this study is to characterise the properties of juvenile and mature heartwood of black locust (Robinia pseudoacacia L.). Content, composition and the subcellular distribution of heartwood extractives were studied in 14 old-growth trees from forest sites in Germany and Hungary as well as in 16 younger trees of four clone types. Heartwood extractives (methanol and acetone extraction) were analysed by HPLC-chromatography. UV microspectrophotometry was used to topochemically localise the extractives in the cell walls. The natural durability of the juvenile and mature heartwood was analysed according to the European standard EN 350-1. Growth as well as chemical analyses showed that, based on extractives content, the formation of juvenile wood in black locust is restricted to the first 10–20 years of cambial growth. In mature heartwood, high contents of phenolic compounds and flavonoids were present, localised in high concentrations in the cell walls and cell lumen of axial parenchyma and vessels. In juvenile wood, the content of these extractives is significantly lower. Juvenile wood had a correspondingly lower resistance to decay by Coniophora puteana (brown rot fungus) and Coriolus versicolor (white rot fungus) than mature heartwood.     

Girdling effects on fruit set and quantum yield efficiency of PSII in two Citrus cultivars

Girdling effects on fruitlet abscission, leaf chlorophyll, chlorophyll a fluorescence and carbohydrate concentration in various flowering and vegetative shoots were studied during natural fruit drop in two Citrus cultivars. Irrespective of shoot type, girdling delayed fruitlet abscission, but only fruitlets borne on leafy shoots had increased final fruit set. Chlorophyll a fluorescence analysis revealed differences in quantum yield efficiency of photosystem II of light adapted leaves (Phi(PSII)) among shoot types and in response to girdling. In young leaves of vegetative shoots, girdling decreased Phi(PSII), whereas Phi(PSII) increased from Day 30 after girdling in young leaves of leafy flowering shoots; however, Phi(PSII) did not change in mature leaves during fruit set in either control or girdled trees. Girdling altered leaf carbohydrate concentrations and the photosynthetic performance of the various shoot types. Our results indicate that, in Citrus, several carbohydrate-based regulatory mechanisms of photosynthesis coexist during carbohydrate accumulation brought about by girdling. It is concluded that the delay in fruitlet abscission and the increase in Phi(PSII )observed in girdled leafy flowering shoots are the mechanisms underlying the enhancement of fruit set after girdling.     

Colour responses of black locust (Robinia pseudoacacia L.) to solvent extraction and heat treatment

The colour parameters (CIE L*a*b*) of black locust (Robinia pseudoacacia L.) wood meals extracted with seven solvents and heated under saturate vapour at 120°C are measured and the UV–vis spectrum analysis of dioxane extractives is performed to investigate the influence of extraction and thermal treatment on wood discolouration. The results show that extractions with polar solvents such as water, ethanol and dioxane can cause substantial decrease of b* but have little effect on a* and that extractions with less or non-polar solvents such as chloroform, ether and hexane can hardly influence both a* and b*. Extractions with ethanol and dioxane can also increase the optical reflection (L*) and arise a higher ΔE change than that with less or non-polar solvents. Heat treatment has much more influence on colour parameters than extractions do. After heat treatment, the lightness index of all the samples declines but a* value increases. The discolouration during thermal treatment is mainly due to the existence of polar extractives. Tannins, flavonoids and hydroxyanthraquinones are found in the dioxane extractives. The heated dioxane extractives have an obvious absorption between 400 and 600 nm. The condensation of the tannin molecules and the oxidation of the hydroxyl groups in flavonol molecules make up the potential reason of the formation of new colour substances during heat treatment. The elimination of the dioxane extractives can effectively reduce the extent of thermally induced discolouration.