Reactivity of secondary hydroxyl groups in methylβ-d-xylopyranoside toward aβ-o-4-type quinone methide

Methyl-d-xylopyranoside was allowed to react with-O-4-type quinone methide without a catalyst to elucidate the reactivities of secondary hydroxyl groups at the C2, C3, and C4 positions. Benzyl ether-type lignin-carbohydrate complex (LCC) compounds linked at the C2 and C4 positions were predominant, at a ratio of 23. However, the reactivity of the hydroxyl group at the C3 position was quite low. These results strongly suggest that the reactivity of the C2 hydroxyl group in xylan toward quinone methide intermediate is higher than that of the C3 hydroxyl group during biosynthesis of LCCs.     

Determination of nitrobenzene oxidation products by GC and1H-NMR spectroscopy using 5-iodovanillin as a new internal standard

The nitrobenzene oxidation method was modified to obtain more reproducible data and more structural information about lignin, not only by gas chromatography (GC) but also by proton nuclear magnetic resonance (¹H-NMR) spectroscopy for quantitative determination of the oxidation products and to simplify the procedures. The nitrobenzene oxidation mixture was directly extracted after acidification without preextraction of by-products. The direct extraction made the extractive step easy and gave reproducible data. 5-Iodovanillin was selected as a new internal standard. The reason for this selection was that 5-iodovanillin did not exist in the nitrobenzene oxidation products from any plant species and had an aldehyde group whose peak did not overlap with the other aldehyde peaks on an¹H-NMR spectrum. Thus, the use of 5-iodovanillin enabled us to quantifyp-hydroxybenzaldehyde, vanillin, and syringaldehyde in oxidation products on the basis of¹H-NMR analysis as well as GC. Furthermore, more information about the condensed structure of lignin was derived by comparing the¹H-NMR and GC analyses.Part of this work was presented at the 42nd Annual Meeting of the Lignin Symposium, Sapporo, October 1997     

Variation in the chemical composition of green leaves and leaf litters from three deciduous tree species growing on different soil types

The chemical composition of green leaves and leaf litters of sweet chestnut (Castanea sativa), oak (Quercus robur) and beech (Fagus sylvatica) were determined for 26 sites grouped into high fertility (HF) and low fertility (LF) soils according to base saturation and N-mineralization potentials. Measurements were made of total carbon, acid detergent fibre (ADF), Klason lignin, holo-cellulose, sugar constituents of hemicellulose and phenylpropanoid derivatives of lignin, and nutrient concentrations (N, Ca, P, Mg, K and Mn). Leaf and litter constituents varied within and between species according to soil groups, but beech showed contrasting responses to oak and chestnut. Beech leaves had lower ADF, lignin and cellulose on HF soils than LF soils, whereas oak and chestnut leaves had higher ADF, lignin and cellulose on HF than the LF soils. Conversely, the same constituents in beech leaf litter were higher on HF soils than LF soils, but lower in oak and chestnut leaf litter on HF soils than LF soils. The phenylpropanoid derivatives of lignin and sugar constituents of hemicellulose also showed similar variations in relation to soil groups with contrasting patterns for in leaves and litters. Re-absorption of N from leaves before litter fall was negatively correlated with soil N mineralization potential for beech (highest on LF soils) but showed an unexpected, positive relationship for oak and chestnut (highest on HF soils). These intra-specific differences of leaf and litter chemistry in relation to soil fertility status are unprecedented and largely unexplained. The observed patterns reflect phenotypic responses to soil type that result in continuum of litter quality, within and between tree species, that have been shown in related studies to significantly influence litter decomposition rates.     

Infrared spectroscopic study of alkaline oxygen treatment of lignin with ATR technique in aqueous state 1: method for determining quantitative spectra of oxygen-degraded lignin

For the fundamental study of oxygen delignification of kraft pulp, structural changes of kraft lignin during alkaline oxygen treatment were investigated with the use of infrared measurement with attenuated total reflectance (ATR) technique. In the neutralized reaction mixture of alkaline oxygen-treated kraft lignin, there is a significant amount of NaCl, so that the spectral changes of water due to the coexistence of NaCl was investigated, and how to remove the huge absorption of NaCl solution is discussed. Sodium vanillate–NaCl solutions were employed as model solutions for the reaction mixture. Partial least square (PLS) regression was applied for the prediction of NaCl concentration, and the spectrum of NaCl solution was subtracted from the spectrum of sodium vanillate–NaCl solution as background measurement. This allowed us to obtain the vanillate spectra free from the absorption of NaCl solution. In addition, the mathematical method for reconstructing the spectrum of NaCl solution is discussed. The spectrum of NaCl solution is reconstructed as the linear combination of basic spectra calculated by singular value decomposition (SVD), and it was subtracted from that of the sodium vanillate–NaCl solution. By this procedure, the vanillate spectra were also obtained quantitatively, as has been demonstrated in PLS regression study. It was also confirmed that the quantitative spectra of high molecular weight fraction of alkaline oxygen-treated kraft lignin were obtained by the use of this reconstruction technique.Parts of this report were presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002 and the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003     

Semi-quantitative method to evaluate the α-carbonyl content in lignin

A method to estimate the content of -carbonyl structures in lignin was developed. This method consists of two successive treatments: NaBD₄ treatment of pulp to reduce an -carbonyl structure in lignin, and nitrobenzene oxidation. NaBD₄ was used to convert an -carbonyl structure to a deuterium-labeled hydroxymethine structure. The ratio of D-vanillin [(HO)(H₃CO)C₆H₃CDO] to H-vanillin [(HO)(H₃CO)C₆H₃CHO] or that of their syringyl analogues obtained by nitrobenzene oxidation was used as the measure of the content of -carbonyl structure. Model experiments demonstrated that when sodium hydroxide was used as alkali for the nitrobenzene oxidation, the retention of deuterium at the side chain -position was very low due to the displacement of deuterium with hydrogen by an unknown reaction mechanism. In order to depress this unexpected displacement, the reaction conditions of the nitrobenzene oxidation were modified. The modified nitrobenzene oxidation employs 0.5mol/l of lithium hydroxide as a reaction medium instead of 2.0mol/l sodium hydroxide. By this modification, this method could successfully trace the formation and the degradation of the -carbonyl structure in milled wood lignins.This paper was presented in part at the 11th International Symposium on Wood and Pulping Chemistry, Nice, France, June 2001 and at the 46th Lignin Symposium, Kyoto, Japan, November 2001     

Spectrophotometrical characteristics in the near infrared region in beech (<Emphasis Type="Italic">Fagus crenata</Emphasis>) and pine (<Emphasis Type="Italic">Pinus densiflora</Emphasis>) litters at the various decomposing stages

We examined the relationships between the absorptional characteristics in the near infrared region and the chemical changes of decomposing beech (Fagus crenata) and pine (Pinus densiflora) litters. Spectra as well as the concentrations of chemical substances approached each other and converged with decomposition, although both initial characteristics differed markedly between beech and pine. This indicated that the fundamental chemical structures were almost the same, although their organochemical composition differed. Specific absorption bands for lignin, polysaccharide, and protein were identified at 2,140 and 1,670 nm, 2,270, 1,720, 1,590, and 1,216 nm, and 2,350 nm, respectively. Absorbance at 1,670 nm, peculiar band of aromatics, showed a positive correlation with lignin concentration, which suggested the relative increment of aromatics due to condensed lignin in decomposing litters. Absorbance at 2,140 nm, characterized as the C–H bond in HRC = CHR, showed a negative correlation with lignin concentration, which suggested the decrements of some structures such as side-chains in lignin polymers unrelated to aromatics. Absorbance at 2,270, 1,720, and 1,216 nm, specified to O–H/C–O/C–H bonds in saccharide, might reflect the change of polysaccharide during decomposition because they showed a positive correlation to polysaccharide concentration. In the same way, absorbance at 2,350 nm, identified to the C–H/CH₂ bonds in protein, showed a negative correlation to nitrogen concentration in decomposing litters, which might indicate that the C–H/CH₂ bonds in protein decreased with decomposition due to microbial consumption of carbon in protein. Our findings suggested the possibility that the spectral changes indicate the litter digestibility during decomposition and that also explain the compositional change in decomposing litters.     

生物质快速热解装置主反应器的研究现状

阐述了现有的生物质热解液化技术中主反应器的研究现状,分析了相应的优势与不足。介绍了在以转锥式快速热解液化设备所做的实验中所总结的问题及经验,提出了未来需要研究的问题,并预测了今后的研究方向,为生物质新能源的研究开发及生产探索了新的途径。     

木材热分解动力学的研究

用ＴＧ－ＤＴＡ热分析联用技术测定了４种常用木材的ＴＧ－ＤＴＡ－５曲线，并用热动力学方法处理的ＴＧ曲线，获得了相应动力学参数。发现各种木材在干燥阶段和煅烧阶段的热性质大致相似，而炭化阶段的热性质则因木材人化学组成不同而有较大差异。     

Delignification of cell walls of <Emphasis Type="Italic">Chamaecyparis obtusa</Emphasis> during alkaline nitrobenzene oxidation

To clarify the behavior of whole lignins in wood cell walls during alkaline nitrobenzene oxidation, the delignification process from cell walls in normal and compression woods of Chamaecyparis obtusa Endl. (Cupressaceae) was observed using ultraviolet and transmission electron microscopies. The lignin content conspicuously decreased to around 10% after 35min in normal wood. The lignin content in compression wood finally leveled off at aroumd 10% after 50min. In gel filtration of oxidation products in ethyl acetate, a high molecular weight fraction was prominent in extracts from the early stage of the reaction. As the oxidation progressed, the high molecular weight fraction became less prominent in both normal and compression wood. Changes in the weights of cell wall residues during reaction indicated that approximately half of the components other than lignin were also removed from the cell walls. This shows that the majority of lignin with relatively high molecular weight is removed from the cell walls together with polysaccharides in the early stage of the reaction and that further oxidative degradation occurs in solution in later stages. Only a small amount of the lignin with low molecular weight could be analyzed by gas chromatography.Parts of this report were presented at the 47th (Kochi, April 1997) and 48th (Shizuoka, April 1998) Annual Meetings of the Japan Wood Research Society, and at the Lignin Symposium, Sapporo, October 1997     

GC-MS and IR spectroscopic analyses of the lignin-derived products from softwood and hardwood treated in supercritical water

Softwood (Cryptomeria japonica) and hardwood (Fagus crenata) were treated in supercritical water (380°C, 100 MPa) for 8 s. The treated woods were fractionated to the water-soluble portion, methanol-soluble portion, and methanol-insoluble residues. For the methanol-soluble portion, which mainly consisted of lignin-derived products, gel permeation chromatography (GPC) and gas chromatographic-mass spectrometric (GC-MS) analyses were conducted to clarify the molecular weight distribution and to identify the monomeric products, respectively. GPC analysis revealed that the methanol-soluble portion contains monomeric and some oligomeric products. GC-MS analysis identified 19 guaiacyl compounds in the methanol-soluble portion from softwood, and 15 syringyl monomeric compounds in the methanol-soluble portion from hardwood. The structures of identified products included not only phenyl propane (C₆—C₃) units but also C₆—C₂ and C₆—C₁ units. In addition, the infrared spectra suggested that the methanol-soluble portion maintains the typical structure of lignin, although it is rich in condensed-type linkages with some changes in the propyl side chain. These results indicate that the supercritical water treatment cleaves not only ether linkages but also part of the propyl chains in lignin to give various aromatic compounds.