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     

Recent progress in the chemistry and topochemistry of compression wood

Summary A review of the chemistry and topochemistry of compression wood with 200 references. Compression wood contains on the average 30% cellulose, 35–40% lignin, 10% galactan, 9% galactoglucomannan, 8% xylan, and 2% of a 1,3-glucan (laricinan). The cellulose is less crystalline, and the xylan has fewer arabinose side chains than in normal wood. The lignin is composed of guaiacylpropane and p-hydroxyphenylpropane units. It is more condensed, has a higher proportion of carbon-carbon bonds, and contains fewer arylglycerol--aryl ether structures than a normal conifer lignin. The ray cells and the primary wall of the tracheids have the same chemical composition in normal and compression woods. The galactan is largely located in the outer region of the secondary wall. Only 5–10% of the lignin in compression wood tracheids is extracellular. The middle lamella is less lignified than in normal wood, while the S₁ and inner S₂ layers have a lignin concentration of 30–40% which is twice as high as in normal wood. The lignin content of the S₂ (L) layer is equal to or higher than that of the intercellular region along the wall. The review is concluded with a brief reference to areas where present information is incomplete or lacking.A portion of an Academy Lecture of the International Academy of Wood Science, presented at the International Symposium on Wood and Pulping Chemistry (Ekmandagarna 1981), held in Stockholm, Sweden, June 9–12, 1981. Reprints of the unabridged review, published under the title Recent Progress in the Chemistry, Ultrastructure, and Formation of Compression Wood in the preprints of the symposium (SPCI Report 38, Vol. 1, p. 99–147) are available from the author. I wish to express my gratitude to my colleague Professor Robert A. Zabel for generous travel assistance     

马尾松正常木与应压木木素结构的比较

采用紫外光谱、红外光谱、核磁共振波谱、凝胶渗透色谱和有机元素分析对从马尾松正常木与应压木中提取的纤维素酶酶解木素的结构进行比较研究。结果表明:马尾松正常木与应压木木素的芳香环结构主要以愈创木基为主,有少量的对羟基苯基;都含有较多的脂肪族羟基;与正常木木素相比,应压木木素含有较多的对羟基苯基单元和酚羟基,其中缩合酚羟基和对羟基酚羟基较多,还含有少量的紫丁香基酚羟基;应压木木素中的甲氧基、羧基、β-O-4键、β-5键,β-β键和β-1键较少;正常木与应压木木素的经验式分别为C9H7.27O1.53(OH)0p.H19(OH)1A.118(OCH3)1.23和C9H7.28O1.54(OH)0p.H20(OH)1A.117(OCH3)1.13。     

Isolation of lignin from spruce by acidolysis in dioxane

Summary Acidolysis of spruce wood (Picea abies) corresponded to a pseudo-first order reaction mechanism. While anhydrous methanolis a better medium for wood acidolysis than anhydrous dioxane, after addition of 10% water dioxane became about twice as effective as methanol. The results are discussed in terms of acidity functions (H), solubility parameters and condensation effects. Infrared spectra of dioxane lignins showed a similar re-arrangement of side chain carboxyl groups from to position, as was observed previously during acidolysis in methanol.     

On the distribution of the diastereomers of the structural elements in lignins: the steric course of reactions mimicking lignin biosynthesis

Summary Stereochemical studies on the formation of the diastereomers of arylglycerol--aryl ether structures during lignin biosynthesis have been carried out with model compounds. The addition of water to quinone methides of the -syringyl ether type gives arylglycerol -syringyl ethers with a predominance of the erythro isomer when the pH of the medium is low. Since erythro forms of arylglycerol -syringyl ethers are prevalent in hardwood lignins, this indicates that the pH of the medium in which lignin biosynthesis occurs is lower than has been assumed until now. Equilibration studies with non-phenolic model compounds of the arylglycerol-guaiacyl ether and -syringyl ether types under acidolysis conditions indicate that the erythro predominance observed in the syringyl ethers in lignins does not correspond to equilibrium conditions. A remarkable resistance to acidolysis is observed in the model compounds of etherified syringylglycerol -syringyl ether type.     

Lignin in woody tissues after chemical pretreatment and bacterial attack

Summary Tangential latewood sections (60 m) of Scots pine sapwood were differently treated with chlorite. The subsequently incubated two strains of Bacillus polymyxa caused a weight loss up to about 25%, including a loss of lignin of about 42%.UV-microspectrophotometry of 1 m-cross-sections prepared from the cultured woody tissues demonstrated that bacteria caused neither quantitative nor qualitative changes of the remaining lignin.The lignin, which was dissociated from the pretreated woody cell wall by bacteria, could not be respired, suggesting that the lignin is a ballast to these bacteria that inhibits the dissimilation of the carbohydrates in the wood.We appreciate the financial support by Deutsche Forschungsgemeinschaft. Thanks are due to Mrs. R. Endeward for her assistance during the microspectrophotometric evaluations and to Mr. U. Engel and Dr. O. Faix for carrying out the IR-measurements     

Structure of small lignin fragment retained in water-soluble polysaccharide extracted from sugi MWL isolation residue

In order to analyze the structural features of small lignin fragments that are closely associated to polysaccharides, lignin carbohydrate complex (LCC) with low lignin content was extracted with water from the residual wood meal (sugi, Cryptomeria japonica) of milled wood lignin (MWL) isolation. This LCC exhibited almost the same neutral sugar composition as those extracted by other LCC solvents (dimethylformamide, dimethylsulfoxide, and others) but the lignin content was only 5.3%, which was much lower than others. Gel filtration chromatography demonstrated that lignin in this LCC was found together with carbohydrates at the higher molecular weight region, but after the treatment with carbohydrate-degrading enzymes the apparent molecular weight of both lignin and carbo-hydrates decreased significantly. Using a mild alkaline treatment, the apparent molecular weight of lignin also decreased while that of polysaccharide was not affected. These data indicated that lignin in this LCC is present as small fragments attached to high molecular weight polysaccharide at least partly by alkali-unstable linkages. Structural analysis by ozonation method revealed that the lignin in this LCC was lower in erythro/threo ratio of -O-4 structure and relatively richer in the threo type structure carrying C-aryl linkages at -position (-5 and/or -1) than other lignin fractions present in MWL, LCCs extracted by other solvents, and their extraction residues. It was suggested that the chemical structure of lignin closely associated to carbohydrates was different from that of the main part of lignin.This paper was presented in part at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002, at the 47th Lignin Symposium, Gifu, Japan, October 2002, and at the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003     

The mechanism of the Mäule colour reaction introduction of methylated syringyl nuclei into softwood lignin

Summary Ezo spruce (Picea jezoensis) wood meal and milled wood lignin were successively reduced with sodium borohydride, methylated with methanol-HCl, oxidized with Fremy's salt, reduced with sodium dithionite, and methylated with diazomethane. Permanganate oxidation of the treated milled wood lignin showed that 0.08–0.1/C9 units of 3,4,5-trimethoxyphenyl groups were introduced into the softwood lignin. Although hardwood meal (beech, Fagus crenata) methylated with diazomethane gave a purple-red colour with the Mäule test, the treated softwood meal gave only a dark brown colour. The aromatic nuclei of lignin were broken down by the Mäule treatment. The consumption of permanganate by treated softwood lignin was higher than by hardwood lignin, which suggests that the guaiacyl nuclei were broken down severely. It is proposed that the purple-red colour obtained from methylated hardwood lignin with the Mäule colour test is generated by reaction of syringyl groups which were liberated by -ether cleavage under the permanganate oxidation conditions.     

Characterization of cellulose in compression and opposite woods of a Pinus densiflora tree grown under the influence of strong wind

Summary Structural factors in a Pinus densiflora tree grown under the influence of strong wind were measured. No difference for cellulose molecules was noticed between compression and opposite wood, but the was somewhat lower in the region where the compression wood was concentrated. The degree of crystallinity of cellulose was 45–50% in compression wood, about 50% in normal wood, and 50–60% in opposite wood. The crystallinity decreased with increasing height above the ground. The maximum point of crystallographic b-axis (fiber axis) orientation distribution for cellulose crystallites in compression wood was located at 30°, in normal wood at 25° and in opposite wood at 0°. The cellulose crystallite dimension in the transverse direction was 3.2 nm, corresponding to four cellulose unit cells, a value that was almost constant throughout the wood. In the longitudinal direction, there were large differences in cellulose crystallite dimensions between compression and opposite woods. In compression wood the cellulose crystallite dimensions was 12 nm corresponding to 11–12 cellulose unit cells. In opposite wood it was 17–32.5 nm corresponding to 17–32 cellulose unit cells. These structural factors were apparently affected by the environmental conditions, and the mechanical properties of the wood were influenced by these factors. Opposite wood had longer crystallites, a higher degree of crystallinity and a better orientation distribution of cellulose crystallites in the longitudinal direction. Compression wood, on the other hand, had shorter crystallites, a lower degree of crystallinity and a large angle between the stem and the direction of the crystallites.     

Analysis of the structure of lignin-carbohydrate complexes by the specific13C tracer method

In the present study the specifically¹³C-enriched lignin precursors of biosynthesis (i.e., coniferin-[side chain–¹³C], coniferin-[side chain-–¹³C] and coniferin-[side chain-–¹³C]) were synthesized and administered exogeneously to ginkgo shoots (Ginkgo biloba L.) to obtain¹³C-enriched lignin-carbohydrate complexes (LCCs). The specifically¹³C-enriched LCCs were isolated from the newly formed xylem of ginkgo shoots administered with the¹³C-enriched precursors and degraded by enzymes. Lignin-rich fractions, so called enzyme-degraded LCCs (EDLCCs), were obtained. By determining their¹³C-NMR spectra, information related to the chemical structure of lignin building units and linkages between phenylpropane units of lignin and carbohydrates were obtained. It was found that these precursors were incorporated in natural lignin successfully. Three lignin-carbohydrates linkages (i.e., ether type, ester type, ketal type) were found at the C -position of the side chain of phenylpropane units in ginkgo LCC. No lignin-carbohydrate bond at the C- or C-position of the lignin side chain was observed in the¹³C-NMR spectra of the¹³C-enriched LCCs. This fact indicates that a specific¹³C tracer technique can be useful in NMR study of the chemical structure of LCCs.Part of this paper was presented at the 5th Pacific Polymer Conference, Kyongju, Korea, October 1997     

A comparative study on stability and decay resistance of some environmentally friendly fire-retardant boron compounds

Environmental concern accelerated development of new wood preservatives having low mammalian toxicity in addition to high protective effectiveness. PHN 130 and PHN 130 G have been developed recently by KOHMIX Ltd. in Japan as environmentally safe, fire-proof boron containing compounds. Beyond their proved fire-proof properties, stability of loaded chemical in wood at humid service conditions and decay resistance are required to be known for effective and broad use of these compounds in wood preservation. Results indicated that PHN imparted complete decay resistance to wood against brown- and white-rot fungi Tyromyces palustris and Coriolus versicolor, respectively. Protection efficacy of PHN also continued despite severe weathering conditions provided that impregnation is done by an undiluted solution. PHN 130 G appeared more effective than PHN 130 in this respect. However, both compounds were leachable from treated wood regardless of retention level or physical restriction of water access into wood by compression.This revised version was published online in April 2005 with a corrected date of receipt of the article.

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Kinetics of acid-catalysed delignification of Eucalyptus globulus wood by acetic acid

Summary The kinetics of HCl-catalysed delignification of Eucalyptus globulus wood by 70% (w/w) acetic acid solution were satisfactorily explained by a model in which 5% of the lignin fraction could not be eliminated and the remaining 95% was eliminated by a single process which, in view of the activation energy calculated from the data was attributed to the hydrolysis of -aryl ether bonds. The selectivity of the process was effectively independent of HCl concentration and operating temperature for pulp yields >50%. At high temperature (160 °C) and catalyst concentration (0.027 MHCl), lignin condensation and precipitation became significant and the data were better fitted by a model comprising two consecutive processes: lignin solubilization followed by lignin condensation.The authors are grateful to the CICYT for financial support of this work (Project AGF93-0605) and also to the DGICYT for a research grant awarded to J. González     

Erythro/threo ratio ofβ-O-4 structures as an important structural characteristic of lignin. I: Improvement of ozonation method for the quantitative analysis of lignin side-chain structure

Ozonation as a quantitative tool to analyze the stereo structures of arylglycerol--aryl ether linkages was examined using wood meal, milled wood lignin, and a lignin model compound, 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol (veratrylglycerol--guaiacyl ether, VG). The procedure was improved. When mild postreduction was conducted for ozonation products, the total yield of erythronic and threonic acids from this model compound was 74%, which is 15% higher than the yield without postreduction. A decrease in the recovery of these two acids under prolonged ozonation treatment was successfully suppressed by postreduction. Theerythro/threo ratio of VG determined by the ozonation method with postreduction is in good agreement with the ratio determined by¹H-nuclear magnetic resonance. Excellent reproducibility of the yield was obtained by adopting a procedure that included trimethylsilylation of ammonium salts of ozonation products using a dimethylsulfoxide-hexamethyldisilazane-trimethylchlorosilane mixture and subjecting it to gas chromatography analysis. It was concluded that arylglycerol--aryl ether structures comprise at least 35% of the C₃-C₆ structure in birch wood meal, with anerythro/threo ratio of 2.8.This paper was presented at the 43rd Lignin Symposium, Fuchu, Japan, October 1998; and at the 10th ISWPC, Yokohama, Japan, June 1999     

Chemical aspects of kraft pulping

Summary Kraft pulping is interpreted in chemical terms on the basis of results from extensive qualitative and quantitative model experiments. In essence, the behavior of lignin is explained as a competition between degradation reactions, mainly involving aryl ether cleavage with participation of neighboring groups, and condensation reactions, comprising conjugate addition of carbanions to quinone methide intermediates. The initial phase of technical delignification is tentatively ascribed to the cleavage of - and -aryl ether bonds in phenolic lignin units, whereas the cleavage of -aryl ether bonds in non-phenolic lignin units is considered to be the rate-determining reaction of the bulk phase. The residual phase may possibly be attributed to the rupture of C-C linkages and to aryl ether cleavage without neighboring group participation. Experimental support for these correlations is provided. The interplay of the various lignin reactions, illustrated in a summarizing scheme, explains some known observations in kraft pulping.Attention is drawn to analogies between reactions involved in the degradation of carbohydrates and those reponsible for the degradation of lignin. From the chemical standpoint, therefore, the selectivity of delignification is due to differences in the reactivity of the wood polymers, rather than to differences in the mechanisms of the degradation reactions. This fact explains the limitations of selective delignification.Parts of this work have been reported at the Fifth Planary Meeting of the International Academy of Wood Science on Copenhagen, Denmark, June 19, 1976, and at the ACS meetings in Appleton, Wisc., May 17–19, 1978, and Honolulu, Hawaii, April 1–6, 1979     

14C-Lignin degradation by three Australian termite species

Summary The termites Nasutitermes exitiosus (Hill), Coptotermes acinaciformis (Froggatt), and Mastotermes darwiniensis Froggatt were examined for their ability to degrade lignin. Several ¹⁴C-(lignin)-lignocelluloses labelled in the 3 side chain position were prepared by infusing plant stems for seven days with the lignin precursor, ¹⁴C-cinnamic acid. Based on acid and alkali solubilites, the lignin precursor was more deeply incorporated into the lignin polymer than usually reported for ¹⁴C-(lignin)-lignocellulose preparations. N. exitiosus was able to degrade a ¹⁴C-(U-ring)-synthetic lignin (5% breakdown) and the lignin component of certain hardwood ¹⁴C-(lignin)-lignocelluloses (about 4–6.5% breakdown), but not the lignin component of softwood ¹⁴C-(lignin)-lignocellulose. Both C. acinaciformis and M. darwiniensis were less able to degrade any of the ¹⁴C-lignins than N. exitiosus. The difference may be due to their possessing different types of gut symbionts. Most of the degradation by N. exitiosus took place during the first week of the 14 day bioassays. Very low amounts (0.03–0.21%) were degraded in the faeces.The author wishes to thank Dr. J. R. J. French and Dr. G. Ettershank for their helpful advice during the work, Dr. T. K. Kirk for his generous gift of synthetic lignin, and J. W. Creffield for collecting the lower termites. E. Longmore and P. J. Pahl provided advice on statistical analysis     

Ozonation of a lignin-carbohydrate complex model compound of the benzyl ether type

Evidence for the presence of lignin-carbohydrate bonds of the benzylic ether type in wood and pulps may be obtained by use of ozonation treatment to selectively degrade the lignin. It was found that the benzyl ether bond in 3-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxy-phenoxy)-3-(methyl--d-glucopyranosid-6-O-yl)-1-propanol was rather stable during ozonation in acetic acid-water-methanol 1631 at 0°C. The corresponding acid, 3,4-dihydroxy-2-(methyl--d-glucopyranosid-6-O-yl)-butanoic acid, was found to be the major reaction product. The use of ozonation followed by acid hydrolysis in connection with studies of lignincarbohydrate linkages is briefly discussed.Part of this paper was presented at the 10th ISWPC, Yokohama, 1999     

Quantitative analysis of lignin using an UV microscopic image analyser. variation within one growth increment

Summary The variation of the lignin content within one growth increment of Abies sachalinensis was investigated with the aid of an ultraviolet microscopic image analyser. The lignin content was determined continuously in each cell within a growth increment. The direct photometric scanning method of UV image is believed to give accurate results for determination of the lignin content of the cell wall, since it contains fewer assumptions. The lignin content of the earlywood was higher than that of latewood in adult wood as same as the others. It was high, however, in the terminal zone of the latewood. The trends of the juvenile wood were quite different from those of the adult wood. The lignin content increased from earlywood to latewood.This paper was presented at the Wood Anatomy Congress of IAWA, Aug. 27, 1979, Amsterdam. The authors wish to express their gratitude to Prof. Dr. J. Bauch for helpful advice     

Characterization of Brauns’ lignin from fresh and vacuum-dried birch (Betula pendula) wood

Brauns’ lignins present in the methanol extracts of fresh birch (Betula pendula) xylem and of sawn birch board subjected to vacuum drying were characterized by ¹H and ¹³C NMR spectroscopy (1D and 2D), IR spectroscopy, gel permeation chromatography (GPC) and colour measurements (CIELab) in order to find out whether Brauns’ lignin could contribute to the colour change of sawn timber that occurred during vacuum drying. The two Brauns’ lignin samples contained about equal amounts of syringylpropane and guaiacylpropane units linked with β-O-4 and β–β side-chain structures. Molecular weight of the Brauns’ lignin of vacuum-dried birch board (acetylated: 5,200 g mol⁻¹) was higher than that of the Brauns’ lignin of fresh birch wood (acetylated: 4,400 g mol⁻¹). The Brauns’ lignin of vacuum-dried wood was also clearly darker and more prominently yellow and red; between the Brauns’ lignin samples was 23.59. The differences in the molecular weights and colours suggest that the Brauns’ lignin underwent a chemical change during vacuum drying of the wood and that this change may have affected the colour of the wood.     

Bromination of different morphological parts of spruce wood (Picea abies)

Summary It has been found that the lignin in a middle lamella fraction isolated by a sieving technique has the same reactivity to bromine as the whole wood lignin. A plataue value of 1 mole bromine/mole C₉-unit was obtained for both samples. The lignin in compression wood had a considerably lower reactivity to bromine than the normal wood lignin. A plataue value of 0.68 mole bromine/mol C₉-unit was obtained with such lignin. The discrepancy between this and earlier results from the bromination of middle lamella and the implication of the results for lignin determination by the SEM- and TEM-EDXA technique are discussed.     

The reaction of guaiacol with iron III and chromium VI compounds as a model for wood surface modification

Summary The reaction of ferric chloride with the lignin model guaiacol affords primarily a complex mixture of coupled guaiacol oligomers. Major components were the symmetrical carbon-carbon coupled dimer 3,3-dimethoxy-[1,1-biphenyl]-4,4diol and the trimer 3,3,5-trimethoxy-[1,1:3,1-terphenyl]-4,4,4-triol which were isolated by preparative HPLC and characterized by ¹HNMR spectroscopy and mass spectrometry. An unstable component believed to be a 4,4-diphenoquinone derived from the trimer was also prominent. The reaction of chromium trioxide with guaiacol yields the same dimer, trimer and diphenoquinone as well as 2-methoxy-p-benzoquinone. The major product with chromium trioxide, however, is an inert, highly insoluble polymer which was shown by degradation to contain guaiacol oligomers bound or crosslinked by hydroxylated chromium species. Magnetic susceptibility measurements clearly indicated that the valency of chromium in the polymer was + 3. It is postulated that similar complexes formed from phenolic lignin units are responsible for the weather resistance of chromium trioxide treated wood surfaces. In a broader context this study is relevant to the fixation of hexavalent chromium from a range of widely used wood preservative formulations.The authors wish to thank the following: Tom Syers (CSIRO Division of Forest Products) for technical assistance, Mary Reilly (CSIRO Division of Forest Products) for NMR spectral determinations and Ivan Vit (CSIRO Division of Chemicals and Polymers) for mass spectral determinations