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1.
Lignin biochemistry: Biosynthesis and biodegradation 总被引：22，自引：0，他引：22
Prof. T. Higuchi 《Wood Science and Technology》1990,24(1):23-63
Summary Lignin biosynthesis via shikimate-cinnamate pathways in plants, and the biosynthetic differences of guaiacyl-and syringyl lignins between gymnosperms and angiosperms have been elucidated by tracer experiments using 14C labeled precursors and the following enzyme reactions. The formation of guaiacyl lignin but not syringyl lignin in gymnosperms was attributed to the following factors; absence of ferulate-5-hydroxylase, poor affinity of O-methyltransferase toward 5-hydroxyferulate, and lack of activation and/or reduction of sinapatc. A mechanism of lignin-carbohydrate complexes formation in wood cell walls was elucidated based on the reaction of the quinone methide of guaiacylglycerol--guaiacyl ether with sugars, and the analysis of DHP-polysaccharide complexes.The main cleavage mechanisms of side chains and aromatic rings of lignin model compounds and synthetic lignin (DHP) by white-rot fungi and their enzymes, lignin peroxidase and laccase have been elucidated using 2H, 13C and 18O-labeled lignin substructure dimcrs with 18O2 and H2
18O. Side chains and aromatic rings of these substrates were cleaved via aryl cation radical and phenoxy radical intermediates, in reaction mediated only by lignin peroxidase/H2O2 and laccase/O2.Academy Lecture presented at the Cellucon 88 in Japan, International Symposium on New Functionalisation Developments in Cellulosics and Wood, held in Kyoto, Japan, November 28 to December 1, 1988This paper is a conclusion of our investigations on the biosynthesis and microbial degradation of lignin for 30 years in the Research Section of Lignin Chemistry, Wood Research Institute, Kyoto University. The author is greatly indebted to Drs. M. Shimada, F. Nakatsubo, T. Yamasaki, H. Ohashi, M. Tanahashi, Y. Nakamura, H. Kuroda, H. Kutsuki, T. Katayama, Y. Kamaya, T. Umezawa and Messrs. H. Fushiki, M. Ohta, A. Noguchi, H. Namba, T. Habe, S. Kawai, S. Yokota, and T. Hattori for their kind cooperation in these investigations. These invstigations were supported in part by Grant-in-Aid Nos. 548047, 57480058, 59760124, 60760130, 60440015, 61760142, 61560193, 62790250 for Scientific Research, and 1980 Grant-in-Aid for Environmental Science (R-33-8), No. 403064 from the Ministry of Education, Science and Culture of Japan, and a 1980 Weyerhaeuser grant 相似文献
2.
3.
Summary Metabolic differences in the formation of guaiacyl and syringyl lignins were explained in terms of the different functions of O-methyltransferases and reducing enzymes which participate in methylation and reduction of the hydroxycinnamic acid intermediates in the biosynthetic pathway of these two types of lignins. Sinapyl alcohol was dehydrogenated with peroxidase and H2O2 under various reaction conditions. Chemical properties of the dehydrogenation polymers (DHPs) formed were characterized, and the possible occurrence of syringyl lignin in hardwood was discussed. DHP and dimers of p-coumaryl alcohol were also characterized and discussed in relation to the formation of grass lignin which contains p-hydroxyphenyl propane as an additional lignin monomer.The authors are indebted to Messrs. Y. Nakamura and H. Kuroda in this Division and Mr. T. Yamasaki at Kagawa University for their cooperation in the course of these investigations 相似文献
4.
Summary The objectives of this work were to begin developing an experimental system for studying the demethylation of lignin by brown-rot fungi and to examine the influence of selected culture parameters. As substrate for demethylation, we used partially 3-O-demethylated lignin that had been isolated earlier from brown-rotted spruce wood; we remethylated with14CH3I, giving a lignin with both [3-14C]methoxyl and [4-14C]methoxyl groups. This lignin was added to pine wood flakes, which were incubated with selected brown-rot fungi, and the evolved14CO2 was trapped and measured. Of eight fungi examined,Gloeophyllum trabeum andWolfiporia cocos gave the highest rates of mineralization of the14C-methoxyl carbons. With the former but not the latter fungus, methoxyl mineralization was over twice as fast in an atmosphere of O2 than in air. Amending the cultures with ammonium tartrate suppressed mineralization to some extent. Further studies withG. trabeum showed that glutamate lowered the rate of mineralization and that glucose and glycerol sharply suppressed it. Addition of Fe2+ and Mn2+ slightly increased the rate of mineralization. Our results suggest that in unsupplemented cultures the rate-limiting step in methoxyl mineralization is the initial demethylation. Thus the two likely initial C1 products, methanol and formaldehyde (as14C compounds), were mineralized much more rapidly than the methoxyl carbon of the lignin (as was formic acid), and no low molecular weight labeled intermediates from the [14C]-methoxyl lignin accumulated in the cultures. Our results also provide evidence that the spruce lignin was partially polymerized byG. trabeum. Mineralization of the methoxyl carbon of a synthetic [3-14C]-methoxyl lignin was slower than that of the spruce lignin, suggesting either that the synthetic lignin was more recalcitrant or that the [4-14C]methoxyl group in the [3,4-14C]-methoxyl spruce lignin was attacked more readily.We thank Karen L. Martinson and Michael D. Mozuch for excellent technical help, and Tor P. Schultz for valuable suggestions. This research was supported in part by the U.S. Department of Agriculture, Wood Utilization Research Program, Project No. 350-0612, to Mississippi State University.The Forest Products Laboratory is maintained in cooperation with the University of Wisconsin. This article was written and prepared by U.S. Government employees on official time, and it is therefore in the public domain and not subject to copyright in the United States. 相似文献
5.
Norway spruce dust was impregnated with aqueous solutions of chromated copper wood preservatives. Immediately after treatment,
observation of CO2 evolution and O2 consumption were performed. Significant quantities of CO2 were released during reaction of chromium (K2Cr2O7) containing solutions with wood or brown rotted wood. Nevertheless, during reaction of cellulose with these preservatives
we did not observe evolution of CO2. The presence of copper did not influence on concentration of CO2. Opposite to CO2 evolution, treatment of wood and brown rotted wood resulted in O2 consumption. The oxygen concentration decrease in the measuring chamber was approximately 5 times greater than increase of
concentration of carbon dioxide. Electron paramagnetic resonance (EPR) observations of chromium fixation showed that chromium
is reduced from Cr(VI) to Cr(III) with Cr(V) as an intermediate on wood, brown rotted wood and cellulose. However, the reduction
on wood and brown rotted wood was faster than the reduction on cellulose, as determined from changes of Cr signals in EPR
spectra. So, evolution of CO2 and consumption of O2 as well as EPR signals of Cr species thus indicate that brown rotted wood, consisting of lignin and hemicelluloses in contact
with Cr(VI) reacts more intensively than cellulose, and possibly, oxidation mechanisms of lignin and cellulose with Cr(VI)
are different.
Received: 20 July 2000 相似文献
6.
7.
Summary To elucidate biochemical features leading to p-hydroxyphenyl-rich lignin in gymnosperm reaction wood the activities of the following five enzymes involved in the biosynthesis of p-hydroxyphenyl lignin were compared in reaction and opposite woods: phenylalanine ammonialyase (EC 4.3.1.5), cinnamate 4-hydroxylase (EC 1.14.13.11), p-hydroxycinnamate: CoA ligase (EC 6.2.1.12), cinnamyl alcohol dehydrogenase (EC 1.1.1.-) and peroxidase (EC 1.11.1.7). The enzyme activities in the reaction woods of Thuja orientalis and Metasequoia glyptostroboides were remarkably higher than those in the opposite woods, reflecting the higher contents of p-hydroxyphenyl lignin in reaction wood.This work was partly supported by the Grant-in-Aid for Scientific Research (548047) from the Ministry of Education, Science and Culture of Japan. We thank the Ministry of Education for the support 相似文献
8.
《Wood material science & engineering》2013,8(4):209-216
Abstract To investigate the role of extractives on heat-induced discoloration of wood, samples of black locust (Robinia pseudoacacia) wood flour were extracted with various solvents prior to heat-treatment. Analysis of their color parameters and chromophoric structures showed that the chroma value of the unextracted sample decreased while that of the extracted sample increased after heat-treatment. Both samples showed broad diffuse reflectance UV-Vis (DRUV) absorption bands with maxima around 360–380 nm after heat-treatment due to the formation of conjugated double bonds, carbonyl functionalities, and quinoid structures. Compared with the unextracted sample, the dominant chromaticity of the extracted samples hypochromatically shifted and the peak became narrower. This result showed that extractives contribute mostly to the reduction in the light reflection on heat-treated wood. In addition to extractives, lignin and hemicellulose also contributed to the formation of color substances upon heat-treatment. The increase in C3/C2 ratio in X-ray photoelectron spectroscopy (XPS) spectra signified the oxidation reactions in the heating process. The increase in O1/O2 for extracted sample after heat-treatment and changes in DRUV and Fourier transform infrared spectroscopy (FTIR) spectra support the hypothesis that discoloration can also arise from the degradation of hemicellulose and the condensation reactions of lignin. 相似文献
9.
Hiroto Homma Hirofumi Shinoyama Yukihiro Nobuta Yoshie Terashima Seigo Amachi Takaaki Fujii 《Journal of Wood Science》2007,53(1):80-84
Strobilurus ohshimae is an edible mushroom, and it specifically forms its fruiting bodies on buried sugi (Cryptomeria japonica) twigs. In this research, we studied lignindegrading activity of S. ohshimae. We isolated 18 strains of S. ohshimae from various regions of Japan, and determined their lignin degradation rates on sugi wood meal medium. All the strains of
S. ohshimae degraded approximately 6%–12% of sugi lignin in 30 days, and these lignin degradation rates were 1.5–3 times higher than those of Trametes versicolor, which is a typical lignin-degrading fungus. Among the three main lignin-degrading enzymes, activity of lignin peroxidase
and manganese peroxidase was not observed, while 4340U/g of laccase was produced in 30 days. To investigate the effect of
wood species on lignin degradation by S. ohshimae, the lignin degradation rate and laccase productivity on sugi wood meal medium were compared with those on beech (Fagus crenata). In T. versicolor, both lignin degradation rate and laccase productivity were higher on beech than on sugi. Conversely, in S. ohshimae, lignin degradation rate and laccase productivity were higher on sugi than on beech. Therefore, it was suggested that coniferous lignin is not always difficult to degrade for the fungi that inhabit
softwood.
Part of this article presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, August 2004 相似文献
10.
Lin Shanzhi Zhang Zhiyi Lin Yuanzhen Liu Wenfeng Guo Huan Zhang Wei Zhang Chong 《中国林学(英文版)》2004,6(3):1-8
To explore the physiological and biochemical mechanism of the occurrence of vitrified shoots of Populus suaveolens in tissue culture, the changes in water, chlorphyll, lignin, H2O2, phenylalanine ammonialyase (PAL), malonaldehyde (MDA), protective enzymatic systems, and some key enzymes involved in the
ascorbate- glutathione cycle were comparatively studied in both normal and vitrified shoots of P. suaveolens. The results show that the lower activities of peroxidase (POD), catalase (CAT), ascorbate peroxidase (APX), dehydroascorbate
reductase (DHAR), glutathione reductase (GR) and PAL, and the less contents of chlorphyll, lignin, ascorbate (ASA) and reduced
glutathione (GSH) as well as the lower ratios of ASA / DHA and GSH / GSSG are observed in vitrified shoots than in normal
ones during the whole culture period. While in comparison with normal shoots, the higher activity of superoxide dismutase
(SOD) and the more concentrations of water, H2O2, MDA, dehydroascorbate (DHA) and oxidized glutathione (GSSG) are found in vitrified shoots. Statistical analysis indicates
that the enhanced activity of SOD and the decreased activities of CAT and POD as well as some enzymes involved in the ascorbate-glutathione
cycle might be closely correlated to the accumulation of H2O2. The less regeneration of ASA and GSH and the lower capacity of the ascorbate-glutathione cycle observed in vitrified shoots
might be due to a significant decrease in APX, MDAR, DHAR and GR activities and a decline in redox status of ASA and GSH.
The decreases in chlorphyll content might result in a decline in photosynthesis. The lower activities of POD and PAL could
result in the decrease of lignin synthesis and cell wall ligination, which might be the key factor leading to the increase
in water content. It is concluded that the deficiency of detoxification capacity caused by the lower capacity of the ascorbate-glutathione
pathway and the decreased activity of protective enzymatic system might lead to the large accumulation of H2O2 and the enhancement of membrane lipid peroxidation, which might be the main cause leading to the occurrence of vitrifying
shoots of P. suaveolens in tissue culture.
[Supported by National Natural Science Foundation of China (Grant No. 30271093) and the Foundation of State-designated Base
for Biology Researching and Teaching in Beijing Forestry University] 相似文献
11.
Summary
13C CP MAS NMR spectroscopy was used to characterize the structural changes of cell wall polymers in beech wood Fagus sylvatica during drying processes. The analysis of five wood samples, namely, untreated, untreated dried, pre-treated by steam and/or
NaOH subjected to drying showed partial depolymerization of lignin component as well as the change of the ratio of the crystalline
and of the amorphous parts of cellulose as the consequence of wood pre-treatment. In addition, T1ρ(1H) relaxation times were determined in beech wood sample pre-treated with steam at 135 °C and the lignin isolated from this
sample. The magnitudes of the relaxation times were found comparable in both samples as well as in the lignin-cellulose model
compound. These unique T1ρ (1H) values indicate that spin diffusion is complete and homogeneous due to spatial proximity of spins and confirmed the formation
of lignin-cellulose complex during thermal treatment of wood.
Received 30 June 1997 相似文献
12.
Summary The one-electron oxidation activity of brown-rot fungi was determined by measuring ethylene production from KTBA. Ethylene
production was related to degradation of lignin, cellulose, and wood itself. Extracellular protein that catalyzed oxidation
of KTBA was isolated from wood-containing cultures. This protein required H2O2 for KTBA oxidation. It was also found to oxidize NADH, producing H2O2 via
in the presence of O2. The protein showed little phenol-oxidase activity under conditions giving high activity against KTBA. The results indicate
that partially reduced oxygen may play a role in the initial degradation of the cellulose and lignin in wood in cultures of
brown-rot fungi. 相似文献
13.
Wataru Aoyama Akira Matsumura Yuji Tsutsumi Tomoaki Nishida 《Journal of Wood Science》2001,47(6):419-424
Seedlings ofEucalyptus viminalis were grown for 50 days with their stems bent so tension wood would form. Every 10 days the lignin content, monomeric composition, and peroxidase activity in the tension wood were compared with those in the lower side (opposite wood) and in vertically grown controls. The lignin content in the developing tension wood started to decrease after 10 days of bending and kept decreasing for 50 days, whereas those in control plants and opposite wood remained almost unchanged. The yields of syringaldehyde from tension wood by nitrobenzene oxidation increased, and consequently the syringyl/ guaiacyl ratio of the lignin was higher in tension wood than in opposite wood and control plants. The peroxidase ionically bound to the cell walls (IPO) catalyzed oxidation of guaiacol and syringaldazine. The syringaldazineoxidizing activity of IPO from tension wood increased, whereas the activities of IPO from opposite wood and control plants did not show any marked change. In tension wood the increase in syringaldazine-oxidizing activity of IPO was consistent with an increase in the syringaldehyde yield. This suggests that IPO contributes to syringyl lignin deposition as other enzymes involved in the monolignol biosynthesis do in tension wood formation.This study was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000 相似文献
14.
Summary Thermogravimetry-mass-spectrometry (TGMS) as a sophisticated analytical instrument is described for the thermal analysis of milled wood lignins from spruce (Picea abies L.), beech (Fagus sylvatica L.) and bamboo (Bambus sp.). The samples were heated on the thermobalance in an inert gas atmosphere (Ar) with 20°C/min heating rate. The weight loss curves (TG) and their 1st derivatives (DTG) were recorded. The evolution of 10 low mass degradation products with m/z below 44 was monitored as a function of the temperature by means of a quadrupol mass spectrometer. Thus the intensity profiles of H2, CH3
, H2O, CO, CHO, HCHO, CH3O, CH3OH, CH3CO and CO2 were recorded and interpreted in terms of lignin structure and the course of carbonization. The results are in agreement with the results of differencial scanning calorimetry (DSC) and pyrolysis-gas-chromatography mass-spectrometry (PyGCMS) of the phenolics. 相似文献
15.
Lignin characteristics of bast fiber and core in kenaf, bark and wood of paper mulberry and mulberry
The structural features of bast fiber and core lignins in kenaf (Hibiscus cannabinus), bark and wood lignin of paper mulberry (Broussonetia papyrifera (L.) Vent × Broussonetia kazinoki Sieb.) and mulberry (Morus bombycis) were characterized by alkaline nitrobenzene oxidation, ozonation and methoxyl group determination. Bj?rkman lignins were
isolated from bast fiber and core, and bark and wood fractions of the plant samples, and structural characteristics were investigated
by 1H NMR and 13C NMR spectroscopies. Kenaf bast fiber gave very high molar ratio of syringaldehyde to vanillin (S/V) of alkaline nitrobenzene
oxidation products, while methoxyl content was about the same as that of the core fraction. Results of 1H NMR and 13C NMR of Bj?rkman lignin suggested the presence of aliphatic fragments in lignins isolated from paper mulberry and mulberry
bark, but not in kenaf bast fiber. The lower yield of alkaline nitrobenzene oxidation products from bast fiber and bark might
be due to the higher content of condensed structure of lignin compared to core fraction. Total yield of erythronic (E) and threonic (T) acids of ozonation products and the molar ratio of erythronic acid to threonic acid (E/T) of the bast fibers and bark were lower than the corresponding core and wood fractions, suggesting that the contents of arylglycerol-β-aryl
ether intermonomer linkages in the bast fiber and bark lignin were lower than those of the core and wood fractions. Methoxyl
content of bark lignin was lower than the corresponding wood lignin. The methoxyl content of the extract-free kenaf bast fiber
was similar to that of the core fraction, while the values of paper mulberry and mulberry bark were about one-half of the
corresponding wood fractions, respectively. In bark lignins, the methoxyl contents of Klason lignin and Bj?rkman lignin from
bark were lower than those of the extract-free barks. This result suggests that the purity of Klason lignin and Bj?rkman lignins
of bark may be rather low. 相似文献
16.
Summary The formation of lignin in the cell wall of compression wood of Pinus thunbergii was examined by selective radio-labeling of specific structural units in the lignin and visualization of the label in the different morphological regions by microautoradiography. Deposition of lignin in the tracheid cell wall of compression wood occurred in the order: p-hydroxyphenyl, guaiacyl and syringyl lignin, which is the same order as observed in normal wood. However, the period of lignification in the compression wood was quite different from those of normal and opposite woods. The p-hydroxyphenyl units were deposited mainly in the early stage of cell wall formation in compound middle lamella in normal and opposite woods, while in compression wood, they were formed in both the compound middle lamella and the secondary wall. The most intensive lignification was observed during the formation of the S2 layer, proceeding from the outer to inner S2 layers for a long period in compression wood. In the normal or opposite woods, in contrast, the lignification became active after formation of S3 had begun, then proceeded uniformly in the secondary wall and ended after a short period.A part of this report was originally presented at the 1989 International Symposium on Wood and Pulping Chemistry at Raleigh, NC, U.S.A. 相似文献
17.
Yoshihiro Katayama Yoko Mashino Nobuyuki Nishikubo Kaori Yoshitomi Ryo Funada Shinya Kajita 《Journal of Wood Science》2002,48(6):457-466
We have investigated the spatial regulation of the accumulation of enzymes involved in the biosynthesis of shikimate and lignin during differentiation of primary xylem from the apical meristem via procambium in hybrid aspen (Populus sieboldii x Populus grandidentata). Immuohistochemical staining revealed that, in the top part of shoots, lignification began in a single or just a few adjacent vessel elements and subsequently spread to neighboring cells. The spatial localization of 3-deoxy-D-arabino-heptulosonate 7-phosphate synthase (DAHPS), which is one of the key enzymes in the shikimate pathway, was tightly correlated with the cell-specific deposition of lignin in the primary xylem. We also found that the spatial localization of enzymes in the general phenylpropanoid pathway and in the lignin-specific pathway was closely associated with the cell-specific deposition of lignin and the accumulation of DAHPS. Our data suggest that enzymes that act in the shikimate, general phenylpropanoid, and lignin-specific pathways are initially produced and function coordinately in a single or a few adjacent elements at the start of primary xylem development. 相似文献
18.
T. E. Timell 《Wood Science and Technology》1973,7(3):163-172
Summary The distribution of lignin in opposite wood has been studied by removing the polysaccharides with hydrofluoric acid and examining the resulting lignin skeletons in the electron microscope. The thick S3 layer was more highly lignified than the S1 and S2 layers in Abies balsamea, Picea rubens, Pinus resinosa, and Tsuga canadensis. In Picea rubens, but not in the other species, there was, adjacent to the S3 layer, a transition zone in S2 with a high concentration of lignin. The S3 layer varied considerably in thickness and was often buckled, especially in the latewood. The structure of the bordered pits was that observed in the original wood. The margo, the torus, and the initial pit border were all highly lignified.This paper is dedicated to Dean Edwin C. Jahn in honor of his 70th birthday. 相似文献
19.
Wood, macromolecular and simple model compounds, were reacted with CrO3 or K2CrO4 aqueous solutions. Extracted lignin, guaiacol, vanillin, vanillyl alcohol and homovanillyl alcohol were chosen as model compounds for lignin, whilst cellulose, gum Ghatti, xylan, extracted hemicellulose from pine, methyl-β-D-glucopyranoside and methyl-β-cellobioside were used as models for wood polysaccharides. The kinetics of the reduction reactions of Cr(VI) were monitored using UV-Vis spectroscopy and the results obtained for several temperatures are discussed. In general terms, wood, lignin and lignin model compounds reduced Cr(VI) faster and to a greater extent than polysaccharides or simple sugar molecules. Moreover, lignin model compounds were reduced even faster than lignin. Simple sugars showed a reduction pattern similar to that of cellulose. Extracted hemicellulose revealed to be a poorer reductant while gum Ghatti was the strongest among the polysaccharides. As expected, CrO3 aq. behaved as a more powerfull oxidant than K2CrO4 aq. for these substances. Even at 100 °C, sugars or polysaccharides did not seem to be oxidised by K2CrO4 aq. 0.01 M. These results suggest that, because of the differences in reactivity, lignin reacts preferentially when wood is treated with Cr(VI)-containing formulations, like those which are applied in wood preservation treatments. 相似文献
20.
Participation of lignin in the reaction between vapor-phase formaldehyde and wood was examined by using gradually delignified
wood meal. A fi rst-order rate equation was successfully applied to the weight gain data. From the estimated reaction parameters
such as rate constant, k, and ultimate weight gain, a, the reactivity toward formaldehyde was discussed among wood components, and compared with that for acetylation. k decreased monotonously with progress of the elimination of lignin, suggesting that the reaction rate of lignin is dominant
over that of whole wood, and the decrease in the ratio of lignin retarded the reaction of wood as a whole. On the other hand,
a increased with decreasing lignin content. This may be attributable to the enhanced reactivity of the remaining lignin due
to some structural changes and to the increase in the number of reactive sites in polysaccharides as a result of their exposure
accompanying the elimination of lignin. The dependencies of k and a on the lignin content were not similar to the case for acetylation, probably because of the difference in the reaction phase.
In vapor-phase formaldehyde treatment, the remaining lignin reacts as it is, whereas in liquid-phase acetylation it would
undergo rearrangement or swelling of the structure in the reaction solution. 相似文献