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1.
Sphingomonas paucimobilis SYK-6 produces unique and specific enzymes, such as-etherases,O-demethylases, and ring fission dioxygenases, for lignin degradation. Cleavage of arylglycerol--aryl ether linkage is the most important process in the lignin metabolic pathway ofS. paucimobilis SYK-6. We reported the genes (ligD, ligE, ligF) for enzymes that cleaved-aryl ether linkage of dimeric compounds in previous studies. In this study we synthesized the fluorescent high-molecular-weight lignin (UBE-DHP) by dehydrogenative polymerization. We investigated the-aryl ether cleavage ability of these enzymes produced in recombinantEscherichia coli. When UBE-DHP was incubated with LigF, 4-methylumbeliferone was released as a result of-aryl ether cleavage of O-methylumbelliferyl--hydroxypropiovanillone (compound III) incorporated in UBE-DHP. Here, we report that-etherase ofS. paucimobilis SYK-6 can be expressed inE. coli and is able to cleave the-aryl ether linkage in synthetic high-molecular-weight lignin.  相似文献   

2.
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.  相似文献   

3.
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  相似文献   

4.
Chemically synthesized (1 5)--d-glucofuranan, (1 5)--d-galactofuranan, (1 5)--d-xylofuranan, (1 5)--L-arabinofuranan, natural xylan, and curdlan were sulfated to investigate their inhibitory activities on B16-BL6 lung metastasis and anticoagulant activities. (1 5)--d-Glucofuranan sulfate, (1 5)--d-galactofuranan sulfate, xylan sulfate, and curdlan sulfate had binding abilities with B16-BL6 melanoma lysate. The inhibitory activities of sulfated polysaccharides on B16-BL6 lung metastasis selected by heparin binding assay were in the order (1 5)--d-galactofuranan sulfate > (1 5)---d-glucofuranan sulfate > xylan sulfate curdlan sulfate. Furthermore, (1 5)--d-galactofuranan sulfate, (1 5)--d-glucofuranan sulfate, and xylan sulfate had not only high inhibitory activity on B16-BL6 lung metastasis but also low anticoagulant activity. The correlation between chemical structure and biological activity is discussed.Part of this paper was presented at the 10th International Synposium on Wood and Pulping Chemistry, Yokohama, Japan, June 1999  相似文献   

5.
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.  相似文献   

6.
Large-scale microwave rapid pyrolysis of cellulosic materials has been investigated. Levoglucosan (1,6-anhydro--d-glucopyranose) was obtained from a larch log as the main anhydrosugar in 2.6% yield on the basis of dry wood weight. This yield would be much higher than that obtainable by conventional pyrolysis in the largescale reaction. Levoglucosenone (1,6-anhydro-3,4-dideoxy--D-glycero-hex-3-enopyranos-2-ulose) was found to be produced in one-quarter the amount of levoglucosan. Other anhydrosugars, such as mannosan (1,6-anhydro--D-mannopyranose), galactosan (1,6-anhydro--d-galactopyranose), and xylosan (1,4-anhydro--d-xylopyranose), were also confirmed to be produced as minor components depending on the proportion of the monosaccharide content in the larch. When microwave pyrolysis of used papers and filter papers was performed, the yields of levoglucosan were about 6% and 12%, respectively, suggesting that a higher content of cellulose gives a larger amount of levoglucosan.  相似文献   

7.
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  相似文献   

8.
When (±)--oxo-guaiacylglycerol--(vanillic acid) ether (1) is degraded byFusarium solani M-13-1, the-ketone is initially reduced to giveerythro andthreo guaiacylglycerol--(vanillic acid) ethers (2), arylglycerol--aryl ethers, both of which are enantiomerically pure. The absolute configuration in each2 was determined by Mosher's method; the products were converted to,-di-(R)--methoxy--trifluoromethylphenylacetates (MTPA esters) (3) oferythro (-)- andthreo (+)-veratrylglycerol--(methyl vanillate) ethers (3), whose1H nuclear magnetic resonance (NMR) spectra were examined and compared with those of four di-(R)-MTPA ester (3) diastereomers from chemically synthesizederythro (±)-3 andthreo (±)-3. To assign the- and-MTPA-OCH3 peaks, the1H NMR scans of several compounds that have substructures of 3 and their 3,4,5-trimethoxyphenyl analogues were examined. When a racemic alcohol reacts with (R)-MTPA to give a pair of (R)-MTPA ester diastereomers, the value was defined as the absolute value of the difference in the1H chemical shifts of the peak between the diastereomers. It was found that the values of-MTPA-OCH3 were larger than those of-MTPA-OCH3 owing to a shielding effect of the veratryl ring located on the-MTPA-OCH3, and that the-MTPA-OCH3 peaks in the 3,4,5-trimethoxyphenyl compounds shifted downfield relative to those in the veratryl compounds. On the basis of the1h NMR data of (R)-MTPA esters, the absolute configuration of the four chemically prepared diastereomers (3) were determined. The catabolicerythro 3 [fromerythro (-)-3] andthreo 3 [fromthreo (+)-3] were identical to (R, S, R)-erythro 3 and (R, S, S)- threo 3, respectively. An hydrogen species in the fungal reduction would attack the-ketone fromre-face of both (R)-1 and (S)-1, givingerythro (S, R)-2 andthreo (S, S)-2, respectively.Part of this paper was presented at the 33rd Lignin Symposium, Tsukuba, November 1988  相似文献   

9.
A modified synthetic method for phenolic-O-4 lignin substructure model dimers was developed involving protection of the phenolic hydroxyl group of acetophenons with benzoyl chloride, bromination with 4-dimethylaminopyridiniumbromide perbromide, condensation with phenols in the presence of 18-crown-6-ether, condensation with paraformaldehyde, reduction with NaBH4 and debenzoylation. This method results in shorter reaction times and increasing yields without the application of strict anhydrous and drastic conditions or chloric solvents. This alternative route could be applied to the-O-4 dilignol syntheses of four combinations of guaiacyl and syringyl derivatives.  相似文献   

10.
Summary A -d-(13)-linked glucan has been isolated from compression wood of tamarack [Larix laricina (Du Roi) K. Koch]. The polysaccharide, which had []D + 17.6°, consumed 0.17 mole of periodate per glucose residue and gave a methyl derivative which consisted of 115 2,4,6-tri- and 2,3,4,6-tetra-O-methyl-d-glucose residues in a ratio of 17.8:1. Partial acid hydrolysis yielded a series of -d-(13)-linked oligosaccharides, while enzymic hydrolysis with a -1,3-glucanase afforded glucose, laminaribiose, and laminaritriose. The glucan occurred in amounts varying from 2 to 4% in compression wood of this and other conifer species and was present in the wall of both tracheids and ray cells. It is proposed that this structural polysaccharide be designated as laricinan to distinguish it from callose and the various -1,3-glucans in lower plants.  相似文献   

11.
Summary The structure of the reducing end group in xylan can be written: --D-Xylp-(14)--D-Xylp-(13)--L-Rhap-(12)---D-GalpA-(14)-D-XylIn alkaline media the reducing xylose group is easily isomerized and removed by a -elimination which leads to a reducing galacturonic acid end group. The 1, 2-linkage between rhamnose and the galacturonic acid explains the retarding effect on the alkaline peeling. Even under fairly mild conditions the galacturonic acid group is converted to other groups which are very stable in alkaline media. Model experiments permit the conclusion that OH-3 in the reducing group is subjected to -hydroxyelimination. The 3-deoxy-2-O--L-rhamnopyranosyl-D-threo-hex-2-enuronic acid group formed is unstable in acid medium and escapes observation by the techniques employed for determination of the end groups.Upon prolonged alkaline treatment and increased proportion of these groups is lost and a rapid peeling proceeds until a xylose group with a 4-O-methylglucuronic acid substituent is liberated. The consecutive reactions of this group are similar to those of the galacturonic acid groups.The formation of 3-deoxyaldonic acid end groups, an important stopping reaction in cellulose, is of minor importance in xylan.The financial support from the 1959 Års Fond för Teknisk och Skoglig Forskning samt Utbildning is gratefully acknowledged.  相似文献   

12.
Lateral fluxes of macrodetritus, particulate matter and dissolved organic carbon were determined. Samples were collected monthly at the mangrove forest–inshore water boundary and within the forest. Floating macrodetritus (mainly mangrove leaves) was collected by a net (2mm mesh size). Dissolved and particulate matter were separated by filtration (0.45m filter) and centrifugation. Dissolved and particulate carbon were determined by a total organic carbon analyser (SHIMADZU model TOC5000). There was a significant export of mangrove litter to the adjacent marine environment during spring tides. Rates of import and export of particulate matter in the forest were not statistically different. Translocation of material within the forest was clearly demonstrated. A relatively high export of macrodetritus was recorded at the marine fringe (mainly colonised by Sonneratia alba). There was low export of litter in the terrestrial fringe zone, a monospecific stand occupied by Avicennia marina (Forsk) Vierh. Net organic carbon export from the entire forest was 79×106g C y–1, dissolved organic carbon accounted for about 78% of the total export.  相似文献   

13.
The effect of isolation method on the chemical structure of residual lignin   总被引：2，自引：0，他引：2  
Two methods are used for the isolation of residual lignin: acidolytic and enzymatic hydrolysis. Recently a two-step procedure that is a combination of enzymatic and acidic hydrolyses was proposed. In this paper, the structures of residual lignins isolated by these three methods are compared. Enzymatic hydrolysis gave lignin with the highest yield (83%); however, it contained high amounts of carbohydrates and protein. The molar mass of enzymatic lignin was the highest, indicating that no cleavage of lignin occurred. Acidolysis gave a significantly lower lignin yield (40%), but this lignin was practically free from impurities. The -aryl ether and lignin-carbohydrate linkages cleaved during the isolation, which was manifested in the decreased molar mass of the lignin as well as in increased phenolic hydroxyl group content. The new two-step isolation procedure gave properties between the preparations of enzymatic and acidolytic hydrolyses. The lignin yield was high (78%), but it contained some impurities, although less than the enzymatic lignin. The lignin-carbohydrate linkages cleaved to some extent, but the -aryl ether linkages remained intact.Y. Sun also affiliated with the Pulp and Paper Research Institute of Canada (PAPRICAN), Pulp and Paper Research Centre, McGill University.  相似文献   

14.
A novel method for analysis of benzylic ether type lignin–carbohydrate bonds has been developed by using model compounds. Four diastereomers of model compound 3-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-3-(methyl -d-glucopyranoside-6-O-yl)-1-propanol (GGMGP), were ozonized in acetic acid/water/methanol 16:3:1 for 1h at 0°C. The product from ozonation of each diastereomer was saponified and the corresponding -etherified tetronic acid (TAMGP) was isolated using ion exchange chromatography. Minor amounts of methyl -d-glucopyranoside (MGP) and small amounts of a gluconic acid etherified with tetronic acid (TAGLCA), tetronic acid, gluconic acid, and glyceric acid were detected in the product mixture of ozonated benzylic ether type model compounds. The results suggest that a benzyl ether bond between lignin and carbohydrate is rather stable during the ozone treatment. Acid treatments with sulfuric acid or trifluoroacetic acid of the derived TAMGP led to cleavage of the glucosidic bond but only a small amount of products (tetronic acid and glucose) resulting from cleavage of the -ether bond were formed. The successful chemical treatments were used for studies of benzylic ether bonds in Japanese red pine. The results suggest the presence of benzylic ether bonds to polysaccharides in the wood.Part of this paper was presented at the 10th International Symposium of Wood and Pulping Chemistry (ISWPC), Yokohama, 1999; the 11th ISWPC, Nice, 2001; and as a rapid comunication in J Wood Sci (2000) 46:263–265  相似文献   

15.
Summary Murine monoclonal antibodies (mAbs) were produced to the extracellular -1,4-xy-lanase fraction of the brown-rot fungus, Postia placenta. The immunizing antigen was derived from decayed southern yellow pine wood blocks extracted in phosphate-buffered saline and Triton X-100, and fractionated by column chromatography. Five IgG monoclonal antibodies were selected for characterization by enzyme-linked immunosorbent assay, (ELISA) and western blot. Each mAb exhibited binding to two major protein bands on western blot at 32 kDa and 36 kDa. Characterization by chemical and enzymatic modification of the antigen determined whether mAbs were protein specific or specific for the carbohydrate portion of the glycoprotein. Affinity chromatography with the protein specific mAbs demonstrated specific binding to -1,4-xylanase and cross-reactivity with -1,3-glucanase, -1,4-glucanase, and -1,4-mannanase. These mAbs were also immunoreactive with polysaccharidases from liquid culture filtrates when tested by ELISA.The mAbs have been utilized to successfully detected P. placenta by ELISA in decayed southern yellow pine at a weight loss of 3.6%.This article was written and prepared by U.S. Government employees on official time, and it is therefore the public domain and not subject to copyright. The Forest Products Laboratory is maintained in cooperation with the University of Wisconsin  相似文献   

16.
The effects of stilbene glucosides and related compounds on termite feeding behavior were investigated using paper disc methods against the subterranean termite Reticulitermes speratus. The stilbene-rich fraction and isorhapontin (3-methoxy-3,4, 5-trihydroxystilbene-3--d-glucoside) from bark extracts of Picea glehnii showed avoidance by termites in choice tests. In the no-choice tests using compounds purified from the stilbene-rich fraction, the largest feeding deterrent effect was observed for piceid (3,4,5-trihydroxystilbene-3--d-glucoside), followed by isorhapontin, and astringin (3,3,4,5-tetrahydroxystilbene-3--d-glucoside), at the concentrations from 0.63 to 2.5µmol/disc. No change in activity was observed at retentions of more than 5.0µmol/disc. When the activities of isorhapontin and its aglycone derivative (isorhapontigenin: 3-methoxy-3,4,5-trihydroxystilbene) were compared with that of taxifolin (3,3,4,5,7-pentahydroxyflavanone) in the no-choice test, the stilbenes exhibited a larger antifeedant potential. Methylation of isorhapontigenin increased its termiticidal activity.Part of this study was presented at the 32nd Annual Meeting of the International Research Group on Wood Preservation, 2001  相似文献   

17.
Xylan prepared from culms of kumaizasa (Sasa senanensis Rehd.), a representative species of bamboo grass, was hydrolyzed with-xylanase ofStreptomyces olivaceoviridis E-86. Four arabinoxylo-oligosaccharides and two glucuronoxylo-oligosaccharides were isolated from the enzymatic hydrolysate of the xylan by chromatography on a charcoal column, a Dowex 1-x8 column, a Toyo-pearl HW-40S column, and a LiChrospher 100 NH2 column and on preparative paper chromatography. The results of the structural analyses of the saccharides showed that the isolated oligosaccharides had the structures of 32--l-arabinofuranosyl-xylobiose, 32--l-arabinofuranosyl-xylotriose, 32--[-d-xylopyranosyl-(1 2)-l-arabinofuranosyl]-xylobiose, 33--[-d-xylopyranosyl-(1 2)-l-arabinofuranosyl]-xylotriose, 23--4-O-methyl-d-glucuronosyl-xylotriose, and 23--d-glucuronosyl-xylotriose. From the structural analysis of the oligosaccharides derived from the xylan, kumaizasa xylan was concluded to be a kind of arabinoglucuronoxylan having not only stubs of singlel-arabinose and singled-glucuronic acid but also stubs of disaccharide units such as-d-xylopyranosyl-(1 2)-l-arabinofuranose.  相似文献   

18.
The enzymatically dehydrogenative polymerization of coniferyl aldehyde and coniferyl alcohol was studied to understand lignins in cinnamyl alcohol dehydrogenase (CAD)-downregulated plants. The sample dimers were prepared by polymerization under three reaction systems (coniferyl alcohol, coniferyl aldehyde, and their combination) with horseradish peroxidase/H2O2 under the conditions of limited reaction time. In addition, the residual amount of substrate in each reaction was determined at specified time intervals. In the reaction system of coniferyl aldehyde, the 5-5-type dimer was formed in preference to- and-5 dimers; in the reaction system of coniferyl alcohol the-5 dimer was preferentially formed. Furthermore, it was revealed when quantifying dimers among reaction systems that the total dimer formation capability of coniferyl alcohol clearly surpassed that of coniferyl aldehyde. However, the dimers cross-coupled with coniferyl alcohol and coniferyl aldehyde were formed in amounts not accounted for by the difference seen in dimer formation abilities with the two substrates.Part of this paper was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999  相似文献   

19.
Zusammenfassung 1. Die in den Pflanzengeweben der Kiefer enthaltenen Terpenoide spielen die Rolle der Pflanzenschutzstoffe gegen Insektenschäden. Biologische Aktivität der einzelnen Terpenoide bewirkt Auswahlvermögen der einzelnen Arten der schädlichen Organismen. Besonders toxisch gegen Insekten sind die Azetate der Terpenalkohole und Monoterpene, dabei haben die Monoterpene im Futter eine anziehende und repellente Wirkung. Sehr toxisch für die pilzlichen Krankheitserreger sind die Terpenalkohole. Man kann deshalb die Komplexe der Pflanzenschutzstoffe der Kiefer als ein Schutzsystem des Baumes gegen Schädlinge und Krankheiten betrachten, die ihrerseits aus einer Reihe von Untersystemen zusammengesetzt sind: Nadeln, Triebe, Stamm, Wurzeln usw. Das Pflanzenschutzsystem des Baumes und die darin enthaltenen Untersysteme sind je nach den Vegetationsbedingungen sehr variabel, dadurch erklärt sich die verschiedene Anfälligkeit der Pflanzen für Schädlinge.Verschiedene Kiefernarten enthalten qualitativ verschiedene Schutzsysteme. Darauf ist ihre verschiedene Widerstandsfähigkeit gegen Schädlinge begründet.Das Pflanzenschutzsystem der Kiefer, die ihren Widerstand gegen den Triebwickler der GattungEvetria bestimmt, kann ausgedrückt werden durch die Formel + l + 3 ± 60% in der der -Gehalt an -Pinen in %, l-Gehalt an Limonen in %, 3-Gehalt an 3-Karen in %, -Gehalt an -Pinen in % bedeuten.  相似文献   

20.
The stilbene glucoside isorhapontin (5,4-dihydroxy-3-methoxystilbene-3--D-glucoside) is the major constituent of the ethyl acetate extracts fromPicea glehnii bark. Isorhapontin inhibited the hydrolytic activity ofTrichoderma cellobiohydrolase I (CBH I) for both bacterial microcrystalline cellulose and the soluble cellooligosaccharide celloheptaitol. The inhibitory effect for celloheptaitol, however, was more drastic than that for bacterial microcrystalline cellulose. The hydrolytic activity of the CBH I core domain for celloheptaitol was also inhibited by isorhapontin to a similar extent, suggesting that the interaction between isorhapontin and the core domain of CBH I is the reason for this phenomenon. The inhibition of CBH I activity by isorhapontin showed mixed noncompetitive and uncompetitive types in a concentration of the inhibitor of less than 125M. TheK i andK i values were estimated to be 57.2 and 33.3M, respectively. Whereas isorhapontin strongly inhibited CBH I activity, its aglycone isorhapontigenin (3-methoxy-3,5,4-trihydroxystilbene) showed almost no inhibition. Consequently, both the stilbenic and the-glucosidic structures in isorhapontin are essential for the inhibitory effect on CBH I activity. Isorhapontin also inhibited the activity ofTrichoderma endoglucanase I for celloheptaitol, whereas almost no effect was observed for the activities of both endoglucanases II and III.An outline of this work was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999  相似文献   

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