Tetsuo Koshijima

Ester linkages between lignin and glucuronic acid in lignin-carbohydrate complexes from Fagus crenata.

Abstract Conjugate acid oxidation of benzyl esters with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and trifluoroacetic acid (TFA) was applied to the binding site analysis of ester linkages between lignin and glucuronoxylan in Fagus crenata wood. Based on the conjugate acid DDQ-oxidation of a watersoluble lignin-carbohydrate complex (LCC-WE) from the beech wood, the frequency of the ester bonds between the lignin and glucuronic acid residue of glucuronoxylan was determined to be 1.6 per molecule of LCC-WE.

Association Between Lignin and Carbohydrates in Wood and Other Plant Tissues

1 Preparation and Characterization of Lignin-Carbohydrate Complexes.- 2 Location of Lignin Moieties Along Polysaccharide Chains in Lignin-Carbohydrate Complexes.- 3 Formation of Lignin-Carbohydrate-Complex Micelles and Pectin/Lignin/Hemicelluloses.- 4 Analysis of Native Bonds Between Lignin and Carbohydrate by Specific Chemical Reactions.- 5 Residual Lignin in Alkaline Pulps.- 6 Functions of Lignin-Carbohydrate Complexes.- 7 Microbial Degradation of Lignin-Carbohydrate Complexes.- 8 Condensation of Lignins with Carbohydrates in Concentrated Sulfuric Acid.- References.

Ester linkages between lignin and glucuronoxylan in a lignin-carbohydrate complex from beech (Fagus crenata) wood

SummaryA water-soluble lignin-carbohydrate complex (LCC) isolated from beech (Fagus crenata) MWL was investigated. Results from gelfiltration chromatography and the infrared spectrum of the LCC treated with alkali under mild conditions indicated that the LCC contained alkali-labile bonds. Decrease of uronic acid content and the detection of 4-O-methylglucose in the sodium borohydride-reduced LCC suggested the presence of an ester linkage between lignin and glucuronic acid in the glucuronoxylan. Conductometric titration also indicated the existence of glucuronic acid ester linked to lignin. From these results, it is concluded that the LCC contained an ester linkage between lignin and glucuronoxylan and that about one-third of the glucuronic acid present in the LCC was involved in this ester linkage.

Lignin-Carbohydrate Complexes and Phenolic Acids in Bagasse

Lignin-carbohydrate complex (LCC-W) which contained ferulic and p-coumaric acids was isolated from milled sugar cane bagasse and separated into three fractions (W— l, 2 and 3) by gel Filtration on Sepharose 4B. These three LCC fractions were different from each other in contents of lignin, carbohydrate and phenolic acids, and in molecular weight. Both W—l and W—2 fractions could be dissociated into a fraction having weight average molecular weight of 1.1 4 which is similar to that of the W—3 fraction. The carbohydrate portions of all LCC fractions are commonly composed of arabinoglucuronoxylan having arabinose to xylose ratio of 1:8. Ferulic and p-coumaric acids were established to be esterified to the different molecular species, polysaccharide and lignin moieties, respectively. Since the carbohydrate portion of LCC was composed of arabinoglucuronoxylan, and the linkages between carbohydrate and lignin could be splitted by alkali, lignin was presumed to link through benzyl ester or benzyl ether linkages to arabinoglucuronoxylan in the cell-walls of sugar cane.

Isolation and characterisation of lignin-carbohydrate complexes from the milled-wood lignin fraction of Pinus densiflora sieb. et zucc.

Abstract The lignin-carbohydrate complex (LCC-W), isolated from the milled-wood, lignin fraction of Pinus densiflora Sieb. et Zucc., comprised three fractions (W-1,2,3) by gel filtration on Sepharose 4B. W-1 was eluted at the void volume, whereas W-2 and W-3 were included in the gel and had apparent weight-average molecular weights of 5.0 × 10 5 and 5.0 × 10 3 , respectively. W-2 and W-3 were homogeneous in ultracentrifugal and electrophoretic analyses. The sedimentation coefficients of W-2 and W-3 were 25.7 and 0.4S, respectively. The chemical composition of W-2 was 38.0% of neutral sugar, 6.2% of uronic acid, 51.5% of lignin, and the corresponding values for W-3 were 73.1, 11.0, and 22.2%. The neutral carbohydrate residues of W-2 and W-3 were l -arabinose, d -xylose, d -mannose, d -galactose, and d -glucose in the ratios 15.8:16.2:37.3:16.7:14.0 and 27.6:16.5:26.1:19.3:10.5, respectively. Based on the results of methylation and Smith-degradation analyses, the carbohydrate moiety of the LCC-W fractions was found to be multiply branched. The major backbone structure was composed of (1→4)-linked d -mannopyranosyl residues. By hydrophobicinteraction chromatography on Phenyl- and Octyl-Sepharsoe CL-4B gels, it is concluded that the LCC-W fractions have a hydrophobic property that is exclusively ascribed to the lignin moiety.

Lignin Garbohydrate Complex. Pt. I. The Influences of Milling of Wood upon the Björkman LCC

Tamolang, F. N., E. O. Mabesa, M. A. Eusebio, M. J. Sagrado and B. A. Lomibao. 1957. Fiber dimensions of certain Philippine broadleaved woods and bamboos. Tappi 40, 671—676. Tamolang, F. N., R. Valbuena, B. A. Lomibao, E. A. Artuz, C. Kalaw and A. Tongacan. 1958. Fiber dimensions of certain Philippine broadleaved and coniferous woods, palms and bamboos. II. Tappi 41, 614—621. Tamolang, F. N., R. Valbuena, B. A. Lomibao, C. L. Kalaw, T. M. Lindayen and B. C. de Vela. 1960. Fiber dimensions of certain Philippine woods, bamboos, agricultural crops and wastes, and grasses. III. Tappi 43, 527—534. Tang, S.-Y. 1962. Magnesium bisulphite process for the pulping of bamboo. In: FAO, Pulp and paper prospects in Asia and the Far East. Proc. Conf. Pulp and Paper Dev. in Asia and the Far East, Tokyo 1960, Vol. II, 386—390. Bangkok. Tono, T. and . no. 1960. Studies on bamboo culm and its fiber as cellulose material. Part i. Microscopical studies on bamboo culm and its fiber. Bull. Univ. Osaka Pref. Ser. B. Vol. 10, 25—32. Ueda, K. 1960. Studies on the physiology of bamboo with reference to practical application. Bull, Kyoto Univ. For., No. 30, 167 S. Ueda, K. 1966. Research and recommendaties on bamboo resources for pulp and paper making in Thailand. Overseas Tech. Coop. Agency Tokyo. Uno, S. 1929. Studies on bamboo fiber (Orig. jap.). Jap. J. For. 12. (Zit. nach Sineath, H. H. et al. 1953). Uno, S. 1930. Studie über die Bambusse (Orig. jap.). J. Jap. For. Soc. (Rin-gaku-kai Zasshi) 12, 529—537.

Synthesis of LCC Model Compounds and Their Chemical and Enzymatic Stabilities

Hydrolysis with dioxane-water (1:1) at 180 °C for one hour allows to break the phenylglycosidic linkage but remains undegraded at least 85% of the glycosidic bond at 7-hydroxyl of lignin side chain. Boron tribromide treatment of all model compounds results in a nearly quantitative Splitting of sugar components. The glycosidic bond between carbohydrate and lignin component is hydrolyzed completely by heating with 1N-H2SO4 at 100 °C for 6 hours, but sugar-lignin bond of ether type locating at 7-position of lignin side chain does not undergo acid hydrolysis. Sodium hydroxide (5%) treatment at ambient temperature never cleavage all of the glycosidic bonds synthesized here except compound III, but benzyl ether type locating at -position of phenylpropane unit is unstable even for very dilute alkali. It was found that methyl ether of this type compound, Villa also suffered alkaline degradation even at near ambient.temperature if the prolonged reaction time was employed. Cellulase preparations (Cellulosin AC and AP) hydrolyze quantitatively all of the glycosidic linkages of lignin-carbohydrate synthesized here even though the aglycon is so bulky äs dimer of phenylpropane unit. Enzymatic hydrolysis rate is larger in alkylated phenolic hydroxyl in comparison to free phenolic hydroxyl, in the former, benzylated one being more faster than the ethylated. Phenylxyloside is subjected to enzymatic hydrolysis more easily compared with phenylgiucoside.

Lignin Carbohydrate Complex Pt. II. Enzymic Degradation of Acidic Polysaccharide in Björkman LCC

alle drei Komponenten in wechselnden Verhältnissen in allen Fraktionen vorhanden. Ob ein Teil dieser drei Komponenten deshalb mit der angewandten Methode nicht zu trennen ist, weil sie als LigninPolysaccharid-Komplexe miteinander verbunden sind, muß durch weitere Versuche geklärt werden. 6. In einem Teil der Fraktionen ist der ArabinoseAnteil gegenüber dem Xylose-Anteil zweibis dreimal größer als in der Literatur angegeben (z. B. Tim eil 1967). Außerdem nimmt der relative Arabinose-Anteil mit steigendem Lignin-Anteil zu. Dies wird als weiterer Hinweis dafür gewertet, daß in Lignin-Polysaccharid-Komplexen Xylan möglicherweise über Arabinose-Einheiten an Lignin gebunden ist (F enge l und Przyklenk 1975, Wegener 1976).

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

SummaryStructural factors in a Pinus densiflora tree grown under the influence of strong wind were measured. No