Zhenfu Jin

Structural changes in lignin of tropical woods during digestion by termite, Cryptotermes brevis

Wood samples of apitong (Dipterocarpus grandiflorua) and ilang-ilang (Ilang-Ilang C. dadloyi) and feces of termites [Cryptotermes brevis (Walker)] fed on these woods were collected from University of the Philippines, Los Baňos. Lignin of each sample was isolated by Björkman’s procedure. There was no significant difference in 1H nuclear magnetic resonance (NMR) spectra or in the methoxyl content between Björkman lignins from original woods and termite feces. Differences were detected in the contents of aliphatic and unconjugated phenolic hydroxyl groups, suggesting minor structural changes of lignin during digestion by termites. In addition, the ratio of syringyl to guaiacyl nuclei of Björkman lignin from termite feces determined by 1H NMR spectra was higher than those from the original woods. The molar ratio of syringyl to guaiacyl nuclei of termite feces was higher than those from the original woods as determined by alkaline nitrobenzene oxidation. These results suggest that the structural changes of lignin in the termite gut are due to the insignificant formation of C-C linkages in guaiacyl nuclei. It was concluded that there were minor changes in the structural features of lignin under mostly anaerobic conditions, in contrast to the significant changes that occur through biological modification under aerobic conditions.

Changes in lignin content of leaf litters during mulching

Alkaline nitrobenzene oxidation, ozonation and methoxyl content determinations were applied to decomposing leaf litter of Ginkgo biloba L., Cinnamomum camphora sieb., Zelkova serrata Makino and Firmiana simplex W. F. Wight, respectively, during mulching to investigate the properties and estimate changes in lignin composition and content. Since the Klason lignin residue originated from components highly resistant to degradation by acid, the methoxyl content of Klason residue was used to estimate the lignin content of leaf litter. Quantitative analysis of presumed lignin-derived fragments, by use of alkaline nitrobenzene oxidation and ozonation methods, suggested that the estimated lignin content approximates that of the real lignin content of leaves, which is greatly overestimated by the Klason procedure. The estimated lignin contents ranged from 3.9 to 10.0% while the Klason lignan residue varied from 37.1 to 46.7% in un-mulched leaf litter. The absolute amounts of the measured lignin somewhat decreased during mulching, while the structure of lignin remaining in leaf litters after mulching was considered not to be very different from its original structure.

Thermo characteristics of steam-exploded bamboo (Phyllostachys pubescens) lignin

Bamboo (Phyllostachys pubescens) internode was subjected to steam explosion treatment to produce an excellent fiber for binderless boards. Lignin was isolated from extract-free bamboo meal with Björkman’s procedure and steam-exploded pulp. The self binding-mechanism was discussed by scanning electron microscopy (SEM), thermo-gravimetry (TG), differential scanning calorimetry (DSC) and analytical ozonation. It is well-known that steam explosion treatment liberates lignin from the cell wall to the fiber surface, which is the most important component relevant to binderless board production. Results of TG and DSC analyses showed that steam-exploded bamboo pulp started mass loss at lower temperature compared to bamboo internode meal. The thermal softening temperature of lignin prepared from steam-exploded pulp was much lower than that of lignin prepared from extract-free bamboo meal. This suggests that intermonomer linkages of lignin, especially β-aryl-ether linkage which is the major intermonomer linkage of lignin, were cleaved during steam explosion treatment resulting in low molecular weight phenolic compounds. The cleavage of β-aryl-ether intermonomer linkage of lignin was also confirmed by ozonation analysis.

Lignin characteristics of peculiar vascular plants

Trochodendron aralioides Sieb. et Zucc. and Chloranthus glaber (Thunb.) Makino [Sarcandra globra (Thunb.) Nakai] belong to primitive angiosperms, and are characterized by the absence of vessels. Ephedra sinica Stapf, which is classified in the gymnosperms, contains vessel elements and fiber together with tracheids. Podocarpus macrophyllus (Thunb. Ex Murray) D. Don var. macrophyllus is reported to give a weak positive Mäule test, although it is classified as a gymnosperm. Podocarpus macrophyllus gave only vanillin on alkaline nitrobenzene oxidation, while E. sinica, T. aralioides, and C. glaber gave both vanillin and syringaldehyde. The molar ratio of syringyl to guaiacyl nuclei (S/V ratio) of C. glaber was significantly low (S/V = 0.08) in comparison with the value for T. aralioides (S/V = 1.56). The erythro form is the predominant diasteromeric form of β-O-4 intermonomer linkages of T. aralioides and E. sinica [molar ratio of erythro to threo forms (E/T ratio): 1.93 and 1.67, respectively]; however, P. macrophyllus and C. glaber lignins, of which S/V ratios were 0 and 0.08, gave approximately equal amounts of erythro and threo forms (E/T ratio: 1.01 and 1.14). Results from 1H NMR spectroscopy agree well with S/V ratios of alkaline nitrobenzene oxidation and E/T ratios of ozonation products. In conclusion differences in guaiacyl lignin and guaiacyl-syringyl lignin do not exactly reflect taxonomical differences, as reported in previous articles. It was found that guaiacyl-syringyl lignin is not necessarily linked to the presence of vessels.

Structural characteristics of lignin in primitive pteridophytes: Selaginella species

The lignin chemical structures of eight species of the Selaginella family, which are primitive vascular plants, were characterized by alkaline nitrobenzene oxidation, acidolysis, and ozonation. Selaginella involvens, Selaginella tamariscina, and Selaginella remotifolia were collected from the University Forest in Chiba, the University of Tokyo, Japan, and Selaginella biformis, Selaginella pennata, S. involvens, Selaginella chrysorrhizos, and unidentified Selaginella species (Selaginella sp.) were collected from northern Thailand. Lignin of all Selaginella species examined in this study was rich in syringyl nuclei. It was confirmed that a considerable portion of syringyl nuclei of Selaginella lignin formed syringylglycerol-β-aryl ether intermonomer linkages. The major diastereomer of arylglycerol-β-aryl ether intermonomer linkages of Selaginella lignins was the erythro-form exhibiting angiosperm lignin characteristics. In addition, lignins of S. involvens, S. tamariscina, and S. remotifolia collected from the University Forest in Chiba, the University of Tokyo, Japan, were isolated according to Björkman’s procedure, and structural features of the lignins were spectrometrically analyzed. It was confirmed that lignin of Selaginella species, which are primitive pteridophytes, was typical guaiacyl-syringyl type as well as being similar to angiosperm lignin.

Lignin as a cross-linker of acrylic acid-grafted carboxymethyl lignocellulose

Cunninghamia lanceolata wood meal samples with different lignin contents after delignification with an acidic NaClO2 system were carboxymethylated, and the degree of substitution (DS) and the distribution of the carboxymethyl (CM) groups were investigated by proton nuclear magnetic resonance (1H NMR) spectroscopy. Cellulose samples prepared from bleached kraft softwood pulp, food-grade konjac mannan, and commercial oat xylan (containing 10% arabinosyl and 15% glucosyl residues) were also investigated. The chemical shift of methylene protons in 1H NMR spectra of CM groups of carboxymethyl konjac mannan and commercial oat xylan appeared in the same region as those of carboxymethylcellulose. The DS of carboxymethyl lignocellulose (CMLC) increased slightly from 1.36 to 1.48 with decreasing lignin content, but the water solubility of CMLC clearly increased with decreasing lignin content. It was suggested that the covalent linkages between lignin and cell-wall polysaccharides play the role of cross-linker in CMLC. Water absorbents were synthesized by graft-copolymerization of acrylic acid onto CMLC samples with different lignin contents. The highest level of water absorbency was obtained from CMLC containing 14% of lignin, suggesting the importance of lignin as the cross-linker.