Changes in chemical characteristics of bamboo (Phyllostachys pubescens) components during steam explosion

Chemical changes in cell wall components of bamboo internode during steam explosion process were analyzed to investigate self-binding mechanism of binderless board from steam-exploded pulp. More than 30% of xylose on initial mass, which is a major hydrolyzate of bamboo hemicelluloses, was lost after steam explosion treatment. Bamboo lignin is characterized by the presence of ester- and/or ether-linked p-coumaric acid to lignin. The content of phenolic hydroxyl groups of lignin isolated from steam-exploded pulp was characterized 2.3 times higher than those of the extract-free bamboo internode due to the cleavage of β-O-4 linkages. Alkaline nitrobenzene oxidation of the bamboo lignin gave vanillin, syringaldehyde and p-hydroxybenzaldehyde as major products. The content of p-hydroxybenzaldehyde decreased after steam explosion treatment, indicating the cleavage of ester- and/or ether-linked p-coumaric acid. The total yield of erythronic and threonic acids in ozonation products of the extract-free bamboo internode lignin was 268 mmol (200 g lignin)⁻¹, while those of lignins in the steam-exploded pulp and powdery fraction were 96 and 129 mmol (200 g lignin)⁻¹, respectively, suggesting the significant cleavage of β-O-4 linkages during steam explosion treatment. The cleavage of β-O-4 linkages was also confirmed by ¹H- and ¹³C-NMR spectroscopic observations.     

Structural characteristics of cell walls of kenaf (<Emphasis Type="Italic">Hibiscus cannabinus </Emphasis>L.) and fixation of carbon dioxide

 Kenaf (Hibiscus cannabinus) plants are widely known for their contribution to the global and regional environment because of their ability to fix CO₂. On the other hand, some scientists have doubts about CO₂ fixation by kenaf and have misgivings about the effect of kenaf on the ecosystem. We have characterized the structural characteristics of cell walls of bast fibers, cores, roots, and leaves of kenaf during the maturation of plants and investigated the rate of photosynthesis. During maturation of the kenaf plant the cellulose (bast fiber 52–59%, core 44–46%) and lignin (bast fiber 9.3–13.2%, core 18.3–23.2%) contents increased significantly. The aromatic composition of the lignin of bast fiber was significantly different from that of the core lignin and of other plants. The lignin of bast fiber appears similar to pure syringyl lignin. Fixation of CO₂ by kenaf plants and their contribution to the global environment are discussed. A significatly high rate of photosynthesis of kenaf plants was observed compared to that of woody plants in Japan, but the amount of CO₂ fixation depends on the characteristics of the plantation. If the kenaf was planted in high density, about twice as much CO₂ was fixed as was fixed by trees in a tropical rain forest. Received: April 22, 2002 / Accepted: July 24, 2002 Acknowledgments This project was supported by the Science and Technology Agency (STA) fellowship of the Japan International Science and Technology Exchange Center (JISTEC), which has been successfully applied by Dr. Shuji Hosoya, Forestry and Forest Products Research Institute. We thank Dr. Toshio Sumizono and Mr. Masao Sakurai, Forestry and Forest Products Research Institute, for their kind help in determining the rate of photosynthesis and cultivating the kenaf plants, respectively. We also express our appreciation to Dr. Quang Hung Le, College of Agriculture and Forestry, Ho Chi Minh City, Vietnam for offering information about the cultivation of kenaf at Thu Duc District, Ho Chi Minh City.     

Structural changes in lignin of tropical woods during digestion by termite, <Emphasis Type="Italic">Cryptotermes brevis</Emphasis>

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.     

Influence of the chemical composition of kenaf bast and core on the alkaline pulping response

The bast and core of kenaf,Hibiscus cannabinus L., have markedly different chemical components and alkaline cooking responses. The bast had about double the hot-water extractives content and only about half the lignin content of the core. The core contained a large amount of hemicellulose, mostly composed of xylan. The lignin structures of bast and core were also quite different: The former had a significant abundance of syringyl structures. Evidence showed that the bast was much more easily delignified than the core. When the bast and core were cooked together in alkaline condition, the pulp yields at the same kappa number were higher than those of the individual pulpings of bast and core. The bast-core pulping gave a positive effect on the yield of bast pulp in the sodaanthraquinone and kraft pulpings. On the other hand, kenaf was abundant in the hot water extractives. These extractives consumed alkali during cooking to a relatively large extent but acted as a protector of hemicellulose and slightly increased the pulp yields.Part of this paper was presented at the 48th and 49th Annual Meetings of the Japan Wood Research Society, Shizuoka, April 3–5, 1998 and Tokyo, April 3–5, 1999     

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.     

Fractional isolation and structural characterization of mild ball-milled lignin in high yield and purity from <Emphasis Type="Italic">Eucommia ulmoides</Emphasis> Oliv

Sequential extractions of the mild ball-milled Eucommia ulmoides Oliv with 80% neutral dioxane, 75% dioxane containing 0.025 M HCl, 75% dioxane containing 0.1 M NaOH, 60% ethanol containing 0.5 M NaOH, 5% KOH, 5% NaOH, and 8% KOH at 75°C for 3 h released 91.3% of the original lignin. The results showed that the procedure for extracting lignin from the mild ball-milled wood with mild alkaline organic solvent was more efficient than the traditional method of neutral and mild acidic dioxane extractions. The structure of the seven lignin fractions were analysed using wet chemical analysis, such as alkaline nitrobenzene oxidation, FT-IR, and solution-state ¹H, ¹³C, and ³¹P NMR techniques. It is clear that the sequential mild acidic and alkaline organic solvent extractions of the mild ball-milled E. ulmoides Oliv offered significant yield improvements over the traditional signal acidolysis procedure for isolating lignin from wood, and the alkaline organic solvent extraction led to more lignin release than that of the mild acidolysis. This new procedure proposed in this study could be used for the lignin structural analysis, whereby wood is mild ball-milled and successively extracted with both mild acidic and alkaline organic solvents as well as aqueous alkalis to produce lignin fractions with high yield and purity and representing the total lignin in wood.     

Anatomy and lignin distribution of reaction wood in two Magnolia species

Summary Anatomical features of reaction wood formed in two Magnolia species, M. obovata Thunb. and M. kobus DC. which are considered to be among the primitive angiosperms, were observed. In addition, the distribution of guaiacyl and syringyl units of lignins in the cell walls of normal and reaction wood was examined using ultraviolet (UV)- and visible light (VL)- microspectrophotometry coupled with the Wiesner and M?ule reactions. The two Magnolia species formed a tension-like reaction wood without possessing the typical gelatinous layer (G-layer) on the upper side of the inclined stem or branch, in which a radial growth promotion occurred. Compared with the normal wood, the reaction wood had the following anatomical features: (1) the secondary walls of fiber tracheids lacked the S₃ layer, (2) the innermost layer of fiber-tracheid walls showed a small microfibril angle, a fact being similar to the orientation of the microfibril angle of the G-layer in tension wood, and (3) the amounts of lignin decreased in the cell walls of fiber tracheids, especially with great decrease in proportion of guaiacyl units in lignins. In addition, VL-microspectrophotometry coupled with the Wiesner and M?ule reactions adopted in the present study showed potential to estimate the lignin contents in the cell walls and the proportion of guaiacyl and syringyl units in lignins. Received: 15 July 1998     

Mineralization of the methoxyl carbon of isolated lignin by brown-rot fungi under solid substrate conditions

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.     

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     

Effect of Coriolus versicolor on physico-chemical properties of Eucalyptus globulus wood

Summary The purpose of this study was to determine the progressive changes in physical and chemical properties of Eucalyptus globulus wood under the action of a representative white rot fungus, Coriolus versicolor. Observations concerning the nature and relative effects on weight loss, hot water solubility, 1% sodium hydroxide solubility, Klason lignin, holocellulose, intrinsic viscosity and degree of polymerisation of holocellulose, pentosans, methoxyl value, neutral sugar composition and nitrobenzene oxidation products are discussed.The authors thank Dr. P. S. Rehill, the then Officer-in-Charge, Forest Pathology Branch, for valuable suggestions and providing facilities for decay experiments     

<Emphasis Type="Italic">Broussonetia papyrifera</Emphasis> (paper mulberry): its growth,yield and potential as a fallow crop in slash-and-burn upland rice system of northern Laos

In northern Laos, shortened fallows in the slash-and-burn upland rice system are not sustainable either from a production or economic standpoint. This paper evaluates the potential for using the indigenous fast-growing tree, Broussonetia papyrifera L. Vent. (paper mulberry) as an economic fallow crop. The objectives of this study are to assess the inner bark yield of paper mulberry, and to evaluate rice productivity following paper mulberry cultivation. In addition, allometric models for estimating the inner bark yield of paper mulberry are developed. Inner bark yield of paper mulberry stands ranging in age from 9 to 48 months ranged from 10 to 208 g m⁻², and increased with age. The models using diameter at breast height and stem height, or diameter at breast height only as independent variables explained well the variation in inner bark yield. When paper mulberry was completely removed during the rice growing season, rice yields in these areas were similar to those following weedy bush fallow. When paper mulberry was allowed to grow, rice yields were negatively correlated to paper mulberry stem density. When paper mulberry lateral branches were pruned back, rice yields could be maintained if the paper mulberry stem density was <0.22 stems m⁻², suggesting that if paper mulberry is managed properly, rice yields can be maintained at current levels. The paper mulberry-upland rice rotation system improves the productivity of a traditional slash-and-burn system through harvesting paper mulberry inner bark; however the long-term sustainability of such a system remains unclear and warrants further investigation.     

Structural characteristics of lignin in primitive pteridophytes: <Emphasis Type="Italic">Selaginella</Emphasis> 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.     

不同年龄构树皮的纤维、化学特性与制浆性能研究

对金沙江干热河谷不同年龄构树皮的化学、纤维特性与制浆性能进行研究.结果表明,构皮纤维长、木素含量低,纤维素含量高,纤维形态好,易于成浆.随着年龄的增大,低龄构皮化学组分稍有增大,但至6-7 a,灰分和木素含量增大,纤维素和硝酸-乙醇纤维素含量明显下降,不利于成浆;1%Na0H抽提物一直呈缓慢上升趋势,第6-7年达到最高;构皮纤维长度、长宽比及长纤维比例都随年龄的增长而增加,3-5 a增至最大,第6年后呈快速下降趋势.2-4年生构皮手抄片有较高的结合强度和耐折度,5-7 a后趋于稳定.因此,优质构皮纤维原料最佳收获期为2-5 a,综合经济效益考虑,纤维原料人工林培育最佳周期为2-3 a.     

Properties of kenaf core binderless particleboard reinforced with kenaf bast fiber-woven sheets

Kenaf composite panels were developed using kenaf bast fiber-woven sheets as top and bottom surfaces, and kenaf core particles as core material. During board manufacture, no binder was added to the core particles, while methylene diphenyldiisocyanate resin was sprayed to the kenaf bast fiber-woven sheet at 50 g/m² on a solids basis. The kenaf composite panels were made using a one-step steam-injection pressing method and a two-step pressing method (the particleboard is steam pressed first, followed by overlaying). Apart from the slightly higher thickness swelling (TS) values for the two-step panels when compared with the one-step panels, there was little difference in board properties between the two composite panel types. However, the two-step pressing operation is recommended when making high-density composite panels (>0.45 g/cm³) to avoid delamination. Compared with single-layer binderless particleboard, the bending strengths in dry and wet conditions, and the dimensional stability in the plane direction of composite panels were improved, especially at low densities. The kenaf composite panel recorded an internal bond strength (IB) value that was slightly low because of the decrease of core region density. The kenaf composite panel with a density of 0.45 g/cm³ (one-step) gave the mechanical properties of: dry modulus of rupture (MOR) 14.5 MPa, dry modulus of elasticity (MOE) 2.1 GPa, wet MOR 2.8 MPa, IB 0.27 MPa, TS 13.9%, and linear expansion 0.23%.     

Studies on the lignin of the bamboo species Phyllostachys makinoi Hay.

Summary Milled wood lignin (MWL) isolated from Phyllostachys makinoi was investigated by chemical and physical methods. The bamboo lignin is rich in syringyl units which is indicated by a high methoxyl content and respective bands in the IR spectrum. The distinct absorption bands for aromatic ring vibrations are attributed to final p-coumaryl ester groups. In the UV spectrum the extinction maximum in the range of 280 nm is shifted to longer wavelengths compared to wood lignin. With NaOH and TFA mainly an arabinoxylan with a Xyl: Ara ratio of 14:1 was extracted from bamboo saw dust. The lignin proportion in the NaOH extract, which derives mainly from the secondary walls has a lower methoxyl content, the lignin proportion in the TFA extract, which derives from the compound middle lamellae has a higher methoxyl content compared to MWL.     

Chemical changes of kenaf core binderless boards during hot pressing (I): influence of the pressing temperature condition

Self-bonding is the main factor of the performance expression of binderless boards, and therefore its clarification is considered to be an important issue. For this purpose, a series of chemical analyses were conducted on kenaf core binderless boards and their chemical changes during the hot-pressing process are discussed in this article. First of all, binderless boards were prepared from kenaf core powder at different pressing temperatures (without steam-explosion process) and were used for chemical analyses after they were reduced into powders and extracted with methanol. To investigate their chemical changes, lignin, holocellulose, and neutral sugar contents were determined, Fourier transform infrared (FTIR) spectra were recorded, and the nitrobenzene oxidation procedure was applied. As a result, it was found that parts of lignin and hemicelullose were decomposed during the hot-pressing process; however, the contribution of the resulting fractions to selfbonding was not observed. In addition, progress of condensation reactions in lignin and the formation of chemical bonds by low molecular weight conjugated carbonyl compounds in methanol extractives were observed. Thermal softening of lignin is also suggested to play an important role in the expression of board performance.     

Studies on milled wood lignins from spruce part 1. Composition and molecular properties

Summary Isolation of six milled wood lignins (MWL) from spruce under different conditions resulted in variable yields between 2.2% and 11.8% related to wood lignin. The composition of crude and purified lignins was evaluated with regard to non-hydrolyzable residue, acid-soluble lignin and polysaccharide content, which varied from 0.9 to 2.5%, depending on isolation conditions. The polysaccharide moiety of the crude and purified lignins contained a high percentage of glucose, probably derived from cellulose. The molecular size distributions determined by gel chromatography on different gels showed a broad distribution for all isolated lignins. A probable maximum of 40,000 for the molecular weight of milled wood lignins was determined by ultracentrifugation. Some of the lignin fractions were examined in the electron microscope.The authors are indepted to Prof. E. Killmann and Mrs. M. Bäumle (Institute for Technical Chemistry, Technical University of Munich) for assistance with the ultracentrifuge measurements and Dr. M. Stoll for precious suggestions and discussions. Submitted by Deutsche Forschungsgemeinschaft (DFG).     

13C NMR studies on lignins depolymerized with dry hydrogen iodide

Summary Spruce (Picea mariana) and birch (Betula verrucosa) milled wood lignins were depolymerized with dry hydrogen iodide. ¹³C NMR spectra of the initial and treated lignins were recorded. The data on chemical shifts of a set of model compounds treated with dry HI were used in the assignment of changes in the spectra of the lignins. The results obtained show that a cleavage of ether bonds in lignin and a substitution of -hydroxy and -alkoxygroups by iodine take place during the treatment.     

“I-214杨”心材、边材木质素的红外光谱、质子和碳-13核磁共振波谱特征研究

对从杨树心、边材提取的磨木木质素进行了元素分析和红外光谱（FTIR）质子和碳－13核磁共振波谱（^1H,^13C NMR)等化学特征研究。研究结果表明：杨树心、边材木质素的经验式分别为C9H7．16O2．38（OCH3）1．99和C9H8．61O2．73（OCH3）1．33。心材木质素甲氧基含量28．16％,比边材高8．73％。两种木质素均具有典型阔叶材的特征,化学结构类型基本一致,碳骨架结构基本相同,但化学官能团和键型的组成上存在差异。     

A comparative study of bamboo (Phyllostachys incarnata Wen) milled wood lignin and the successively alkali-fractionated lignins

The chemical composition and structural characterization of the milled wood lignin (MWL) and successively alkali-fractionated lignins from bamboo (Phyllostachys incarnata Wen) were comparatively investigated using Fourier transform infrared (FT-IR), gel permeation chromatography (GPC), 2D heteronuclear single quantum coherence (HSQC), and alkaline nitrobenzene oxidation. It was found that bamboo MWL (S/G?~?1.3) is of SGH type with a considerable amount of esterified p-coumaric acid and etherified ferulic acid. Molecular weights of 3,320?g/mol for MWL and varying weights between 970 and 3,430?g/mol for the alkali-fractionated lignins were obtained. Moreover, 2D HSQC of MWL showed a predominance of β-O-4′ linkages (65%), followed by β–β′ linkages (15%) and lower amounts of β-5′ (7%), β-1′ (4%), 5–5′ (4%) linkages, and cinnamyl acetate end groups (5%). In addition, a percentage (~45%) of the lignin side chain was found to be acylated at the γ-carbon. However, the alkali-fractionated lignins lost parts of these linkages during successive alkaline fractionation processes.