Formation of a complex with aluminum by ozone-treated kraft lignins and their low molecular weight fragments

The formation of a complex with aluminum by low molecular weight compounds and saponified ozone-treated kraft lignins was evaluated based on the decrease in pH of their solutions on the addition of 0.1 M AlCl₃. Decreases in pH were observed with the solutions containing compounds having adjacent carboxyl groups (oxalic acid), carboxyl/alcoholic hydroxyl groups (glycolic acid), carboxyl/formyl groups (glyoxylic acid), and phenolic hydroxyl groups (protocatechuic acid) on the addition of 0.1 M AlCl₃. The malonic and phthalic acids, having two carboxyl groups, were also effective. These results show that the compounds were effective in forming complexes with aluminum. This finding corresponds to the fact that aluminum toxicity is reduced by formation of a complex with aluminum, except in phthalic acid. The chemical structures stated above in ozone-treated kraft lignins contribute, at least partly, to the complex with aluminum. The pH of solutions containing saponified ozone-treated kraft lignins and alkaline-treated kraft lignin decreased more than that without modified kraft lignins on the addition of 0.1 M AlCl₃, showing that they were effective in forming a complex with aluminum. The high molecular weight part of saponified ozone-treated kraft lignin was effective in forming a complex with aluminum and in reducing its toxicity.     

Reduction of aluminum toxicity to radish by alkaline oxygen treated kraft lignin

To obtain a soil-conditioning agent for acid soil containing excess aluminum ions (AL), kraft lignin was modified by alkaline oxygen treatment. The growth of radish root in solution and in soil containing AL with or without addition of these lignins under controlled pH was examined. We concluded the following. Growth inhibition of radish roots by AL can be removed by adding alkaline oxygentreated lignins in the range of pH 4.5–4.8 in soil. A similar result was obtained at pH 4.5 in a culture solution. The reduction of AL toxicity to plant may be due to the aggregation between AL and the modified lignin at low concentrations of modified lignin because soluble AL could not be detected. On other hand, elongation of radish root was not obviously inhibited, although the soluble AL in the solution culture was at an extremely high level when the dosage of a modified lignin was high. This suggests that the reduction in AL toxicity to plants was due to formation of a complex between AL and acidic groups of the modified lignin.Part of this report was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999 and the 44th Lignin Symposium, Gifu, October 1999     

Development of acid soil conditioning agent from lignin by ozone treatment II

Kraft lignins (KLs) modified with ozone were saponified with 0.1 M NaOH at room temperature overnight and the abilities of the modified KLs in reducing aluminum toxicity in acidic soil were assayed by planting experiments with radish (Raphanus sativa var. radicula Pers.). The abilities of ozone-treated KLs in reducing aluminum toxicity and accelerating root elongation increased markedly by saponification. Furthermore, KL treated with 0.1 M NaOH at room temperature overnight also effectively reduced aluminum toxicity and accelerated root elongation. These results suggest that KL contains chemical structures that contribute toward these favorable effects. Saponified ozone-treated KLs reduced aluminum toxicity at lower dosages than the alkaline-treated KL. This report was presented in part at the 57th Annual Meeting of the Japan Wood Research Society, Hiroshima, Japan, August 2007, and at the 52nd Lignin Symposium, Utsunomiya, Japan, November 2007     

Effective combinations of functional groups in chemically modified kraft lignins for reduction of aluminum toxicity

Plant growth tests were performed with radish (Raphanus sativa var. radicula Pers.) in culture solutions containing low molecular weight compounds in the presence of aluminum to determine the types of functional groups in kraft lignin (KL) modified with ozone and alkali that contributed to reducing aluminum toxicity. The low molecular weight compounds used in this study contained carboxyl, formyl, methoxyl, alcohol hydroxyl, and phenolic hydroxyl groups. The compounds that had adjacent two carboxyl groups (oxalic acid), carboxyl/alcohol hydroxyl groups (glycolic acid), or carboxyl/formyl groups (glyoxylic acid) were effective in reducing aluminum toxicity. Malonic acid, having two carboxyl groups, also reduced aluminum toxicity. The ability of ozone-treated KLs to reduce aluminum toxicity was considered to be partly due to these chemical structures. Protocatechuic acid, having two adjacent phenolic hydroxyl groups, was also effective in reducing aluminum toxicity. This indicated that the effectiveness of the alkaline-treated KL was partly due to its catechol structure. This report was presented in part at the 58th Annual Meeting of the Japan Wood Research Society, Tsukuba, Japan, March 2008     

Characterization of lignin fragments in alkaline oxygen-stage waste liquor as soil-conditioning agent

We characterized the lignin fragments in the alkaline oxygen delignification-stage waste liquor from a pulp and paper mill as a soil-conditioning agent. Chemical reactions of this lignin fragment should be very similar to those of alkaline-oxygen treatment of kraft lignin. Alkaline oxygen delignification-stage waste liquor was subjected to gel filtration chromatography and four different molecular weight fractions (F1, F2, F3, and F4) were obtained. These four fractions were used in plant growth experiments. A very clear positive effect in removing the aluminum (Al) toxicity to root growth of radish was found for all four fractions. When aluminum concentration in the nutrient solution was as low as 0.5 ppm, root elongation was practically inhibited, but if 12.5 ppm of lignin fragment was added, the toxic effect was practically removed and root elongation better than that in the control was observed. However, each fraction showed different performance in removing aluminum toxicity, and the highest molecular weight fraction, which contained some aromatic structures, showed better performance in removing Al toxicity. The reason for their different behaviors on Al toxicity was also examined.Parts of this report were presented at the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003 and the 48th Lignin Symposium, Fukui, Japan, November 2003     

Mechanism of detoxification of aluminum ions by kraft lignin treated with alkaline oxygen

 Kraft lignins modified by radical sulfonation or alkaline oxygen treatment were rich in acidic groups, such as sulfonic acid, carboxylic acid, and phenolic hydroxyl groups, and were effective as soil-conditioning agents, especially because of their ability to trap aluminum ions eluted from soil under acidic conditions. Formation of complexes between aluminum ions and modified lignins was examined using potentiometric titration and ²⁷Al nuclear magnetic resonance (NMR) spectroscopy. Changes in the titration curve of a modified lignin by the addition of aluminum ions suggest the release of protons after the formation of complexes between them. Disappearance of ²⁷Al-NMR signals assigned to various aluminum ions by the addition of kraft lignin treated with alkaline oxygen was also attributed to the formation of complexes. The relative ease of proton release because of complex formation between a modified lignin and metal ions was as follows: Fe³⁺ > Al³⁺ > Cu²⁺ > Pb²⁺ > Mn²⁺ > Ca²⁺. This indicates that aluminum complexes are quite stable, and the aluminum ion is not exchanged with cations other than Fe³⁺. Received: October 24, 2001 / Accepted: January 16, 2002 Present address: Asian Natural Environmental Science Center, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan Tel. +81-3-5841-7506; Fax +81-3-5841-5230 e-mail: ukyoko@mail.ecc.u-tokyo.ac.jp Part of this study was presented at the 11th International Symposium on Wood and Pulping Chemistry, Nice, June 2001 Correspondence to:K.S. Katsumata     

Development of an acid soil conditioning agent from lignin by ozone treatment III: improvement of ability of lignin to form an aluminum complex and to reduce aluminum toxicity after ozone treatment

Lignin prepared by a modified Klason method (KSL) was modified with ozone followed by alkaline treatments. The original and modified KSLs were subjected to a plant growth test with radish (Raphanus sativus L. var. radicula Pers.) in the presence of AlCl₃ (37.5 μM) to assess their ability to reduce aluminum toxicity. The formation of an aluminum complex with these KSLs was also examined by potentiometry. Neither the original nor alkaline-treated KSLs had an effect on aluminum toxicity or the formation of a complex, except for the alkaline-treated KSL at a maximal dose of 250 mg/l, which reduced aluminum toxicity. However, all the KSLs modified with ozone and alkali were effective at forming a complex and reducing aluminum toxicity. The dose of saponified ozone-treated KSLs required to reduce aluminum toxicity became lower and their water solubility increased as the ozone treatment was prolonged. These findings clearly show that water solubility and the ability to form a complex with and reduce the toxicity of aluminum were improved by ozone treatment of KSL.     

Characterization of lignin-carbohydrate linkages in the residual lignins isolated from chemical pulps of spruce (<Emphasis Type="Italic">Picea abies</Emphasis>) and beech wood (<Emphasis Type="Italic">Fagus sylvatica</Emphasis>)

To investigate the linkage types between carbohydrates and lignin, residual lignins were isolated from three different unbleached pulps [kraft, alkaline sulfite anthraquinone methanol (ASAM), and soda with anthraquinone (AQ) and methanol] of spruce and beech wood and then characterized by oxidation with 2,3-Dichloro-5,6-dicyanobenzoquinone and followed by Prehm’s methylation. In residual lignins, sugar moieties were bound to lignins via benzyl ether bonds. In particular, galactose and mannose are predominantly linked to lignin fragments in residual lignins of spruce wood, while xylose and galactose are favored in the formation of LC bonds in the residual lignins of beech wood. In the case of hexoses, primary hydroxyl groups (C6 position) preferentially take part in benzyl ether linkages. Hydroxyl groups in the C2 and C3 positions of xylose participate in LC bonds and a small portion of arabinose was notably connected to lignin via the C5 position. Approximately seven or eight sugars were connected in soda/AQ/methanol residual lignin per 100 C9 lignin units, while the frequencies of LC bonds in kraft and ASAM residual lignins were distinctively less at one to three sugars per 100 C9 lignin units. The publication of this article was made possible by an Emachu Research Fund. The authors are grateful for the fund.     

Thioacidolytic analysis of residual lignins isolated from the chemical pulps of spruce (Picea abies) and beech (Fagus sylvatica) wood

Eight different residual lignins isolated from unbleached chemical pulps [sulfite, kraft, alkaline sulfite-anthraquinone-methanol (ASAM), soda/AQ/MeOH] of spruce and beech were characterized using gel permeation chromatography (GPC), thioacidolysis, and desulfurization to determine average molecular weight, amounts of uncondensed β-O-4 linkages, and dimeric linkage patterns, respectively. The total amounts of G-CHSEt-CHSEt-CH₂SEt and S-CHSEt-CHSEt-CH₂SEt were markedly reduced in residual lignins to 40% to 80% of the values for the corresponding milled wood lignins (MWLs). The number of dimeric units determined by thioacidolysis and desulfurization of the residual lignins was decreased by onehalf to one-fifth compared to the MWLs. Among the diverse types of dimeric units, reduction of β-1 and β-5 units was significant in most of the residual lignins, with the exception of beech ASAM residual lignin. Compared to beech MWL, 40% more C6–C3 main monomers were detected, whereas the relative composition of the dimeric units in the beech residual lignin was very similar to that in the beech MWL. The average molecular weights of residual lignins were less than those of the MWLs. However, the average molecular weights of the spruce kraft and soda residual lignins were determined to be higher than those of the corresponding MWLs.     

Application of the amount of oxygen consumption to the investigation of the oxidation mechanism of lignin during oxygen-alkali treatment

The dioxygen consumption by kraft lignin and several lignin model compounds during oxygen-alkali treatments were directly analyzed using a dioxygen fl owmeter. The average dioxygen consumption by 200 g of kraft lignin was about 3 moles. Because this value was as much as those obtained for monomeric phenolic lignin model compounds, guaiacol and vanillyl alcohol, it was postulated that not only phenolic but also nonphenolic moieties in kraft lignin are extensively oxidized. The dioxygen consumption by 0.5 moles (one equivalent of aromatic units) of a dimeric lignin model compound, guaiacylglycerol-β-guaiacyl ether (GG), was also similar to that for 1 mole of guaiacol and vanillyl alcohol, regardless of the type of the aromatic moiety, which supports the above postulation. The most plausible mechanism for the oxidation of nonphenolic moieties is the oxidation of side chains of residual β-O-4 substructures by active oxygen species. By this mechanism, nonphenolic moieties in kraft lignin and GG are converted into corresponding phenolic moieties, and the oxidation by dioxygen progresses. Part of this article was presented at the 13th International Symposium on Wood, Fiber, and Pulping Chemistry (13th ISWFPC), Auckland, New Zealand, May 2005     

Preparation of activated carbon moldings from the mixture of waste newspaper and isolated lignins: mechanical strength of thin sheet and adsorption property

To expand the utilization of waste newspapers and lignin, activated carbon (AC) sheets, as an example of AC moldings, were prepared from those mixtures. The isolated lignins used were softwood and hardwood acetic acid lignins (SAL and HAL), softwood kraft lignin (KL), and wheat-straw lignin (WSL). The mixtures were molded into precursory sheets by thermal compression and then converted to AC sheets by carbonization and steam activation. The flexural strength of the precursory sheets was dramatically improved by additing the lignins compared to that of sheets without lignin. The strength of several sheets was more than 25 MPa. This suggested that lignins act as adhesives. SAL and HAL sheets with 40% newspaper were strengthened by the carbonization, whereas the strength of other lignin sheets was depressed. Finally, the AL-based AC sheets showed higher flexural strength (>6MPa) than others. Most of the AC sheets had adsorption ability comparable to that of commercially available AC powder and granules. The capacities were almost independent of paper content. Among the AC moldings tested, the AL-based AC sheets showed the fastest adsorption top-chlorophenol. Thus, viable AC moldings can be prepared from lignin-wastepaper mixtures, particularly SAL and HAL.     

“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。     

Degradation of pine kraft lignin by Coriolopsis gallica growing on a fibre-glass support

Summary Coriolopsis gallica was grown in static liquid cultures on an inert support consisting of fibre-glass impregnated with Indulin AT (pine kraft lignin). The fungus developed well in such conditions enabling the study with the SEM of the morphology and penetration of the fungus. The method also pemits the recovery of degraded lignin, the characteristics of which was monitored by direct analysis of its elementary composition, methoxyls groups, and by spectroscopic techniques and gel permeation. Degraded lignin differed from sound lignin by its higher percentages of oxygen, and lower percentages of C, H, and OCH₃ was richer in oxygen. The IR and vis-UV spectra as well as the fractionation by gel filtration showed that the structure of the lignin incubated in the presence of the fungus had been modified.     

Characteristics of lignin obtained from steam-exploded softwood with soda/anthraquinone pulping

Lignins were obtained from a mixture of softwood sawdust using a hydrolytic pretreatment and a subsequent soda-anthraquinone delignification/pulping stage. Their potential uses and the effect of the pretreatment conditions on the yield (% of recovered lignin from black liquors) and chemical composition of isolated lignins were evaluated. The severity factor used combined the temperature and time of the hydrolytic process in a single ordinate (R_o). The severity range was modified from log R_o = 2.6 to log R_o = 4.6 and the pulping conditions were constant throughout the experiments. The effect of the cooking time on the chemical composition of precipitated lignins was also studied between 135–170 min for original (non-pretreated) material. Yield, elemental analysis, molecular weight distribution, Fourier transform infrared spectra (FTIR), structure, and the methoxyl and aliphatic/aromatic alcohol content of the various lignins, were compared.     

臭氧胁迫对树木根系影响研究进展

对流层中高浓度的臭氧是一种严重危害植物的大气污染物,臭氧浓度的升高会对农作物、林木等产生一系列的损害。根系是树木生存的基本要素,臭氧对根结构的根本性改变会最终影响根功能,从而影响树木的整体健康以及对环境胁迫的抗性,通过综述臭氧胁迫对森林树木根系影响的研究进展,可以为我国学者进一步了解臭氧对森林树木根系生态影响提供科学素材。有关大气臭氧浓度升高对森林树木根系生态的影响,目前研究主要包括森林树木根系生长、细根动态和周转、根系呼吸、根系碳水化合物、菌根、根际微生物的响应变化等几个方面。臭氧对树木根系的影响与臭氧浓度、树种、树龄、群落组成及种植条件相关。目前有关臭氧胁迫对树木根系的机制研究还比较缺乏,今后应该加强臭氧胁迫下根系形态构型的原位观察测定和定量分析研究,内源激素响应,胁迫信号感受、转导与其它信号途径的互作关系以及分子生物学机制方面的研究。     

Structural changes of residual lignin in softwood kraft pulp treated with manganese peroxidase

Structural changes of residual lignin in unbleached softwood kraft pulp (SWKP) during manganese peroxidase (MnP) treatment were investigated to obtain some understanding of the biobleaching action of SWKP with MnP treatment. Alkaline-extracted lignin from darkened SWKP by MnP showed more intense color and contained moreo-quinone than that from control SWKP. However, no difference in the conjugated-carbonyl was observed between the lignins from MnP-treated and control SWKP. The nitrobenzene oxidation analysis revealed that oxidative condensation of non-condensed lignin in SWKP occurs during an early stage of MnP treatment. These observations were supported by the model experiment in which the lignin prepared from control SWKP was subjected to MnP treatments three times, and the changes of color and functional groups in the lignin were determined after each treatment. These results suggested that an increase ino-quinone and the condensation reaction of non-condensed lignin in SWKP are responsible for the characteristic darkening of SWKP during MnP treatment. It was also ascertained that darkened lignin was degraded and brightened by repeated MnP treatments.     

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.     

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     

Differences in biosyntheses of guaiacyl and syringyl lignins in woods

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     

Biobleaching of unbleached and oxygen-bleached hardwood kraft pulp by culture filtrate containing manganese peroxidase and lignin peroxidase fromPhanerochaete chrysosporium

Unbleached and oxygen-bleached hardwood kraft pulp (UKP and OKP), respectively, were bleached with a culture filtrate containing manganese peroxidase (MnP) and lignin peroxidase (LiP) fromPhanerochaete chrysosporium Burds. The brightness increases of UKP upon biobleaching with the culture filtrate with and without MnSO₄ were the same. The brightness increase of OKP with MnSO₄ decreased to about half that seen without MnSO₄. Changes in the brightness of UKP and OKP by treatment with the culture filtrate were determined. The brightness increased sharply by about eight points during the first 3h. The 3-h treatment was repeated seven times. The brightness increased linearly with the bleaching of UKP. On bleaching of OKP, the brightness increased slowly and stopped at about 78%.Part of this report was presented at the 62nd Pulp and Paper Research Conference of the Japan Tappi, Tokyo, June 1995