茉莉酸甲酯和水杨酸甲酯诱导杨树叶片内酚酸含量的变化

用茉莉酸甲酯(MeJa)及水杨酸甲酯(MeSa)熏蒸合作杨(P.Simonii×P.Pyramibalis c.v)和黑杨(P.deltoids)植株,采用高效液相色谱技术(HPLC)检测杨树叶片内没什子酸、儿茶酸、邻苯二酚、咖啡酸、香豆酸、阿魏酸和苯甲酸的含量变化,分析MeJa与MeSa诱导植物叶片内酚酸含量的差异。结果表明:在不同的处理条件下,不同酚酸含量存在显著差异。MeJA及MeSa熏蒸后的黑杨叶片内没什子酸、香豆酸、咖啡酸、阿魏酸和苯甲酸含量均增加,且没什子酸含量在MeJa处理24h后达到最大量,在MeSa处理12天后达到最大量。MeJa及MeSa熏蒸后的合作杨叶片内没什子酸、邻苯二酚和阿魏酸含量也增加,儿茶酸和苯甲酸含量略有下降,咖啡酸和香豆酸在对照叶片和熏蒸叶片内都没有检测到。说明MeJa与MeSa可作为气体信号诱导植株产生防御反应。图4参23。     

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     

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

A purified softwood kraft lignin was modified by ozone treatment and its activity as an acid soil conditioning agent, mainly focusing on elimination of aluminum toxicity, was assayed by planting experiments. The growth of radish root was examined in nutrient solution containing CaCl₂ and AlCl₃ at pH 4.8 with and without modified kraft lignins. The modified kraft lignins that absorbed 1.8 and 3.9 moles of ozone per C6-C3 unit (M _w 180) showed two effects: the elimination of aluminum toxicity and the acceleration of root growth. The effect on the elimination of aluminum toxicity was observed even with modified kraft lignin that absorbed 1.0 mole of ozone per C6-C3 unit. The high molecular weight part of the modified kraft lignin that absorbed 3.9 moles of ozone per C6-C3 unit also proved to be effective not only in elimination of aluminum toxicity but also in acceleration of root growth. The acceleration effect of ozone-treated lignins on root growth was also observed under the absence of aluminum in planting experiments. This report was presented in part at the 56th Annual Meeting of the Japan Wood Research Society, Akita, Japan, August 2006     

Ready chemical conversion of acid hydrolysis lignin into water-soluble lignosulfonate III: Successive treatment of acid hydrolysis lignin and a lignin model compound by phenolation and arylsulfonation*

The chemical conversion of red pine sulfuric acid lignin (Klason lignin) (SAL) as an acid hydrolysis lignin sample to water-soluble arylsulfonates of lignin derivation (i.e., phenolized SAL) was investigated. Treatment of phenolized SAL with chlorosulfonic acid followed by alkali hydrolysis gave water-soluble sulfonated products with a sulfonic acid group on their aromatic nuclei quantitatively. The products possess 2.0 SO₃Na/C₉ C₆. In contrast, the content of sulfuric acid group in sulfonated SAL was only 0.33C₉. Chlorosulfonation of 1-guaiacyl-l-p-hydroxyphenylethane as a phenolized guaiacyl lignin model compound revealed that the sulfonyl chloride group was introduced at thepara position of an aromatic methoxyl group, theortho position of a phenolic hydroxyl group, or both.     

Ready chemical conversion of acid hydrolysis lignin into water-soluble lignosulfonate II: Hydroxymethylation and subsequent sulfonation of phenolized lignin model compounds

Highly condensed lignin can be transformed by three reactions — phenolation, hydroxymethylation, and neutral sulfonation — to water-soluble lignosulfonate. To elucidate reactivities and products in the latter two reactions, simple compounds were selected as lignin model compounds. With hydroxymethylation of creosol at 60°C, the yield of a condensed-type product with the diarylmethane structure was less than 10%. Hydroxymethylation of 1-guaiacyl-1-p-hydroxy-phenylethane (compound VI) as a phenolized guaiacyl lignin model compound gave four compounds. The initial reaction introduced the hydroxymethyl group mainly in the guaiacyl nucleus, and the additional reaction created two hydroxymethyl groups in the p-hydroxyphenyl nucleus. Contrary to our estimation, treatment of the models with ¹³C-labeled formaldehyde (H¹³CIIO) did not form any diarylmethane structure. Neutral sulfite treatment of hydroxymethylated products gave corresponding sulfonates in high yields. Phenolized guaiacylglycerol--aryl ether (compound XVI) showed a reactivity similar to that of compound VI.This paper was presented at the 45th and 46th annual meetings of the Japan Wood Research Society at Tokyo and Kumamoto, April 1995 and April 1996, respectively     

Origin of free radicals produced from the syringyl end groups in lignins

Enzyme lignin was prepared from reed; it was acid-hydrolyzed and reduced with NaBH₄. Spin concentrations of radicals produced by oxidation of the lignins with K₃[Fe(CN)₆] or H₂O₂ were determined from electron spin resonance spectra. The radicals were observed by the oxidation of sinapyl alcohol. It was found that the two radicals observed by the oxidation of dioxane lignins were deprotonated 2,6-dimethoxyp-benzosemiquinone and 6-hydroxy-2-methoxy-p-benzosemiquinone, and that they were produced from syringyl end groups. The production rate of radicals from syringyl end groups possessing an-carbonyl group was greater than that possessing an-hydroxyl group. It was suggested that stilbene-type syringyl end groups were produced from phenylcoumaran moieties in lignins by acidolysis. The radicals produced from guaiacyl end groups were not observed by the oxidation process.     

Preparation of anion-exchange resins from pine sulfuric acid lignin,one of the acid hydrolysis lignins

To utilize acid hydrolysis lignin effectively, chemical conversion to anion-exchange resin was investigated by two methods. Sulfuric acid lignin (SAL) was selected as a typical acid hydrolysis lignin in this experiment. Because it is less reactive, SAL was phenolated with sulfuric acid catalyst to yield reactive phenolized SAL (P-SAL) with p-hydroxyphenyl nuclei. One method was the restricted resinification of P-SAL followed by the Mannich reaction with formaldehyde and dimethylamine to yield a weakly basic anion-exchange resin with an ion-exchange capacity of 2.4mEq/g. Another method was to react resinified P-SAL with glycidyltrimethylammonium chloride to yield a strongly basic anion-exchange resin with an ion-exchange capacity of 2.0mEq/g. The reaction of a simple P-SAL model compound with an epoxide suggested that the phenolic hydroxyl group of the p-hydroxyphenyl nucleus had slightly higher reactivity than that of the guaiacyl nucleus.Part of this report was presented at the 47th Lignin Symposium, Fukuoka, October 2002     

Preparation of strongly acidic cation-exchange resins from gymnosperm acid hydrolysis lignin

The chemical preparation of strongly acidic cation-exchange resin from sulfuric acid lignin (Klason lignin) (SAL), a typical acid hydrolysis lignin, was investigated. Sulfonation of resinified SAL itself gave a resin with an ion-exchange capacity of 2.3 mEq/g. After resinification with formaldehyde, the phenolized SAL with a reactivep-hydroxyphenyl group yielded a resin with an ion-exchange capacity of 3.2 mEq/g. The latter capacity is superior to that of the corresponding commercial phenol-type resins (2–3 mEq/g), but did not reach the level of the corresponding commercial styrene-type resins (4-5 mEq/g).This paper was presented at the 43th Lignin Symposium, Fuchu, October 1998     

硼酸催化制备木屑活性炭工艺及孔结构特征

以木屑为原料,磷酸为活化剂,硼酸为催化剂制备活性炭。通过正交实验考察了活性炭制备过程中磷屑比、硼酸添加量,活化温度和活化时间等因素对活性炭性能的影响。实验结果表明:生产活性炭的最佳工艺条件为磷屑比为1.5∶1,硼酸的添加量为1%,活化温度是400℃,活化时间为60 min,此时活性炭的得率为33.5%,亚甲基蓝吸附值为225 mg/g,碘吸附值为855 mg/g。添加硼酸的制备方法要比传统的用磷酸制备时的条件更加温和,通过调整工艺条件,可以改变活性炭产品的孔隙结构,生产出用于不同环境的液相吸附专用活性炭。     

乙酸乙酯法分离板栗壳木质素的研究

主要研究了乙酸乙酯水溶液质量分数(ω)、液固比(m/m)、反应温度、保温时间等因素对分离板栗壳木质素的影响。优化的工艺条件为:板栗壳经粉碎、苯醇浸提后作为反应原料,乙酸乙酯(ω)60%,液固比(m/m)为8:1,在高压釜内于180℃保温1h;提取液经减压蒸发回收溶剂,浓缩液在80℃真空干燥,得到棕褐色的粗木质素,然后用1,4-二氧六环溶剂提纯;得到提纯木质素。同时,测定木质素的溶解性能,并对其进行红外与紫外光谱分析。     

Formation and chemical structures of acid-soluble lignin I: sulfuric acid treatment time and acid-soluble lignin content of hardwood

To elucidate the formation mechanism of acidsoluble lignin (ASL) formed in the Klason lignin determination, beech wood meals were treated with sulfuric acid (SA) under various conditions, and the ASL solution was extracted with CHC1₃. The results indicated the following: (1) wood components yielding ASL are dissolved in 72% SA during the initial stage; (2) the quantity of ASL is highest during the initial stage, then decreases with prolonged time of 72% SA treatment and finally reaches a constant value; (3) soluble lignin prepared by 72% SA treatment and subsequent standing in 3% SA again yield insoluble Klason lignin and ASL after boiling in 3% SA; and (4) about half the amount of ASL is dissolved in CHC1₃. The foregoing suggest that wood components yielding ASL are dissolved in 72% SA at the beginning and finally change to ASL after being subjected to depolymerization, hydrolysis, and other reactions. ASL may thus be composed of low-molecular-weight degradation products and hydrophilic derivatives of lignin.     

竹材氨法木质素高效分离试验

本文研究了利用氨水作为蒸煮液对天然原料竹材中木质素的高效分离作用,并探讨了在不同氨水浓度,液固比,最高反应温度,最高反应温度下保温时间等条件对氨水分离竹材中木质素的影响,研究结果表明:当氨水浓度为25%,液固比为6:1,最高反应温度为180℃下保温3 h,氨水对竹材中木质素的分离效果最佳.并就反应得到的氨黑液的资源化利用提出自己看法.     

Enhancement of the biological resistance of wood by phenylboronic acid treatment

Phenylboronic acid (PBA) was tested in terms of boron leachability from treated wood. In addition, the fungal and termiticidal efficacy of PBA-impregnated sugi (Cryptomeria japonica D. Don) wood was tested against the decay fungi Coriolus versicolor (L. ex Fr.) Quel. and Tyromyces palustris (Berk. et Curt) Murr., representing white-rot and brown-rot fungi, respectively, and the Formosan subterranean termite Coptotermes formosanus Shiraki. Ion chromatography analysis of hot water extracts of treated wood before and after leaching indicated that PBA is considerably resistant to water leaching, and saturation of the treatment solution increased the fixation ratio of boron in wood, whereas boric acid could not remain in wood impregnated even with the saturated solution. Decay test results revealed the excellent bioactive performance of PBA. Wood treated with 0.34% PBA solution was found resistant to both decay fungi, even after running-water leaching for 10 days and treatment with 1.00% PBA completely inactivated the Formosan subterranean termite for the leached specimens. Weight gain levels were 0.18% w/w (0.46kg/m³) and 0.99% w/w (2.49kg/m³) for these concentration levels, respectively, after being leached by running water. Contrary to the general belief that boron is a slow-acting toxicant against termites and unable to prevent mass loss of treated wood, PBA acted rapidly, and the mass loss caused by termites was low.This study was presented in part at the 47th annual meeting of the Japan Wood Research Society, Kochi, April, 1997     

Application of cationic polymer prepared from sulfuric acid lignin as a retention aid for usual rosin sizes to neutral papermaking

Cationic polymers that acted as the retention aids for usual rosin sizes in neutral papermaking were prepared from sulfuric acid lignin (SAL), one type of acid lignin. To convert SAL to the cationic polymer (MP-SAL), SAL was phenolated and then treated by the Mannich reaction to introduce the amino groups. In the MP-SAL single system, MP-SAL exhibited high sizing effectiveness in neutral papermaking with the rosin emulsion size. However, MP-SAL showed no sizing effectiveness when soap rosin size was used. MP-SAL showed increased sizing effectiveness as the pK _a of the introduced amino group increased. From this and comparison of the sizing degrees of MP-SAL and polyethylenimine, which possesses a linear structure, it was suggested that the sizing effectiveness was not only affected by the charge density and molecular weight, but also by the basicity of the introduced amino groups and the molecular structure of the retention aid. In the alum–MP-SAL dual system, alum and MP-SAL synergistically enhanced the sizing effectiveness in the rosin emulsion sizing at neutral pH. In turn, this allowed a decrease in the MP-SAL dosage and resulted in a small decrease in brightness.Part of this report was presented at the 48th Lignin Symposium, October 2003, Fukui     

Preparation of board-like moldings from composites of isolated lignins and waste paper II: effect of inorganic salt addition on board performance and evaluation of practical use of MDF

Board-shaped composites with medium density (MDF) were prepared from isolated lignins and waste newspaper, in addition to preparation of the composites with high density (HB). The board properties of both composites concerning bending strength and water resistance were improved by the addition of hardwood acetic acid lignin (HAL). The internal bond strength and water resistance of MDF, in particular the degree of thickness swelling (TS), were also improved by prolonged molding time. Adding inorganic salts contributed to the improvement of TS. The effect depended on the charge of the cation. Considering practical utilization of lignin-based MDF as a structural material, its performance was evaluated by combination of the single-shear test of nailed joints and the modulus of rigidity. As a result, this MDF had sufficient strength to be utilized as an internal shear wall material. Therefore, lignin can be considered as an alternative to conventional adhesives for the production of boards such as HB and MDF.     

不同产地油茶籽油脂肪酸组成研究

运用气相色谱技术分析了河南、湖北、湖南及广西地区产茶籽油脂肪酸的组成。结果表明:茶籽油中油酸、亚油酸、亚麻酸含量及不饱和脂肪酸总含量与产地纬度有关。其中,油酸、亚麻酸含量及不饱和脂肪酸总含量随产地纬度的降低呈现出升高的趋势,而亚油酸的含量随产地纬度的降低呈现出先降低后升高的趋势。     

Formation and chemical structures of acid-soluble lignin II: reaction of aromatic nuclei model compounds with xylan in the presence of a counterpart for condensation,and behavior of lignin model compounds with guaiacyl and syringyl nuclei in 72% sulfuric acid

To elucidate the formation and chemical structures of water-soluble material in acid-soluble lignin (ASL), lignin aromatic nuclei model compounds of creosol (I) and 5-methoxycreosol (II) were reacted with xylose or xylan in the presence of apocynol as a counterpart for condensation in 72% sulfuric acid (SA). The reaction of I gave mainly condensation product. However, the condensation reaction of II with apocynol was suppressed because of steric hindrance from the methoxyl group, and II yielded a C-xyloside after refluxing in 3% SA together with condensation products. To obtain information on CHCl₃-soluble material in ASL, model compounds of arylglycerol--aryl ethers with guaiacyl (VIII) and syringyl (X) nuclei were treated by the Klason procedure. VIII gave only insoluble polymerized product, while X gave insoluble polymerized product and CHCl₃-soluble low molecular weight products, which were dissolved in 3% SA. These results prove earlier views that water-soluble material in ASL consists of condensation products formed from syringyl lignin and monosaccharide units in hemicellulose. In addition, the CHCl₃-soluble material in ASL appears to be composed of low molecular weight degradation products from SA treatment of Klason lignin with the syringyl nucleus.Part of this report was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001 and at the 47th Lignin Symposium, Fukuoka, October 2002, and was reviewed in Mokuzai Gakkaishi (2002) 48:55–62     

西藏不同居群核桃核仁中脂肪酸成分的含量变化

为给挖掘具有优质营养成分的核桃种质资源提供科学依据,对西藏核桃5个地理居群的50个实生农家类型脂肪酸成分进行了分析。结果显示:核桃仁中总脂肪酸含量范围在0.646 1~0.743 6 g/g之间,均值为0.702 8 g/g。核仁中饱和脂肪酸的变化范围为0.039 2~0.095 6 g/g。不饱和脂肪酸的变化范围为0.514 5~0.677 9 g/g,其中单不饱和脂肪酸为0.121 5~0.292 3 g/g,多不饱和脂肪酸含量变化范围为0.242 7~0.504 0 g/g。脂肪酸组成成分变异程度较大,主要表现在单不饱和脂肪酸含量的差异水平上。西藏核桃种仁中单不饱和脂肪酸含量较高,均值为0.198 6 g/g,多不饱和脂肪酸的含量处于中等水平,均值为0.416 g/g。亚油酸和亚麻酸的比值为5.17,大多集中在4.0~6.0之间。居群间饱和脂肪酸含量的差异达到显著水平,其余的组成成分在居群间差异均未达到显著水平。     

Synthesis of new amino acid-type amphoteric surfactants from tall oil fatty acid

Two new amino acid-type amphoteric surfactants — disodiumN-(2-fatty acyl amino) ethyliminodiacetate and disodiumN-(2-fatty acyl amino) ethyl-N,N-bis[3-(2-hydroxy) propylsulfonate] amine — were synthesized using tall oil fatty acids as the raw material. Suitable processing conditions for synthesizing the intermediates and final products were probed. In addition, the chemical structures of the intermediates and the final products were identified by infrared spectroscopy, hydrogen nuclear magnetic resonance spectroscopy, and elemental analysis.     

八角有效成分莽草酸提取新工艺

八角是我国特色林产品,除可以提取茴油外,还含有合成"达菲"的重要成分——莽草酸。本文介绍一种从八角中提取莽草酸的生产新工艺,主要利用离子树脂交换、树脂吸附法、溶剂法等分离提纯方法制备莽草酸,莽草酸纯度达99%以上,得率大于3.5%。