杨木预水解过程中化学组分的降解行为及P因子调控作用

预水解具有环境友好性,符合生物炼制的理念。前期关于预水解的研究多集中于半纤维素的降解、分离和利用,而有关预水解过程中木质素降解的系统研究鲜有报道。以杨木为原料,在130~210℃条件下保温30~120 min进行预水解,结合P因子研究得率、葡聚糖、木聚糖、酸不溶木质素和酸溶木质素的降解率,揭示P因子对木质素降解行为的调控作用,探讨各化学组分在预水解过程中的相互作用。研究表明,预水解过程中木质素发生了一定程度的碎片化。随温度升高和时间延长,酸不溶木质素降解率均逐渐升高;当温度为190和210℃时,随时间延长,酸溶木质素降解率先升高后降低。试验证明,P因子对杨木木质素的降解具有调控作用。随着P因子增加,酸不溶木质素降解率呈指数上升,且分为快速降解(P因子<1500)和缓慢降解(P因子>1500)两个阶段;酸溶木质素降解率先上升后下降,在P因子为1926时达到最大值45.9%。此外,预水解过程中碳水化合物和木质素的降解具有相互作用关系。碳水化合物的降解为木质素的溶出打开了物理通道,同时木质素的重新吸附阻碍了其进一步降解。     

竹浆GIF仿酶漂白木质素降解产物气相色谱-质谱解析

利用气相色谱-质谱联用(GC-MS)方法对GIF仿酶漂白中的木质素降解产物进行了分析,进一步探讨这种仿酶系统对木质素的降解机制.结果显示GIF仿酶处理使竹浆残余木质素进一步氧化降解,降解的主要方式有脱甲基作用、醌型结构的产生和开环、烷基-芳基醚键的开裂、侧链碳-碳连接的氧化断裂等.GC-MS检测所得的降解产物中,含羰基的化合物较多,这是GIF仿酶系统催化氧化的结果.一些醌式结构、共轭羰基和酚类的脱除,也使纸浆因发色基团减少而白度提高.此外,检测出一些糖类降解产物,说明GIF仿酶系统对纸浆碳水化合物有一定的降解作用.     

Characterization of the lignin-derived products from wood as treated in supercritical water

Sugi (Cryptomeria japonica D. Don) and buna (Fugus crenata Blume) woods were treated with supercritical water (>374°C, >22.1 MPa) and fractionated into a water-soluble portion and a water-insoluble residue. The latter was washed with methanol to be fractionated further into a methanol-soluble portion and a methanol-insoluble residue. Whereas the carbohydrate-derived products were in the water-soluble portion, most of the lignin-derived products were found in the methanol-soluble portion and methanol-insoluble residue. The lignin-derived products in the methanol-soluble portion were shown to have more phenolic hydroxyl groups than lignin in original wood. The alkaline nitrobenzene oxidation analyses, however, exhibited much less oxidation product in the methanol-soluble portion and methanol-insoluble residue. These lines of evidence suggest that the ether linkages of lignin are preferentially cleaved during supercritical water treatment. To simulate the reaction of lignin, a study with lignin model compounds was performed;-O-4-type lignin model compounds were found to be cleaved, whereas biphenyl-type compounds were highly stable during supercritical water treatment. These results clearly indicated that the lignin-derived products, mainly consisting of condensed-type linkages of lignin due to the preferential degradation of the ether linkages of lignin, occurred during supercritical water treatment.This study was presented in part at the 45th lignin symposium, Ehime, Japan, October, 2000; and the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1988     

Sulfuric acid bleaching of kraft pulp III: reactivity of kraft pulping-resistant structures under acidic conditions

To investigate the bleaching mechanism, a lignincarbohydrate complex (LCC) model compound, a vinyl ether-type lignin model dimer, and a hexeneuronic acid model compound were treated with dilute sulfuric acid of different pHs. Beech kraft pulp and red pine kraft pulp were also treated with dilute sulfuric acid and then extracted with aqueous alkali. The amount of hexeneuronic acid degradation products in acid effluents and lignin dissolved in alkali effluents were determined. It was found that the benzyl ether-type LCC bond and the vinyl ether bond in lignin were effectively cleaved under the pH where sulfuric acid bleaching of kraft pulp was effective. Hexeneuronic acid group was also effectively degraded during sulfuric acid bleaching. In beech kraft pulp bleaching, both lignin removal and hexeneuronic acid removal contributed to the kappa number reduction. In red pine bleaching, the contribution of hexeneuronic acid removal was negligible, and most of the kappa number reduction was achieved by the lignin removal.Part of this report was presented at the 9th International Symposium on Wood and Pulping Chemistry, Montreal, July 1997     

木质素生物降解的化学反应机制

从化学反应的角度探讨了木质素过氧化物酶催化木质素生物降解的反应机制，通过对木质素结构和其化学反应性的分析，并结合白腐菌（Ｐｈａｎｅｒｏｃｈａｅｔｅｃｈｒｙｓｏｓｐｏｒｉｕｍ）的木质素降解酶类对木质素模型化合物的降解研究，总结出木质素多聚物生物降解的整个过程．     

The chemistry of chromated copper arsenate II. Preservative-wood interactions

 The reactions which cause chromated copper arsenate preservative  to fix strongly into wood are reviewed. A number of the mechanisms proposed in the literature appear chemically implausible. A new model is advanced in which the final fixation products are dominated by chromium (III) arsenate, chromium (III) hydroxide, and copper (II)- wood carboxylate complexes. Carboxylate groups should be generated in large numbers in the reduction of chromium (VI) by primary alcohol groups in lignin and carbohydrate fractions, or in the oxidative degradation of lignin. The model is supported by a recent X-ray absorption fine structure analysis. Received: 13 November 1998     

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     

麦草碱木质素的氧化降解及产物特性的研究(Ⅰ)

对不同氧化条件下 ,麦草氧化碱木质素的分子质量、酸溶木质素含量、酚羟基、羧基、甲氧基含量、表面活性的变化进行了研究。研究表明 ,当用碱量较高 (60 % ,30 % )时 ,其分子质量均一化程度较高 ,加入H2 O2 后分子质量 >10 0 0 0的高分子组分含量明显下降 ,但用碱量较低(10 % ,5 % )时则变化不大 ,说明在O2 /H2 O2 氧化时碱有着明显作用。对酸溶木质素含量来说 ,也呈现出这一规律。木质素经氧化后 ,酚羟基含量升高 ,而羧基、甲氧基含量下降。在高用碱量条件 (60 %、30 % )下 ,氧化木质素的表面张力下降较大 ,添加H2 O2 后下降更为明显。当用碱量为60 %、H2 O2 用量 10 %时 ,氧化木质素 4 %水溶液的表面张力可由原木质素的 4 6.8mN/m降至 38.8mN/m。     

有效降解可再生资源木质素的研究进展

在常见木质素结构特征的基础上,综述了木质素常见的降解利用方法：生物法、化学法、物理法,总结了各种木质素处理方法存在的问题,并对采用物理化学复合降解法处理木质素前景进行了展望。     

碱木质素和PUF的降解产物对聚氨酯材料结构和性能的影响

以碱木质素和聚氨酯泡沫(PUF)的降解产物为添加剂制备复合聚氨酯泡沫材料,并表征了微观结构、表观密度、压缩性能、保温性能等。结果显示,碱木质素可提高与复合基体之间的相容性,原因是其存在强烈的氢键缔合作用。扫描电镜测试显示,碱木质素和PUF的降解产物对材料的微观结构有很大的影响,加入碱木质素有利于提高压缩模量,其压缩模量为146.44 MPa,加入PUF的降解产物会降低压缩模量,其压缩模量为101.59 MPa,而没有加碱木素也没有加PUF降解产物的其压缩模量108.53 MPa。PUF的降解产物的添加降低了样品的保温性能,加入PUF的降解产物的样品的导热系数为PUF降解产物的样品的导热系数为0.032 5 W/(m.K)而不加PUF降解产物的样品的导热系数为0.022 6 W/(m.K)。     

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.     

下的降解

对木质素磺酸盐在紫外光/双氧水(UV/H2O2)体系下的降解过程进行了研究,通过对比处理前后木质素磺酸盐溶液的紫外可见光谱、凝胶渗透色谱(GPC)谱图、红外光谱谱图、1H NMR谱图及溶液化学耗氧量(COD)的变化对其降解过程进行了跟踪和讨论。此外,通过对木质素的模型化合物——愈创木酚降解的研究,推测了降解中苯环的开环过程。实验结果表明,木质素磺酸盐在UV/H2O2体系处理下能够发生降解,降解过程中首先生成一些中间产物,随着反应时间的加长,最终能够降解成CO2、H2O等小分子化合物。     

用FTIR法研究木材阻燃剂FRW的阻燃机理

采用FTIR显微分析技术,对FRW阻燃处理红松木材限制燃烧固相产物的结构进行分析;采用GC_FTIR联机分析方法,对经FRW阻燃剂及其主要组分处理的紫椴木材试样的热解挥发性产物进行分析和鉴定;讨论FRW阻燃处理木材的热解炭化过程、阻燃剂的作用以及热解产物的结构特点。结果表明:FRW阻燃木材受热时,随着温度的升高,在FRW及其分解产物的催化下,木材逐步发生聚糖脱水、半纤维素脱乙酸、聚糖降解、木质素降解、木材热解产物聚合、脂肪族聚合物脱氧及芳构化等反应,最终炭化;FRW阻燃剂改变了木材的热解途径,并且显著降低了挥发性有机化合物的生成量。     

FTIR-PAS study of light-induced changes in the surface of acetylated or polyethylene glycol-impregnated wood

The objective of this study was to characterize the surface changes in acetylated and polyethylene glycol (PEG)-impregnated wood caused during light irradiation by Fourier transformed infrared photoacoustic spectroscopy analysis to determine their effects on the reduction of light deterioration. Light irradiation made the color of the chemically modified wood lighter or more vivid, whereas it deepened the color of the untreated wood. The color difference during light irradiation was less in the chemically modified wood than the untreated wood. The color difference of PEG-impregnated wood increased with increasing irradiation time. The light irradiation generated much carbonyl and significantly degraded lignin in the untreated wood. The generation of carbonyl and lignin degradation diminished in the acetylated wood in comparison with the untreated wood, indicating that acetylation restrained the photochemical degradation of wood. Deacetylation did not occur during light irradiation of the acetylated wood. The PEG impregnation decreased the generation of carbonyl and degradation of lignin during light irradiation. However, the irradiation occurred a little photochemical degradation of PEG, generating the carbonyl. Therefore, longer light irradiation should increase the degradation of PEG, thus reducing the effect of treatment. The correlation between the color difference and lignin degradation was high, indicating that the color changes during light irradiation significantly depended on lignin degradation. The chemical modification reduced the degradation of lignin and consequently decreased the color difference. Some of the compounds containing the carbonyl generated during light irradiation were water-soluble.This paper was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000     

Lignin-degrading activity of edible mushroom <Emphasis Type="Italic">Strobilurus ohshimae</Emphasis> that forms fruiting bodies on buried sugi (<Emphasis Type="Italic">Cryptomeria japonica</Emphasis>) twigs

Strobilurus ohshimae is an edible mushroom, and it specifically forms its fruiting bodies on buried sugi (Cryptomeria japonica) twigs. In this research, we studied lignindegrading activity of S. ohshimae. We isolated 18 strains of S. ohshimae from various regions of Japan, and determined their lignin degradation rates on sugi wood meal medium. All the strains of S. ohshimae degraded approximately 6%–12% of sugi lignin in 30 days, and these lignin degradation rates were 1.5–3 times higher than those of Trametes versicolor, which is a typical lignin-degrading fungus. Among the three main lignin-degrading enzymes, activity of lignin peroxidase and manganese peroxidase was not observed, while 4340U/g of laccase was produced in 30 days. To investigate the effect of wood species on lignin degradation by S. ohshimae, the lignin degradation rate and laccase productivity on sugi wood meal medium were compared with those on beech (Fagus crenata). In T. versicolor, both lignin degradation rate and laccase productivity were higher on beech than on sugi. Conversely, in S. ohshimae, lignin degradation rate and laccase productivity were higher on sugi than on beech. Therefore, it was suggested that coniferous lignin is not always difficult to degrade for the fungi that inhabit softwood. Part of this article presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, August 2004     

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.     

真菌降解木质素的研究现状

在介绍木质素结构的基础上 ,从降解木质素的菌种及主要酶、产酶的条件 ,分析了真菌降解木质素的研究现状 ,介绍了真菌降解木质素及其酶的应用 ,并提出了存在的问题及发展方向     

13种食用菌对稻草生物降解能力的研究

通过对13种食用菌对稻草生物降解能力的研究,结果表明除蒙古白蘑(Tricholamamongolicum)外,其他12菌株对稻草中的木素及纤维素均有一定的降解能力。其中侧耳(Pleurotus.ostreatus)表现出了很强的木素降解能力及较低的综纤维素降解能力,其木素降解率为17.86%,综纤维素降解率为2.44%,SF指数为7.97,为理想的木素降解菌。其他菌株木素降解率为2.30%~16.54%,综纤维素降解率为5.60%~17.32%,而SF指数均较低,介于0.14~2.24。通过线性回归得出菌落直径与变色圈直径比值(d1/d2)和选择性指数(SF)为负相关,其相关系数r=-0.1476,相关性不大。表5参9。     

离子液体[Hmim][CF_3SO_3]在木质素及其模型化合物生物降解中的应用

研究了在室温下,离子液体[Hmim][CF_3SO_3]溶解木质素及其模型化合物后,与酶液在小分子有机酸作用下形成的三元液相平衡体系,及在此体系中进行酶促反应的过程。结果表明:小分子有机酸使水-离子液体形成的两相转化为均相的主要贡献是由羧基提供的,[Hmim][CF_3SO_3]在溶解木质素后依旧保留与有机酸和水形成三元相平衡体系的能力;以酶液作为水相,以溶解了木质素的离子液体作为疏水相,甲酸的掺入在起到平衡水相和疏水相的同时也作为木质素降解酶反应过程中的自由基稳定剂;在三元液相体系的反应中,离子液体引起酶的部分失活;随着反应的进行,碱木质素和木质素脱氢聚合物(DHPs)的降解率分别为56.5%和66.5%,甲氧基分别降低了46.7%和45.3%,生成的酚类化合物分别为204.7和207.0 mg/L,甲酸分别消耗了0.57和0.76 g。DHPs在降解过程中,由于甲酸的过度消耗导致了平衡体系的解体。