核桃壳木质素的结构研究

核桃加工过程会产生大量核桃壳,而核桃壳中木质素含量较高,可作为潜在商业木质素的来源。为充分利用核桃壳中的木质素,必须了解核桃壳木质素的结构特点。用不同浓度的碱溶液对核桃壳中的木质素进行逐级提取,得到了4种碱木质素,并探索了各浓度梯度下木质素的得率。随后,通过深度酶水解得到了酶解残渣木质素。利用凝胶色谱(GPC)、红外光谱(FT-IR)和二维核磁共振(2D HSQC)技术对分离所得木质素样品的结构进行定性和定量表征。对各木质素样品的纯度及分子结构特点进行综合分析后发现,通过逐级碱提核桃壳得到的碱木质素总得率仅为27.25%,但碱提核桃壳残渣酶水解后得到的酶解残渣木质素的得率却高达62.44%。研究中木质素总得率达到了89.69%,代表性良好。4种碱提木质素样品的相对分子质量(1 930~2 330 g/mol)明显低于酶水解木质素样品的相对分子质量(3 190 g/mol),且所有木质素样品的分子质量分布都相对较窄(M_w/M_n1.5)。核桃壳木质素为典型的SGH型木质素,该木质素分子中S型单元与G型单元比例相近,且含量远高于H型结构单元。核桃壳木质素中主要联结键为β-O-4'醚键结构、β-β'树脂醇结构及β-5'苯基香豆满结构。研究结果可为核桃壳木质素的高效分离和高值化利用提供理论指导。     

竹子高沸醇溶剂法制备纸浆纤维与木质素的研究

以竹子为原料，在70％～90％的1，4-丁二醇水溶液中添加少量助剂，并在180～200℃条件下反应30～90min，制备得到竹子纸浆纤维和高沸醇木质素高沸醇溶剂(HBS)法制得的竹子纤维经进一步改性可用于造纸或加工成其他纤维素产品，高沸醇木质素较好地保持了木质素的化学活性，灰分含量低于小质素磺酸盐，在材料科学与工程领域有潜在的应用前景。高沸醇溶剂1，4-丁二醇经回收处理可以循环使用。     

低共熔溶剂提高积雪草有效成分提取效率的研究

本研究采用低共熔溶剂法提取积雪草中有效成分,通过气相色谱法分析馏出液中β-石竹烯的浓度;采用高效液相色谱法分析水提取液中羟基积雪草苷和积雪草苷的浓度,并计算得率;检测积雪草提取前后纤维素、半纤维素和木质素的含量,并且采用扫描电镜进行组织结构形态观察。结果显示：(1)低共熔溶剂法馏出液中β-石竹烯的浓度为6.58μL·mL^-1,较水蒸气蒸馏法提高6.15倍;(2)低共熔溶剂法提取羟基积雪草苷和积雪草苷得率分别为1.03%和0.89%,分别较水提取法提高1.40倍和3.68倍;(3)低共熔溶剂提取后的积雪草渣中纤维素、半纤维素和木质素含量分别较原料下降61.39%、59.19%和59.33%,而水蒸气蒸馏法仅下降31.29%、12.43%和2.30%;(4)低共熔溶剂提取后的积雪草渣中的组织结构破坏程度较水提取更严重。由此可知,低共熔溶剂可显著提高积雪草中有效成分的得率,其作用机制是通过溶解植物体的纤维素、半纤维素和木质素,破坏植物组织结构,从而促进有效成分溶出。研究成果为高效提取积雪草工艺提供了研究基础。     

微波辅助山毛竹全组分分离

利用微波辅助加热,在丙酮/乙二醇二元溶剂体系中对山毛竹原料进行全组分分离,得到粗纤维素、木质素和生物基多元醇,并以得到的生物基多元醇为原料制备聚氨酯泡沫。对反应时间、反应温度、催化剂浓硫酸添加量以及两种溶剂比例等条件进行了优化,采用傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)和凝胶渗透色谱(GPC)等分析手段对分离得到的粗纤维素和木质素的结构进行了表征,分析了生物基多元醇添加量对制得的聚氨酯泡沫微观结构、力学性能和热稳定性的影响。结果表明:溶剂与物料的质量比为10∶1、反应温度为120℃、反应时间为20 min、浓硫酸添加量为1.5%(质量分数)以及丙酮/乙二醇二元溶剂的质量比为1∶1时,山毛竹全组分分离效果最好,粗纤维素得率为41.7%,木质素去除率和木质素回收率分别达到85.1%和72.3%。XRD结果表明,与原料相比,经过分离得到的粗纤维结晶度明显上升; GPC结果表明,分离得到的木质素分子量较小且分布均衡。通过对添加不同质量比生物基多元醇聚氨酯泡沫的性能对比可知,当生物基多元醇添加量低于50%时,聚氨酯泡沫可以保持较好的泡孔结构;但随着生物基多元醇的添加量逐渐增加,泡沫的力学性能和热稳定性有所下降。     

毛白杨木材乙二醇醇解过程中木质素结构的FT-IR、1H NMR分析

为探讨木材乙二醇醇解过程中木质素结构的变化机理,以毛白杨磨木木质素(MWL)为研究对象,采用红外光谱和核磁共振等手段对醇解前后的木质素结构变化进行了分析.发现毛白杨木质素属于典型的愈创木基-紫丁香基型(GS型)木质素,G/S比值为1.37.醇解过程中木质素单元间β-O-4连接键大量断开,共轭羰基减少,甲基芳基醚键部分断开,产物中发现了大量新的酚羟基结构.醇解产生的低分子组分有芳香醚类、脂肪醚类、酚类、芳香酸类、不饱和酮类等物质.木质素大分子断裂的同时也有缩合反应发生.     

超声-弱碱协同作用下巨龙竹木质素的分离及表征

巨龙竹是一种具有极高研究和开发价值的大型经济用材竹种,其基础理化性质有待进一步解析研究。为表征巨龙竹木质素的化学结构,在超声-弱碱协同作用下处理竹材原料,脱蜡竹粉在2%NaOH溶液中分别经超声处理5,20,40,60和90 min,并设置仅在2%NaOH溶液中抽提90 min的对照组,最后得到6个木质素样品L_1~L_6。采用红外光谱(FTIR)、核磁共振碳谱(~(13)C NMR)和二维核磁共振(2D HSQC)分别对分离得到的巨龙竹木质素进行结构分析。结果表明:超声-弱碱协同处理对竹材木质素具有良好的促溶效果,随着超声作用时间的增加,木质素得率从6.6%提高到22.9%;巨龙竹木质素大分子主要由愈创木基(G)、紫丁香基(S)和对羟基苯基(H)结构单元构成,属于禾草类木质素(GSH型);巨龙竹木质素大分子的主要联接键为β-O-4'醚键,其次是β-β'和β-5'结构;但随着超声处理时间的增加,巨龙竹木质素中一定量的β-O-4'联接键会被打断。     

半乳糖醛酸-木质素复合体结构的研究

以果胶前驱物α-D-半乳糖醛酸和木质素前驱物松柏醇-β-D-葡萄糖苷为起始物,在复合酶(β-葡萄糖苷酶、葡萄糖氧化酶、漆酶和辣根过氧化物酶)的协同作用下,合成出半乳糖醛酸-DHP复合体(GDHPC).通过FT-IR及13C NMR测试,发现产物中DHP的主要结构单元为β-O-4、β-β、β-5和β-1结构.另外,还含有较多的松柏醇/醛和少量的香草醛结构,以及Ar-Cα H2-和醚化5-5’结构.产物GDHPC中,木质素结构单元主要通过α碳与α-D-半乳糖醛酸以酯键、缩醛键和苯甲醚键的方式结合.     

三十烷醇和6-糠基氨基嘌呤对黄瓜果实生长的影响

黄瓜幼果(长5～8 cm)期,用三十烷醇(20～200ppm)和6-糠基氨基嘌呤(50～200ppm)处理,结果表明:80和120ppm三十烷醇使果实纵向增加42.10%和33.70%,横向增加39.80%和51.00%;200ppm 6-糠基氨基嘌呤处理后上述二项指标分别增加26.37%和28.57%,表明80和120ppm三十烷醇和200ppm 6-糠基氨基嘌呤分别为该二种植物激素处理黄瓜幼果的最佳浓度,在幼果期进行果面喷施可极显著加快果实生长速度,从而提高黄瓜产量.     

木质素模型化合物与松柏醇-β-D-葡萄糖苷-[α-~(13)C]的聚合反应的研究

为了探讨造纸废水中残余木质素与木质素前驱物之间的聚合反应机理,研究了β-O-4型木质素模型化合物与木质素前驱物松柏醇-β-D-葡萄糖苷-[α-13 C]的聚合反应方法及其反应机理.采用红外光谱、13 CNMR波谱分析聚合产物的特性及结构,并用偏光显微镜对产物进行了观察;采用凝胶渗透色谱法(GPC)测定了产物的数均相对分子质量(Mn).研究表明:在漆酶的催化作用下木质素前驱物松柏醇-β-D-葡萄糖苷与木质素模型物能很完全的发生聚合,产物中不存在起始物的晶体,Mn也大大的增加了.松柏醇-β-D-葡萄糖苷能与木质素模型物聚合,为进一步研究木质素前驱物松柏醇葡萄糖苷用于废水处理的研究奠定了基础.     

两步法预处理对杨木酶水解及木质素吸附性能的影响

研究了不同的两步法预处理对杨木酶水解和木质素吸附性能的影响,结果显示:未处理原料中木质素为29.05%,其酶水解得率仅为15.24%;蒸汽爆破一步法预处理后物料中木质素为34.88%,酸性基团仅为10.16 mmol/kg,酶水解得率为56.88%,预处理过程中木质素几乎没有脱除,因此未能回收作为吸附剂使用。碱性氧化-蒸汽爆破和碱性磺化-蒸汽爆破两步法预处理后物料中木质素减少至21.06%和17.68%,酸性基团增加至101.34和107.69 mmol/kg,酶水解得率由一步法的56.88%提高至74.38%和81.09%,两步法预处理脱除了原料中50%左右的木质素,经回收可作为重金属离子吸附剂使用,对Pb(Ⅱ)的最大吸附量分别为158.73和142.86 mg/g。分析表明:碱性磺化-蒸汽爆破两步法预处理既可大量脱除木质素,增强纤维素酶水解,又可对木质素进行改性,提高木质素对重金属离子Pb(Ⅱ)的吸附性能。     

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.     

Characterization of Brauns’ lignin from fresh and vacuum-dried birch (Betula pendula) wood

Brauns’ lignins present in the methanol extracts of fresh birch (Betula pendula) xylem and of sawn birch board subjected to vacuum drying were characterized by ¹H and ¹³C NMR spectroscopy (1D and 2D), IR spectroscopy, gel permeation chromatography (GPC) and colour measurements (CIELab) in order to find out whether Brauns’ lignin could contribute to the colour change of sawn timber that occurred during vacuum drying. The two Brauns’ lignin samples contained about equal amounts of syringylpropane and guaiacylpropane units linked with β-O-4 and β–β side-chain structures. Molecular weight of the Brauns’ lignin of vacuum-dried birch board (acetylated: 5,200 g mol⁻¹) was higher than that of the Brauns’ lignin of fresh birch wood (acetylated: 4,400 g mol⁻¹). The Brauns’ lignin of vacuum-dried wood was also clearly darker and more prominently yellow and red; between the Brauns’ lignin samples was 23.59. The differences in the molecular weights and colours suggest that the Brauns’ lignin underwent a chemical change during vacuum drying of the wood and that this change may have affected the colour of the wood.     

Analysis of Chinese larch (L. gmelini) SCMP bleachability

The dissolution of lignin and major ploysaccharides from sulfonated chemimechanical pulp (SCMP) ofL. gmelini during sulfonation and defibration, the tharacteristics of lignin and bleachability of larch SCMP were studied using gas chromatography (GC), IR, UV spectrometry, ’H-NMR, “C-NMR and chemical analyses.     

Reaction behavior of lignin in supercritical methanol as studied with lignin model compounds

 The reaction behavior and kinetics of lignin model compounds were studied in supercritical methanol with a batch-type supercritical biomass conversion system. Guaiacol, veratrole, 2,6-dimethoxyphenol, and 1,2,3-trimethoxybenzene were used as model compounds for aromatic rings in lignin. In addition, 5-5, β-1, β-O-4, and α-O-4 types of dimeric lignin model compounds were used as representatives of linkages in lignin. As a result, aromatic rings and 5-5 (biphenyl)-type structures were stable in supercritical methanol, and the β-1 linkage was not cleaved in the β-1-type structure but converted rapidly to stilbene. On the other hand, β-ether and α-ether linkages of β-O-4 and α-O-4 lignin model compounds were cleaved rapidly, and these compounds decomposed to some monomeric compounds. Phenolic compounds were found to be more reactive than nonphenolic compounds. These results indicate that cleavages of ether linkages mainly contribute to the depolymerization of lignin, whereas condensed linkages such as the 5-5 and β-1 types are not cleaved in supercritical methanol. Therefore, it is suggested that the supercritical methanol treatment effectively depolymerizes lignin into the lower-molecular-weight products as a methanol-soluble portion mainly by cleavage of the β-ether structure, which is the dominant linkage in lignin. Received: December 19, 2001 / Accepted: April 30, 2002 Acknowledgments This research has been done under the research program for the development of technologies for establishing an ecosystem based on recycling in rural villages for the twenty-first century from the Ministry of Agriculture, Forestry and Fisheries, Japan; by a Grant-in-Aid for Scientific Research (B)(2) (no.12460144, 2001.4–2003.3) from the Ministry of Education, Culture, Sports, Science and Technology, Japan; and under the research program from Kansai Research Foundation for Technology Promotion, Japan. The authors thank them for their financial support. This study was presented in part at the 45th Lignin Symposium, Ehime, Japan, October 2000 and the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002 Correspondence to:S. Saka     

Structural characterization of lignin from wheat straw

Enzyme/mild acidolysis lignin (EMAL) was isolated from wheat straw. The structural characterization of wheat straw EMAL was investigated by FT-IR, ¹H NMR, quantitative ³¹P NMR and DFRC, and DEPT CH (θ = 135C°) techniques. The wheat straw EMAL was a GSH-lignin with β-O-4′ structures and several condensed units (β-5′, β-β′, β-1′, 5-5′) and vinyl ether moieties; the contents of DBDO substructures and total β-aryl ether in the wheat straw EMAL were 0.257 mmol·g⁻¹ and 0.818 mmol·g⁻¹, respectively. Meanwhile, the structure features of the hemicelluloses residues attached to lignin were also investigated using DEPT CH (θ = 135C°) spectra.     

Spectrochemical characterization by FT-Raman spectroscopy of wood heat-treated at low temperatures: Japanese larch and beech

Test samples of Japanese larch (Larix leptolepis) heartwood and Japanese beech (Fagus crenata) sapwood were heated for 22 h at constant temperatures (50°–180°C) under three water content conditions. Raman spectra of the samples were recorded before and after the heat treatments, and spectral changes in the range from 1000 cm⁻¹ to 1800 cm⁻¹ were evaluated using the difference spectrum method. For both wood species, the Raman band intensity at 1655–1660 cm⁻¹ due mainly to the C=C and C=O groups in lignin clearly decreased with increasing heat-treatment temperature (HTT). The spectral change was thought to reflect the progress of condensation reactions of lignin molecules during the heat treatment. Moreover, the decrease in band intensity was considerably facilitated by the presence of water in the cell wall, suggesting that the condensation is closely related to the softening of lignin. From the spectral changes in the wavenumber region of 1200–1500 cm⁻¹, it was considered that wood constituents are partially decomposed at the higher HTT. Part of this article was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, March 2003     

Analysis of the structure of lignin-carbohydrate complexes by the specific13C tracer method

In the present study the specifically¹³C-enriched lignin precursors of biosynthesis (i.e., coniferin-[side chain–¹³C], coniferin-[side chain-–¹³C] and coniferin-[side chain-–¹³C]) were synthesized and administered exogeneously to ginkgo shoots (Ginkgo biloba L.) to obtain¹³C-enriched lignin-carbohydrate complexes (LCCs). The specifically¹³C-enriched LCCs were isolated from the newly formed xylem of ginkgo shoots administered with the¹³C-enriched precursors and degraded by enzymes. Lignin-rich fractions, so called enzyme-degraded LCCs (EDLCCs), were obtained. By determining their¹³C-NMR spectra, information related to the chemical structure of lignin building units and linkages between phenylpropane units of lignin and carbohydrates were obtained. It was found that these precursors were incorporated in natural lignin successfully. Three lignin-carbohydrates linkages (i.e., ether type, ester type, ketal type) were found at the C -position of the side chain of phenylpropane units in ginkgo LCC. No lignin-carbohydrate bond at the C- or C-position of the lignin side chain was observed in the¹³C-NMR spectra of the¹³C-enriched LCCs. This fact indicates that a specific¹³C tracer technique can be useful in NMR study of the chemical structure of LCCs.Part of this paper was presented at the 5th Pacific Polymer Conference, Kyongju, Korea, October 1997     

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     

A study on the shade tolerance ofMuehlewbeckia complera

Muehlewbeckia complera was introduced to China in 2002 as indoor-hanging ornamental foliage plant. The experiment of the shade tolerance for this species was carried out in different light intensities (0.14–946.00 μmol·m⁻²·s⁻¹). After 40 days in experimental areas, leaf photosynthentic characteristics indexes ofM. complera in different photosynthesis active radiation (PAR) were measured with LI-COR6400 apparatus, such as the light compensation point, light saturation point, and maximum net photosynthesis rate, at the same time, the increments of total leaf area and leaf amount were measured. The results showed that the optimum light intensity range forM. complera was from 9.26 μmol·m⁻²·s⁻¹ to 569.00 μmol·m⁻²·s⁻¹ (463–28150 lx, relative humidity (RH) for 46–60%, temperature at 16–22°C). Under this condition, leaf photosynthetic efficiency was tiptop. AlthoughM. complera belonged to the moderate sun-adaptation plant species, the plant growth was inhibited when PAR increased to the level of 569.000 μmol·m⁻²·s⁻¹ or above.M. complera could sprout new leaves in photosynthesis active radiation of 0.16–19.22 μmol·m⁻²·s⁻¹ (8–961 lx), or 10 μmol·m⁻²·s⁻¹ for above 6 h. Foundation item: This study was supported by the Research Foundation of Northeast Forestry University. Biography: YUE Hua (1962-), female, Associate professor in Northeast Forestry University, Harbin 150040, P. R. China. Responsible editor: Zhu Hong     

Estimation of the carbon storage of forest vegetation and carbon emission from forest fires in Heilongjiang Province, China

The forest resource of Heilongjiang province has important position in china. On the basis of the six times of national forest inventory data （1973-1976, 1977-1981, 1985-1988, 1989-1993, 1994-1998, 1999-2003） surveyed by the Forestry Ministry of P. R. China from 1973 to 2003, the carbon storage of forests in Heilongjiang Province are estimated by using the method of linear relationship of each tree species between biomass and volume. The results show that the carbon storage of Heilongjiang forests in the six periods （1973-1976, 1977-1981, 1985-1988, 1989-1993, 1994-1998, 1999-2003） are 7.164×10^8 t, 4.871×10^8 t, 5.094×10^8 t, 5.292×10^8 t, 5.594×10^8 t and 5.410×10^8 t, respectively., which showed a trend of decreasing in early time and then increasing. It indicated that Heilongjiang forests play an important role as a sink of atmospheric carbon dioxide during past 30 years. Based on the data of forest fires from 1980 to 1999 and ground biomass estimation for some forest types in Heilongjiang Province, it is estimated that the amount of mean annual consumed biomass of forests is 391758.65t-522344.95t, accounting for 6.4%-8.4% of total national consummation from forest fires, and the amount of carbon emission is 176 291.39t-235 055.23t, about 8% of total national emission from forest fires. The emission of CO2, CO, CH4 and NMHC from forest fires in Heilongjiang Province are estimated at 581761.6-775682.25 t, 34892.275-46523.04 t, 14091.11-18788.15 t and 6500-9000 t, respectively, every year.