The Fractionation and Composition Properties of Wheat Straw Lignin and LCC Extracted by Alkaline Solution at Ambient Temperature

采用酸化沉淀法程序分级分离室温麦草碱抽提液中本质素、木质素-碳水化合物复合体(LCC),得到了pH值10.5、9.0和2.0三个级分.pH值10.5级分得率较高,为12.24％,该组分含有大量的碳水化合物,可能是以水不溶性LCC为主.随着pH值的降低,级分中的木质素含量逐渐增加,碳水化合物含量逐渐减少,pH值9.0和2 0组分均是以木质素为主.pH值2.0级分中碳水化合物含有较多的阿拉伯糖和半乳糖,该级分中LCC组成与pH值10.5和9.0级分LCC组成可能不同.抽提液中的SiO2大部分沉淀在pH值10.5和9.0级分中,pH值9.0级分中灰分质量分数高达13.29％.酸化沉淀程序分离法是一种分级分离麦草碱抽提液中木质素、LCC的有效方法.     

麦草室温碱提取木质素、LCC级分程序分离及其组成特性

采用酸化沉淀法程序分级分离室温麦草碱抽提液中木质素、木质素-碳水化合物复合体(LCC),得到了pH值10.5、9.0和2.0三个级分。pH值10.5级分得率较高,为12.24%,该组分含有大量的碳水化合物,可能是以水不溶性LCC为主。随着pH值的降低,级分中的木质素含量逐渐增加,碳水化合物含量逐渐减少,pH值9.0和2.0组分均是以木质素为主。pH值2.0级分中碳水化合物含有较多的阿拉伯糖和半乳糖,该级分中LCC组成与pH值10.5和9.0级分LCC组成可能不同。抽提液中的SiO2大部分沉淀在pH值10.5和9.0级分中,pH值9.0级分中灰分质量分数高达13.29%。酸化沉淀程序分离法是一种分级分离麦草碱抽提液中木质素、LCC的有效方法。     

水性油墨用聚酰胺树脂的合成与性能研究

由油酸二聚酸(ODA)、聚合松香(PR)、乙二胺(EDA)经缩聚反应得到低相对分子质量端羧基聚酰胺树脂(CLMPA),而后再与己二酸(AA)、环氧树脂(E-51)开环聚合反应得多羟基聚酰胺树脂(PHPA),最后与甲基四氢苯酐(Me-THPA)酯化,得到多羧基聚酰胺树脂(PCPA),中和成盐,得阴离子型水性聚酰胺树脂(AWPA)。通过考察目标产物水溶性、涂膜的耐水性、相对分子质量(Mr)、黏度及玻璃化转变温度(Tg)研究了PR和ODA的物质的量之比(PR/ODA)、CLMPA和AA的物质的量之比(CLMPA/AA)对AWPA性能的影响,并通过红外光谱和核磁共振氢谱对各中间体及目标产物进行了表征。结果表明:当PR/ODA为4∶6、CLMPA/AA为2∶10时,合成的聚酰胺树脂溶于水,Mr7 264,吸水率27.6%,黏度42.3 Pa.s(100℃),Tg 47.15℃。     

蓝花楹木质素-碳水化合物复合体在硫酸盐法蒸煮过程中的变化

以蓝花楹为原料提取木质素-碳水化合物复合体(LCC),并对LCC的结构进行分析,同时模拟硫酸盐法蒸煮过程,采用蒸煮的方法对LCC进行处理,并对处理后的产物进行红外光谱和核磁共振分析,研究蓝花楹LCC的结构变化,探讨其在硫酸盐法蒸煮过程中LCC的形成和降解情况。研究发现:蓝花楹LCC中的碳水化合物在蒸煮过程中非常不稳定,大部分发生降解,而蒸煮产物中含有对碱稳定的LCC结构,也含有新形成的LCC结构,这种新形成的LCC是5-5缩合型木质素结构与木聚糖形成的以化学键连接的LCC结构,且其对碱也非常稳定。     

磨木木质素在硫酸盐法蒸煮过程中的降解及与木糖的缩合

在木糖存在的条件下,采用硫酸盐法蒸煮对蓝花楹磨木木质素(MWL)进行处理,然后对处理后的产物进行红外光谱和13 CNMR分析,研究蓝花楹MWL的结构变化,探讨在硫酸盐法蒸煮过程中木质素-碳水化合物复合体(LCC)的形成情况.研究发现:蓝花楹MWL结构单元之间的α-烷基芳基醚键、β-O-4型连接键很容易发生断裂,而在这些连接键发生断裂的同时,形成的木质素中间体与木糖通过化学键的结合,形成新的LCC结构.这种新形成的LCC结构主要是由β-O-4型木质素结构和5-5′缩合型木质素结构与木糖形成的以苯甲醚键连接的LCC,这种新形成的LCC结构对碱非常稳定.     

木质素脱氢聚合物生物合成的探讨

模拟自然条件,以松柏醇葡萄糖苷为原料,在β-葡萄糖苷酶、葡萄糖氧化酶及过氧化物酶存在下,分别用混合法和滴加法,来合成木质素脱氢聚合物(DHP).通过凝胶渗透色谱(GPC)、FT-IR、13C NMR与1H NMR分析,发现混合法所得DHP中β-5结构含量略高,而滴加法所得DHP中β-O-4结构含量较高.从GPC分析可以得到,混合法DHP的相对分子质量(Mr)低于滴加法DHP的Mr.从而,说明滴加的方法优于直接混合的方法.证实了β-O-4,β-β,β-5,β-1为DHP中的主要结构单元,此外还含有大量的松柏醇结构、少量香草醛及带有亚甲基结构的苯丙烷结构和以醚键与木质素相结合的少量碳水化合物.     

桉木APMP制浆废液中主要有机组分的热解特性

采用高温静态水平管式炉对桉木碱性过氧化氢机械浆(APMP)制浆废液固形物(ASLS)及其3种主要组分,即碱木质素(AL)、多糖(PLS)与木质素-碳水化合物复合体(LCC)在400~800℃进行快速热解,利用GC、GC/MS、FT-IR和SEM等手段,分析了各相热解产物组成与分布规律。结果表明,AL对ASLS热解液相产物得率影响较大,PLS对气相产物与固相产物得率的影响较大。ASLS热解产生H2能力较强而与组分热解关系不大,高温阶段PLS热解生成CO能力显著提高,AL热解产生烃类化合物的能力明显高于其他组分。ASLS热解液相产物中的苯环化合物主要源自于AL热解产生,酚类与稠环化合物主要源自于AL和LCC组分热解产生,而酮类、呋喃类和酸类则是由AL、LCC和PLS热解后共同产生。ASLS、AL、PLS和LCC热解半焦表观形貌的差异比较明显。     

纤维素前驱物6-~(13)C标记示踪研究纤维素与木质素连接方式

从细胞壁多糖的角度分析糖单元与木质素苯丙烷结构单元之间的共价键连接方式,合成了带6-13C标记的纤维素前驱物尿苷二磷酸葡萄糖,并将其与苯丙氨酸解氨酶(PAL)的抑制剂L-2-氨氧基-3-苯基丙酸(AOPP)及外源性木质素前驱物松柏醇-β-D-葡萄糖苷一起投入生长中的银杏植物体内,分析结果证明了(6-13C)尿苷二磷酸葡萄糖是对植物中纤维素进行选择性13C标记的合适的前驱物。从正常生长的银杏新生木质部组织提取木质素-碳水化合物复合体(LCC),并用纤维素酶和半纤维素酶酶解LCC得LCC酶解产物(EDLCC)。红外光谱及13C NMR检测LCC和EDLCC,分析证实了纤维素6位碳与木质素以苯甲醚键方式连接。     

植物细胞壁中甘露糖单元与木质素间化学键连接的研究

从甘露糖单元的角度分析半纤维素中糖单元与木质素苯丙烷结构单元之间的连接方式,从而阐明裸子植物中木质素-碳水化合物复合体(LCC)的木质素与半纤维素之间的相互关系。为了使生长中的植物细胞壁甘露糖单元上的碳原子被13C同位素示踪并抑制甘露糖向木质素转化,将带D-13C6-甘露糖、外源性木质素前驱物松伯醇-β-D-葡萄糖苷以及苯丙氨酸解氨酶的抑制剂AOPP一起投入到银杏(Ginkgo biloba L.)植株中。结果表明,新生木质部的LCC中甘露糖单元被13C同位素标记,而且对银杏的正常代谢没有明显的影响。从带13C标记的新生木质部组织提取LCC,并用纤维素酶和半纤维素酶酶解LCC得酶解LCC(EDLCC)。用FT-IR及13C NMR分析LCC和EDLCC,结果证明半纤维素中的甘露糖C-6位与木质素侧链的α-C以苯甲醚键方式连接。     

银杏LCC制备多孔生物载体及在人体肝细胞培养中的应用

以银杏木质素-碳水化合物复合体(LCC)为原料,通过洗脱支架的方法制备医用多孔生物载体,并利用红外光谱、液相色谱、核磁共振波谱及扫描电子显微镜对该生物载体的主要成分含量、化学结构以及表面形态进行分析。结果表明:以银杏LCC为原料可以制备性能优良的生物载体。该载体不仅含有愈创木基型苯丙烷结构单元,而且糖组分中对人体肝细胞有较高生物相容性的半乳糖和甘露糖分别占3.30%和21.94%。制备的多孔生物载体孔隙率可达60%以上,平均孔径约为130μm。用多孔生物载体进行人体肝细胞培养,发现人体肝细胞能够成功地在银杏LCC多孔生物载体上生长,且细胞增殖较快,白蛋白分泌和葡萄糖代谢活性的测定结果表明肝细胞具有较高的代谢活性。研究结果表明银杏LCC多孔生物载体具有良好的生物相容性。     

Structure of small lignin fragments retained in water-soluble polysaccharides extracted from birch MWL isolation residue

To analyze the structural features of lignin in the vicinity of lignin–carbohydrate linkages, water-soluble lignin–carbohydrate complex (LCC) with low lignin content was prepared from residual birch wood meal after the extraction of milled wood lignin (MWL). The molecular weight distribution of lignin in this LCC appeared together with carbohydrate in the relatively high molecular weight region of the gel permeation chromatogram. This result was consistent with our previous results obtained for the same fraction of Japanese cedar (sugi); however, after treatment with polysaccharide-degrading enzyme, the molecular weight distribution of carbohydrate and that of lignin shifted significantly to the lower region. These results demonstrated that molecular size of this LCC is determined by carbohydrates while lignin is present as a minor fragment in this fraction. The syringyl/guaiacyl (S/V) ratio of this LCC was higher than other lignin fractions. Ozonation analysis implied that this LCC has a relatively high number of β-1 structures. It is likely that lignin that exists near lignin–carbohydrate linkages has more endwise-type features than other lignin fractions.This paper was presented in part at the 48th Lignin Symposium, Fukui, Japan, October 2003 and at the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003     

Molecular properties of lignin-carbohydrate complexes from beech (Fagus crenata) and pine (Pinus densiflora) woods

Summary Lignin-carbohydrate complexes (LCC) were isolated from pine (Pinus densiflora) and beech (Fagus crenata) milled-wood lignins. The LCCs were treated with enzyme to obtain precipitates (A-P, B-P) and water soluble fractions. The water soluble fraction from beech LCC was subjected to gel filtration to give LCC fragments (B-E-I). In order to protect the phenolic hydroxyl group, B-E-I and B-P were methylated with diazomethane, resulting in nonphenolic LCC fractions B-E-Ip and B-Pp, respectively. On treatment of B-E-I and B-P with sodium hydroxide, a remarkable amount of xylose and a trace of arabinose were detected as monomeric sugars. However, the same alkaline treatment of B-E-Ip and B-Pp gave only a faint trace of xylose. With DDQ treatment of acetylated B-E-I and B-P, monomeric sugars were released in the same amount as those obtained on alkaline treatment. Methylation of the monomeric sugars gave monomethylated xylose. From these results, it was concluded that xylose residues participate in lignin-carbohydrate linkages, and that lignin is linked to xylose at the 0–2 or 0–3 positions through an alkali-labile benzyl ether bond. The molecular-weight distributions of the lignin moieties, measured by HPLC, indicate that the lignin moieties of beech LCC are 100 times larger but less frequent than those of pine LCC. This nonuniformity of distribution of lignin and carbohydrate moieties in hardwood LCC molecules would result in less hydrophobic interaction in aqueous solutions.     

Combinations of wood and silicate Part 6. Biological resistances of wood-mineral composites using water glass-boron compound system

Summary Wood-mineral composites were made by introducing inorganic substances into wood using the water glass (sodium silicate)-boron compound system (double treatment). Composites were also prepared with boron compounds alone (single treatment), and biological resistances of the two types of composites were evaluated and compared.After the leaching procedure, the composites using the water glass-boron compound system showed generally excellent termite resistances with the negligible weight losses of specimens and high mortalities of workers and soldiers. On the contrary, the single treatment and the double treatment using the reactants of non-boron compounds showed slight or little resistances against termite attacks, accounting for the high leachability of the inorganic substances formed in wood and/or low effectiveness of the chemicals.Also, the water glass-boron compound system was found to enhance greatly the decay resistances if water-soluble inorganic substances were fully removed out from the specimens. The formation of insoluble inorganic substances in the water glass-boron compound system proved to contribute much to the enhancement of biological resistances.The authors express their appreciation to Mr. Ryuji Tadokoro and Mr. Tsuyoshi Kuriu for their assistance in sample preparation and biological testing, respectively.     

Ester linkages between lignin and glucuronoxylan in a lignin-carbohydrate complex from beech (Fagus crenata) wood

Summary A water-soluble lignin-carbohydrate complex (LCC) isolated from beech (Fagus crenata) MWL was investigated. Results from gelfiltration chromatography and the infrared spectrum of the LCC treated with alkali under mild conditions indicated that the LCC contained alkali-labile bonds. Decrease of uronic acid content and the detection of 4-O-methylglucose in the sodium borohydride-reduced LCC suggested the presence of an ester linkage between lignin and glucuronic acid in the glucuronoxylan. Conductometric titration also indicated the existence of glucuronic acid ester linked to lignin. From these results, it is concluded that the LCC contained an ester linkage between lignin and glucuronoxylan and that about one-third of the glucuronic acid present in the LCC was involved in this ester linkage.     

Effect of the presence of lignin on the structure and reactivity to hydrolysis of lignincarbohydrate complexes of poplar wood obtained by sulfate pulping

Summary Lignincarbohydrate complexes (LCC) of poplar wood obtained by sulfate pulping and containing lignin in amounts of 0.9–8.3% have been studied by X-ray diffractometry. Heterogeneous hydrolysis methods have been used to determine their reactivity. The content of the crystalline fraction in LCC depends on the lignin removal and increases with the decrease of the lignin content. The degree of crystallinity of cellulose in sawdust and in LCC is fairly high and changes slightly with the lignin removal. The presence of lignin plays a blocking role in the heterogeneous hydrolysis and decreases the rate constant. It is suggested that lignin is bonded to cellulose on the outer surfaces of the crystalline part of the cellulose fibril. Some possible variants of these bonds are discussed.     

Differential scanning calorimetric analysis of the lignin-carbohydrate complex degraded by wood-rotting fungi

Differential scanning calorimetric (DSC) analysis was applied to the lignin-carbohydrate complex (LCC) fractions degraded by the wood-rotting fungiTyromyces palustris andCoriolus versicolor. Based on changes of the thermogram, it is assumed that the brown-rot fungusT. palustris split the hemicellulose fragment from the LCC during incubation. On the other hand, in the case of the white-rot fungusC. versicolor, the peak temperature of the LCC fraction became higher and then lower, indicating that this fungus first degraded the hemicellulose portion and then decomposed the lignin polymer. Furthermore, the appearance of a lignin-rich fraction was found in the fraction fromC. versicolor, which was not determined by gel-permeation chromatographic analysis. These results demonstrated that DSC analysis can be used to analyze the decay mechanism of solid lignocellulosic samples.Part of this report was presented at the 41st Lignin Symposium, Nagoya, October 1996     

盐分胁迫对土沉香苗木生长和生理指标的影响

通过测定土沉香幼苗在盐分胁迫下生长与生理特征,探讨其耐盐性。结果表明,土沉香幼苗的苗高和地径的增长率随着盐分浓度的增加而减少;叶片膜透性、MDA摩尔浓度、SOD含量、游离脯氨酸含量随着盐分浓度的增加而增加,当NaCl质量分数≤0.4%时,叶片膜透性、MDA摩尔浓度、SOD含量、游离脯氨酸含量与对照相比增加不显著;土沉香叶片中叶绿素含量随着NaCl质量分数的增大呈先增加后减少的趋势,低浓度的盐分胁迫能使叶片中的叶绿素含量增加。由此说明,土沉香苗木具有一定的耐盐性。     

The aging effects of water immersion treatments in wet-bending for standardized testing of wood panels

The durability of wood-based panels is one of the most important properties when they are used in residential construction. The main objectives of this study were to investigate the quantitative relationship between the Wet-bending A test and the Wet-bending B test, examine the aging effects of the treatments specified in the wet-bending methods, and discuss the relationship between wet-bending and outdoor aging tests conducted in Shizuoka, Japan. Wet-bending tests, internal bond tests after humidity treatment, and outdoor aging tests in Shizuoka were conducted using eight types of commercial wood-based panels. A linear relationship was found between the load-carrying capacity (LCC) from the Wet-bending A test and the LCC from the Wet-bending B test. The LCC from Wet-bending B could be obtained from LCC from Wet-bending A by multiplying it by 0.9, which may be applicable as a quantitative ratio of aging effects between the two. LCC for methylenediphenyl diisocyanate-bonded panels recovered to almost 100% of the initial strength. A certain relationship was found between the LCC after Wet-bending A and the LCC after a 1-year outdoor exposure in Shizuoka. Internal bond strength showed a good correlation between the JIS-A treatment and the 1-year outdoor exposure treatment.