Application of Solid-State C NMR Spectroscopy and Dipolar Dephasing Technique to Determine the Extent of Condensation in Technical Lignins

Solid-state ¹³C NMR spectroscopy and dipolar dephasing technique was used to determine the extent of condensation in various technical lignins. The accuracy of dipolar dephasing method was first investigated with the aid of some lignin model compounds and two various methods to determine the degree of condensation were compared. On the basis of the model compound experiments both methods based on dipolar dephasing technique can be applied to investigate the extent of condensation in lignin. The lignin results indicate that technical softwood lignins, as well as enzymatically isolated wood lignin, are more condensed than milled wood lignin, which is generally assumed to represent native lignin. Residual lignins isolated after oxygen delignification and peroxide bleaching stages were found more condensed than residual lignin in unbleached pulps. In studies of the spent liquor lignins of flow-through kraft pulping the extent of condensation was found to increase as the cooking proceeded.     

Conversion of wood pyrolysates to PCDD/F

This contribution assesses the propensity of wood components to form polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) in fires and in combustion in stoves, heaters and burn barrels. Volatiles generated from model lignocellulosic compounds or fractions isolated from wood are reacted with a surrogate ash positioned in a tubular reactor under inert pyrolysis atmospheres. The surrogate ash contains copper and chlorine salts to simulate heterogeneous PCDD/F formation during combustion of preservative-treated wood. Pyrolysis temperatures were selected to fall within the range in which the component decomposes, while the surrogate ash temperature was set at 400 °C which is typical of pyrolysis during fires, and corresponds to conditions which were favourable to PCDD/F formation. PCDF are favoured over PCDD in all experiments. Lignin yields considerably more PCDD/F than the carbohydrates. The ratio of PCDD to PCDF varies according to the chemical structure of the feed; with carbohydrates demonstrating greater relative preference for PCDD than lignin. PCDD/F formation via direct chlorination of dibenzofuran and dibenzo-p-dioxin dominates the pyrolysis of lignin, as evidenced by a significant preference for 2,3,7,8 congeners. Carbohydrates likely produce PCDD/F as a result of formation and condensation of chlorophenol.     

碱木素的近红外光谱吸收机理的研究

通过碱木素模型物对醌、邻醌和香兰素的溶液在800～900 nm的近红外光谱波段内的吸收谱图的对比发现,对醌和邻醌在此波段产生较强的吸收,而香兰素基本上没有吸收,证明了碱木素的醌型结构在800～900 nm波段内产生特征吸收。对银杏和夹竹桃磨木木素碱处理前后的溶液在800～900 nm波段内的吸光度的差别分析,发现夹竹桃的磨木木素的吸光度的相对变化更大,这是由于夹竹桃磨木木素经碱处理后产生了更多的醌型结构。这也是在硫酸盐法蒸煮过程中在800～900 nm波段内阔叶材的蒸煮液吸光度大于针叶材的蒸煮液吸光度的主要原因。     

植物纤维原料的近红外光谱吸收机理的研究

研究发现,植物纤维原料中的木素、纤维素、半纤维素和提取物等主要成分的近红外光谱吸收、同一成分中的不同基团的近红外光谱吸收、不同结构的基团的近红外光谱吸收相互重叠,导致植物纤维原料的近红外吸收光谱十分复杂。然而研究结果表明木素与碳水化合物在C—H键的第一倍频区(1600—1800nm)有明显的吸收差别,木素的苯环在1668nm处有吸收峰,而碳水化合物由于没有苯环C—H键而没有发现有此吸收峰。这反映了植物纤维原料中木素组分在近红外光谱区的信息具有特征吸收,为植物纤维原料的性质分析提供了理论基础。     

NMR spectroscopy applied to the Cultural Heritage: a preliminary study on ancient wood characterisation

High and low resolution solid state NMR methods have been applied to characterise a few samples of ancient wood. In an ancient larch wood sample, by applying ¹H low resolution NMR methods as a function of the temperature, the average pore size and its distribution have been determined. In addition, high resolution NMR techniques have allowed addressing of the question of the proximity of water pools to cellulose and lignin. In particular, a model can be hypothesized in which water pools are surrounded by thin layers of amorphous cellulose and/or lignin while the crystalline domains of cellulose surround the layers of amorphous cellulose. Preliminary results obtained using a fully non invasive and portable NMR unilateral relaxometer, the Eureka-Mouse10 (EM10), are reported. This instrumentation is shown to be perfectly suitable for characterizing degradation in ancient wood samples. PACS 76.60 k     

近红外光谱技术快速识别针叶材和阔叶材的研究

对一种针叶材和一种阔叶材的横切面采集波长范围为780～2 500 nm的近红外漫反射光谱,结合偏最小二乘判别分析法(PLS-DA)对针叶材杉木和阔叶材桉树快速识别的可行性进行了研究,结果表明：(1)利用近红外光谱结合PLS-DA法建立的识别模型对建模样品的识别正确率达到100%,识别模型预测的分类变量值与实际值之间相关系数r达到0.99,SEC为0.07;(2)即使采用短波区域780～1 100 nm的近红外光谱也可以获得理想的识别结果(识别正确率为100%),识别模型的r也达到0.99,SEC为0.07;(3)利用近红外光谱建立的识别模型对未知样本的识别正确率都为100%,说明近红外光谱技术可以快速、准确识别针叶材和阔叶材,这为木材识别提供了一种新方法和技术,也为开发低成本的近红外光谱识别仪器提供了科学依据。     

黑杨受拉木纤维细胞组分及孔隙分布拉曼光谱成像数据研究

倾斜阔叶木枝干弯曲部位的上端在拉伸应力影响下通常会形成受拉木.区别于受拉伸部位下方的对应木,受拉木细胞壁通常会出现理化特性变异的现象,主要归因于细胞次生壁内侧胶质层的形成.采用透射电子显微成像技术揭示了黑杨受拉木与对应木纤维细胞壁分层结构特点,并借助532 nm共聚焦显微拉曼光谱成像(空间分辨率约为0.5μm)及图像叠...     

SEM-EDXA分析不同生长应力木材细胞壁微区木质素沉积

选取具不同生长应力水平的人工林尾巨桉(Eucalyptus uroph ylla×E.grandis)正常木为研究对象,借助场发射环境扫描电子显微镜系统,结合以溴元素做标记的X射线能谱分析技术,分析了尾巨桉细胞壁微区木质素沉积与生长应力的关系.研究结果表明,木纤维细胞壁各微区间木质素含量的大小关系与生长应力高低无关,其...     

马尾松木材褐腐降解的红外光谱研究

用傅立叶变换红外光谱(FTIR)研究了马尾松木材被茯苓褐腐菌降解过程中化学成分的变化。测量了木质素和综纤维素的相关红外吸收峰的峰高比值,用湿化学方法测定了未褐腐和不同褐腐时间木材的Klason木质素含量和综纤维素含量,分析了红外吸收峰峰高比值与Klason木质素含量和综纤维素含量的相关性。褐腐15周内,1736和1372cm-1处归属于综纤维素的吸收峰强度逐渐减弱,1510和1225cm-1处归属于木质素的吸收峰强度逐渐增强;但褐腐15周后,1736和1372cm-1处的吸收强度却开始略微增强,1510和1225cm-1处吸收强度略微下降。I1510/I1736,I1510/I1372,I1225/I1736和I1225/I1372与Klason木质素和综纤维素含量之间均存在非常好的线性相关,R2为0.96～0.99。I1736/I1510和I1372/I1510与综纤维素含量之间存在高度线性相关,R2=0.96。结果说明用红外光谱技术可以对木材褐腐过程中的综纤维素含量和Klason木质素含量进行准确分析。     

Ellipse detection and phase demodulation for wood grain orientation measurement based on the tracheid effect

The methods of ellipse detection and phase demodulation for determining wood grain orientation are proposed. These methods are based on the tracheid effect—laser beam impinging upon a wood surface forms an elongated laser spot with its direction indicative of the grain orientation. Experimental results show that the method of ellipse detection is suitable for the grain orientation measurement on planed softwood surfaces, while the method of phase demodulation is capable of extracting the grain orientation precisely from laser images with low signal-to-noise ratio, such as the images on the surfaces of hardwood species or roughsawn materials.     

二氧化氯氧化云杉木质素的光谱研究

采用傅里叶变换红外光谱(FTIR)、紫外-可见光谱(UV-visible)、傅里叶变换拉曼光谱(FT-Raman)以及核磁共振(1H NMR)分析技术对云杉木质素被二氧化氯氧化前后的结构变化进行了研究。当木质素被二氧化氯氧化时,其骨架结构中的芳香环基团被有效地氧化开环。红外光谱显示木质素中的愈疮木基特征峰强度显著降低,紫丁香基苯基以及对羟基苯基特征吸收峰完全消失,在被氧化后的木质素中出现CO 共轭羰基伸缩振动特征峰。紫外光谱显示木质素在被氧化后位于280 nm处的紫外吸收显著降低。1H核磁共振波谱显示,木质素中连接在芳香环侧链的甲氧基数量被氧化后出现显著的降低,同时与苯环相连的脂肪族侧链在后也相应地减少。研究结果说明二氧化氯能有效地氧化木质素中的芳香环,并将其氧化为带有CO基因的粘康酸及其酯类物质或带有醌型基团的物质。     

木材、竹材密度的CT技术检测

CT在木质材料无损检测中应用日趋广泛,其密度检测是这一应用的关键技术之一。本文用CT对木材、竹材气干材密度进行了研究。通过分析气干材密度(0.303～1.061 g·cm-3)与相应CT值的相互关系,获得24种木材气干材密度与相应CT值之间的线性模型,以及25种木质材料(24种木材及1种竹材)气干材密度与其CT值的混合数学线性模型,相关系数R均达0.99以上,实现了木质材料密度的高效连续精确无损检测,是木质材料CT技术量化检测的突破,为CT技术更好应用于木竹材科学研究与生产加工提供了技术支持和参考依据。     

真空热处理人工林落叶松木材吸湿性变化机理研究

热处理是一种环境友好型的木材改性方法,可提高木材的耐腐性和尺寸稳定性。研究以落叶松木材为试验材料,在处理温度200 ℃的条件下,对其进行了不同时间的真空热处理。利用动态水蒸气吸附(DVS)对热处理前后木材吸湿性的变化进行了表征,通过傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)和X射线衍射(XRD)分析了热处理前后木材化学组分和结构变化,通过化学变化分析阐明了热处理木材吸湿性变化的作用机制。结果表明：真空热处理落叶松木材的平衡含水率降低,热处理木材的平衡含水率随热处理时间的延长呈逐渐下降的趋势。结合红外光谱和光电子能谱发现,热处理后木材纤维素和半纤维素等化学成分发生降解,木质素发生交联缩合反应,使得吸湿性基团含量减少,碳元素与氧元素含量发生变化,氧碳比降低,从C原子的结合形式来看,热处理材的C1含量增加,C2和C3含量降低,这些化学变化使得热处理材的吸湿性降低。此外,真空热处理未破坏木材的结晶结构,木材的相对结晶度随真空热处理时间的延长而增大,结晶度的增大减少了纤维素分子链上吸水性基团的数量,从而降低了木材的吸湿性。     

Triboelectrification of wood with PTFE

Triboelectrification for a rolling contact between hardwood and softwood spheres and a polytetrafluoroethylene (PTFE) plane is studied. For a variety of experimental parameters, the saturation charge developed on the spheres was measured. The results are compared with those reported previously where PTFE spheres were rolled on wood planes. The observations suggest that different principles are involved in the two experimental situations; however, in both cases the saturation charge developed depends on the apparent area of contact.     

基于显微拉曼光谱的稀酸预处理马尾松细胞壁解构机理研究

稀酸预处理可打破木质纤维原料天然抗降解屏障,提高后续酶解和发酵效率,从而使其更高效地转化为生物燃料,然而在亚细胞水平上纤维细胞壁的解构机理仍有待深入研究。采用共聚焦显微拉曼光谱技术与主成分聚类分析法结合,研究了稀酸预处理前后马尾松细胞壁区域化学变化特点。结果表明,累计贡献率高达94.61%的第一与第二主成分空间中光谱样本散点呈现规律性分布;聚类分析可准确提取细胞壁不同形态区域平均拉曼光谱。结合拉曼成像分析发现,细胞角隅木质化程度高,含有较多木质素,次生壁木质化程度低,含有较多碳水化合物。稀酸预处理导致马尾松细胞壁发生了不均一解构,其致密空间结构被破坏,次生壁中碳水化合物典型特征峰2 890 cm-1处信号强度降低了26.9%,表明碳水化合物从该区域大量脱除;碳水化合物在复合胞间层少量脱除,而细胞角隅则出现了其轻微富集。木素在稀酸预处理后发生了重新分布,细胞角隅区拉曼信号显著增强。碳水化合物(主要为半纤维素)的溶出及木质素的重新分布削弱了生物质原料的抗降解性,有利于后续酶解糖化。该研究不仅提供了一种快速、高效的纤维细胞壁区域化学分析方法,还为林木生物质高值转化的研究奠定了重要的理论基础。     

基于光谱和图像特征的阔叶木材与针叶木材同时分类算法研究

木材是人们生活中必不可少的可再生资源,同时在建筑、工艺、家具、结构材料等方面有着举足轻重的地位。市场中常见的木材品种繁多,其品质和价格千差万别,使用智能化技术对木材进行正确的分类不仅可以防止不法商贩“以次充好”,也可以大幅度降低木材分类人员的工作难度。通过木材的遗传信息和解剖学信息可以得到较为准确的木材分类结果,这类方法识别工艺相对复杂,对非专业人员并不友好。借助木材切面的图像信息或光谱信息可以简单方便地对木材进行分类,然而由于不同种木材之间存在的近似性,这类方法往往分类精度不高或只适用于某些阔叶木材。提出了一种基于木材横切面图像信息和光谱信息的多特征木材分类算法,首先分别采集木材横切面的光谱信息以及图像信息;再使用Segnet图像分割方法将待分类样本分成含管孔木材和不含管孔木材两组,并对含管孔样本组中的木材进行管孔分割;然后对含管孔样本组中的木材提取管孔特征、光谱特征以及纹理特征,对无管孔样本组木材提取光谱特征和纹理特征;最后根据这些特征使用支持向量机分别对木材进行分类并记录其木材的分类结果,对分类结果不一致的样本使用相似性判据判断最佳分类结果。为了验证该方法的有效性,以20种常见的阔叶木材和针叶木材的混合样本集为研究对象,对其进行了分类。实验结果显示三种特征均可以对木材进行分类,单独使用光谱特征、纹理特征以及管孔特征对木材进行分类的最高正确率分别为93.00%,89.33% 和69.23%,通过相似测度的判断后三个特征可以相互补充从而进一步提高木材的分类正确率,最高正确率可达98.00%。综上所述,该方法可以对包含阔叶木材和针叶木材的混合样本集中的木材进行分类,木材横切面的光谱特征、纹理特征以及管孔特征可以相互补充,从而使分类正确率进一步的提高。与目前的主流木材分类方法进行对比,发现该算法的分类正确率高于其他算法。     

ESR Study in Reactive Oxygen Species Free Radical Production of Pinus kesiya var. langbianensis Heartwood Treated with Laccase

Enzymatic oxidation of lignin phenolic hydroxyl groups can enhance the level of autoadhesion between wood fibers or particles depending upon the bonding mechanism of wood-based materials without synthetic adhesives such as urea and phenol formaldehyde. The adhesive effect is caused by an increased number of reactive oxygen groups at the fiber surface. The parameters of laccase-treated wood fibers play vital roles in generating reactive oxygen species (ROS) free radicals. Laccase I (white-rot fungi) and laccase II (Aspergillus sp.) are used to catalyze the oxidation of heartwood powder of Pinus kesiya var. langbianensis in suspension under different pH values, temperatures, treatment times and different laccase concentrations. Electron spin resonance spectroscopy and spin trapping technique were used to detect the ROS free radicals generated in the laccase-treated heartwood powder and it was found that in it the concentration of ROS free radicals was higher than that in the control. Analysis of variance indicates that there was a significant difference between the ROS concentration values of laccase-treated heartwood powder under different pH values, treatment temperatures and times, and laccase dosages for both laccase I and II. Furthermore, the concentration of ROS free radicals generated by laccase I is higher than that generated by laccase II. It was found that the optimum conditions for generation of ROS in laccase-treated heartwood powder by the two kinds of laccase are pH 3.0; treatment temperature, 50 °C; treatment time, 2 h; enzyme concentration, 20 units/g of wood powder. Authors' address: Xinfang Duan, Research Institute of Wood Industry, Chinese Academy of Forestry, Wan Shou Shan, Beijing 100091, People's Republic of China     

Fiber modification by steam-explosion: 13C NMR and dynamic mechanical analysis studies of co-refined wood and polypropylene

Wood-plastic material from a novel reactive processing method (co-refining by steam-explosion) was investigated by ¹³C solid state nuclear magnetic resonance (NMR) and dynamic mechanical analysis (DMA). NMR spectra indicated chemistry of the material changed as a result from co-steam-explosion. It was also observed from NMR analysis that the crystallinity of the cellulose increased in the presence of iPP during steam-explosion co-processing. By using variable contact time cross pulse experiments, the relaxation parameters (T _CH and T _1ρ ) for the constitutive components were evaluated to reveal the level of interactions. T _1ρ values for steam-exploded wood had values similar to those published in literature, which are independent relaxation values for lignin and cellulose. However, for co-steam-exploded wood and iPP, the independent value of lignin relative to the amorphous cellulose was absent. It is proposed that lignin adopts an alternate arrangement during co-steam-explosion processing. This arrangement is transient because the independent relaxation of lignin is recovered after the application of heat during compression molding. DMA demonstrated a mechanical reinforcing effect of the steam-exploded wood without influencing the glass transition of polypropylene for the compression molded co-steam-exploded sample. The paper concludes by describing a hypothetical scheme for a meta-stable interaction of wood bio-polymers and iPP.     

Near‐IR surface‐enhanced Raman spectrum of lignin

Compacted powders of commercially available nano‐ and microparticles of silver were used to successfully induce the surface‐enhanced Raman scattering (SERS) effect in spruce milled‐wood lignin (MWL). For the two silver particle sizes used in this investigation, the spectra were mostly similar. Some general characteristics of the lignin SERS spectrum are described. The SERS technique was found to be sensitive for detecting lignin. Significant spectral changes were present between the SERS and normal Raman spectra of MWL. The SERS spectrum was assigned on the basis of literature‐reported vibrational assignments of lignin and its models. Based on significant changes in Raman features, we propose that the lignin is strongly adsorbed on silver. To determine whether SERS of lignin can be obtained directly from wood without its isolation, Wiley‐milled spruce wood (WMW) adsorbed on silver was studied. The results indicated that not only the surface‐enhancement effect was successfully induced in the WMW, but that its spectrum was similar to MWL SERS. Moreover, for WMW, no signals from the carbohydrate components were observed, and therefore, lignin was detected selectively. This nano‐ and microparticle‐based molecularly specific method is expected to make a significant contribution in identifying and investigating lignin in various lignin‐containing materials. Published in 2009 by John Wiley & Sons, Ltd.     

人工降解饱水木材制备方法与光谱研究

考古出土/出水的饱水木质文物保存状态千差万别,内部降解不均匀、差异大,又有取样的限制,造成许多必需的材性定性定量分析和保护效果评价测试难以进行,因此亟需开发实验室可控制备的人工降解饱水木材技术,以获取大量重复性好、性质均匀的样品供研究使用。以健康黄松为原料,探索使用NaOH-真空浸渍-高压水热的联用法制备人工降解饱水木材,取得了初步的成功。制备的人工降解饱水木材的最大含水率（MWC）为260%,340%和575%,分别达到国际上普遍认定的低、中、高度降解饱水考古木材的MWC水平。红外光谱（FTIR）显示制备的人工降解饱水木材纤维素结构保存较为完好,氢键部分断裂;半纤维素显著降解,主链、侧链有断裂现象,1 732 cm-1特征峰消失;木质素有部分降解,1 508 cm-1处木质素芳香环骨架振动等吸收峰相对强度降低并发生偏移。近红外反射光谱（NIR）显示,制得的样品的三大素均发生降解,半纤维素降解程度最高,木质素次之,木质素相对含量升高,表现为C═O相对含量增加。在1 536～1 580 nm区域形成宽峰且峰强度降低,表明纤维素结晶区分子内部、分子间氢键结构均发生断裂。NaOH-真空浸渍-水热联用法与国际上现用的常压高浓度NaOH浸渍法相比,所需NaOH溶液浓度从50%以上降低到1%、处理时间从数月缩短至10 h,制备效率大大提升,所制得的饱水木材的最大含水率显著增大,与考古木材相近,细胞壁化学结构降解程度显著增大。NaOH-真空浸渍-水热联用法有望实现在实验室可控、快速、大量制备不同降解程度的人工降解饱水木材,对饱水木质文物保护水平的提高具有一定的促进意义。