γ射线辐照处理竹材化学组分及结晶度变化研究

利用核磁共振波谱仪和X射线衍射仪,对γ射线辐照处理前后的竹材进行CP/MAS13C-NMR图谱、XRD光谱分析,得出竹材细胞壁主要化学组分在辐照过程中结构和性质的变化规律.随着辐照剂量升高,竹材纤维素结晶度呈现先升高后降低的趋势,半纤维素发生降解,木质素由非酚型向酚型转变.     

γ射线辐照处理竹材化学组分及结晶度变化研究

利用核磁共振波谱仪和X射线衍射仪,对γ射线辐照处理前后的竹材进行CP/MAS 13C-NMR图谱、XRD光谱分析,得出竹材细胞壁主要化学组分在辐照过程中结构和性质的变化规律。随着辐照剂量升高,竹材纤维素结晶度呈现先升高后降低的趋势,半纤维素发生降解,木质素由非酚型向酚型转变。     

拉曼光谱对高地钩叶藤纤维S2层主要成分的预测

棕榈藤(rattan)属于棕榈科(Palmae)省藤亚科藤类植物,是一种产于热带森林中,仅次于木材和竹材的、重要的非木材林产品,具有很高的经济价值和开发前景。全球棕榈藤总共有13个属660余种,其中我国自然分布有4属37种5变种,但有较高经济价值的不到30种。由于目前对棕榈藤的细胞结构,尤其是藤纤维的细胞壁结构知之甚少,严重限制了对棕榈藤材的研究和加工利用。因此,为构建棕榈藤材纤维细胞壁结构模型,以高地钩叶藤(Plectocomia himalayana Griff.)为研究对象,对其基部、 2 m处、中部和梢部四个部位分别截取试样、软化、聚乙二醇包埋、切片。切片在室温下经0.2 mol·L-1的硼氢化钠(NaBH4)溶液浸泡5~6 h后用蒸馏水洗净,利用LabRam XploRA显微共聚焦拉曼光谱仪,采用逐点扫描显微探针成像方法获取光谱数据集。将获得的光谱数据利用LabSpec5软件进行处理,从而得到藤茎不同部位藤皮、藤中、藤芯处纤维细胞次生壁中层(S2)主要成分,即纤维素、半纤维素、木质素相对含量,并就相对含量在径向、轴向变异进行了分析。结果表明,在径向上,高地钩叶藤藤皮处纤维细胞S2层纤维素与半纤维素相对含量最高,木质素相对含量最低;而藤芯处纤维细胞S2层纤维素与半纤维素相对含量最低,木质素相对含量最高;藤中处纤维素、半纤维素及木质素相对含量居中。在轴向上即不同藤龄处,藤皮纤维细胞S2层纤维素和半纤维素的相对含量在2 m处最大,木质素的相对含量在梢部最大;藤芯纤维细胞S2层纤维素、木质素、半纤维素的相对含量分别在中部、 2 m处、基部处最大。藤皮、藤芯与藤茎一样,纤维细胞S2层纤维素相对含量最小值在梢部,半纤维素和木质素相对含量均在中部最少。分析可知,棕榈藤藤茎不同部位,藤纤维细胞壁中层(S2)纤维素、半纤维素及木质素相对含量是不同的。     

共聚焦显微拉曼光谱研究碱处理对稻秸发酵制沼气的影响

碱水解法以其方便高效成为稻秸发酵制沼气中广泛采用的化学预处理方法,但是碱水解对于稻秸细胞壁中高聚物成分及其空间致密交联结构的作用机理有待深入研究。采用共聚焦显微拉曼光谱和透射电镜研究了NaOH碱处理对稻秸厌氧发酵产沼气的影响。首先对未处理稻秸和碱处理稻秸进行微米级空间分辨率的拉曼光谱面扫描,然后对这两类样本进行主成分分析,发现累计贡献率达99%的前两个主成分空间中两类样本分别呈射线状分布,两类样本分界线清楚表明碱处理导致稻叶组织的拉曼光谱响应特性发生了明显变化;进一步分析前两个主成分的载荷图,发现拉曼峰1 739,1 508和1 094 cm-1是影响主成分的重要谱带,而这三个拉曼峰分别归属于半纤维素、木质素和纤维素的拉曼散射效应;结合半纤维素、木质素和纤维素的拉曼特征峰和显微图像信息实现了组织细胞中三种成分的化学成像分析,发现碱处理破坏了稻叶组织中上述三种成分的致密空间结构,并使它们的含量明显减少,尤其是木质素。由此得出结论：共聚焦显微拉曼光谱可实现稻叶组织细胞中半纤维素、木质素和纤维素的无损检测,结合显微空间信息可实现稻秸中三种成分的化学成像分析,该研究有助揭示碱处理促进秸秆厌氧发酵产沼气的作用机理。     

结香纤维素与木素分布的显微激光拉曼光谱研究

显微激光拉曼光谱技术可以实现纤维素与木素在木材细胞壁中原位状态分布规律的观察研究。首先采用透射电子显微镜(TEM)研究了结香细胞壁的超微结构。进而采用显微激光拉曼光谱技术对细胞壁各层中纤维素与木素分布特点进行了原位分析测定,拉曼图像及光谱分析结果表明,纤维素与木素在细胞壁各形态区分布不均一,纤维素的分布情况与木素相反。     

纤维素13C同位素示踪法研究纤维素与木素连接方式

为了阐明裸子植物中纤维素与木素之间的连接方式,从多糖的角度分析糖单元与木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PAL酶的抑制剂AOPP及外源性木素前驱物松柏醇-β-D-葡萄糖苷一起投入生长中的银杏植物体内。碳13丰度检测得知纤维素在细胞壁的沉积主要是从在初生壁开始,高分辨率固体核磁13C NMR分析证实了纤维素6位碳与木素以苯甲醚键等方式连接。     

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0.5 μm）及图像叠加技术在原位状态对比了受拉木与对应木纤维细胞壁主要组分分布规律、分布相关性以及细胞壁水平的孔隙分布特点。通过纤维素、半纤维素及木质素-CH非对称伸缩振动（2 942 cm-1）特征峰峰面积积分成像成功地区分出受拉木与对应木纤维细胞壁各个亚层。在此基础上采用数据归一化处理实现平均拉曼光谱中纤维素（1 094 cm-1）与木质素（1 598 cm-1）、木聚糖（904 cm-1）与木质素（1 598 cm-1）特征峰成像叠加,结果表明相比于临近的次生壁及胞间层,受拉木胶质层含有更高浓度的纤维素;与对应木相比,受拉木纤维素和木聚糖浓度在整个细胞壁形态区域呈增强趋势,木质素浓度在次生壁区域有所增强。相邻细胞壁线扫描分析结果表明沿着细胞腔向复合胞间层区域过渡时纤维素、木质素及木聚糖的浓度均呈现明显的区域选择性及梯度变化规律。特征峰积分成像得出受拉木胶质层孔隙结构最为丰富,但其次生壁及胞间层区域孔隙分布程度较对应木低。以上研究结果有助于深化对受拉木特殊理化特性及形成机制的理解,同时拓展了显微拉曼光谱技术在植物细胞壁孔隙结构研究领域的应用。     

共聚焦显微拉曼光谱在木质纤维细胞壁预处理中的应用进展

在能源紧缺和环境恶化的双重压力下,利用农林生物质替代化石资源生产生物燃料、生物基化学品和材料逐步发展成为世界范围内的研究热点,而细胞壁中纤维素、半纤维素、木质素以及其他少量组分的空间分布不均一性和化学结构复杂性构成了天然抗降解屏障,严重阻碍生物质的转化效率,因此需要对木质纤维原料进行预处理,以期破坏细胞壁的宏观壁垒,实现生物质的低成本高效转化。在此过程中,全面了解木质纤维细胞壁的化学组成、结构特性及其在生物质转化过程中的解构机理是高效利用农林生物质的重要前提。由于拉曼光谱具有样品制备要求低、灵敏度高、且能在原位状态下对样品进行定性、定量分析等特点,使得拉曼光谱成为研究木质细胞壁结构的有力工具。尤其与显微技术相结合时,可以同时获得木质纤维细胞壁主要组分的微区分布与超分子结构信息,实现生物质转化过程中化学组分动态变化的可视化研究。首先介绍了拉曼光谱成像的工作原理,并对纤维素、半纤维素和木质素的拉曼特征信号进行了归属。其次,总结了近几年拉曼光谱在生物质转化领域内的应用与研究进展,综述了拉曼光谱在未处理状态下以及稀酸、水热、稀碱等不同预处理过程中的分析方法,对细胞壁主要组分的分布进行表征,以揭示预处理过程中各组分的溶出过程及迁移规律,为在细胞及亚细胞水平探究预处理诱导细胞壁主要组分动态溶解机制提供了有效路径。此外,针对检测中收集的光谱数量过多、分析难等问题,文章重点介绍了主成分聚类分析法和顶点成分分析法两种拉曼数据分析方法,用于提取特征信息并对光谱进行分类研究,以深入探究特定组分的空间分布和分子结构。最后,根据上述分析展望了拉曼光谱在生物质转化领域的研究趋势,为相关研究提供技术参考。     

热处理竹材的化学成分傅里叶变换红外光谱分析

化学热处理是实现可再生木质生物能源中纤维素高效利用及半纤维素糖化转换的关键步骤。通过预处理过程可以快速去除难溶木质素,实现细胞壁中半纤维素的物理化分离,使得植物细胞壁中化学成分发生变化,从而增加木质纤维素的产出量。以硫酸(H₂SO₄)、稀碱(NaOH)及甘油(glycerol)为预处理介质,采用不同的热处理温度(硫酸(H₂SO₄)、稀碱(NaOH)热处理温度为117和135 ℃;甘油(glycerol)热处理温度为117 ℃)),对竹材处理前后的主要化学组分进行对比分析,并通过傅里叶变换红外光谱进一步证实化学热处理前后竹材化学组分的变化,以获得不同的化学热处理介入下竹材化学成分转换的主要变化规律和机理。结果表明：热化学处理后竹材的纤维素产出量明显增加。纤维素得率及木质素的去除率在不同的处理介质条件下的变化规律为,稀碱(NaOH)处理效果优于稀酸(H₂SO₄)和甘油(glycerol);此外,在相同介质条件下135 ℃热处理效果比117 ℃热处理效果显著。对于不同处理条件的半纤维素的降解程度大小变化结果与此相同。通过红外光谱分析可知,热处理后纤维素环状C-O-C不对称伸缩振动峰出现峰值分解,半纤维素的红外吸收特征峰出现明显陡降变化,木质素苯环特征吸收峰明显减弱,证明纤维素产出量明显增加,半纤维素降解趋势明显,木质素去除效果良好。傅里叶红外变换光谱分析结果与标准测定结果一致。     

Multiscale modelling strategies and experimental insights for the solvation of cellulose and hemicellulose in ionic liquids

ABSTRACT

The present study investigates the dissolution behaviour of cellulose and hemicellulose in potential ionic liquids (ILs) using both the quantum chemical and experimental validation. For converging upon the recommended IL, 1428 ILs consisting of 42 cations and 34 anions were studied with the conductor like screening model for real solvents (COSMO-RS) model. Based on the infinite dilution activity coefficient of the components in IL, the selected anions and cations were visualised by observing their interactions with cellulose and hemicellulose using interaction energies, natural bonding orbital analysis and molecular dynamics simulations. The dissolution order of cellulose and hemicellulose in ILs was primarily determined by the evaluation of hydrogen bonds between the oxygen atom of anion and hydroxyl proton of cellulose/hemicellulose. From this discernible fact, the anion of the IL was observed to play a leading role in the solvation process as compared to the cation. Eventually, acetate [OAc]^– anion and 1-ethyl-3-methylimidazolium [EMIM]⁺ cation were found to be good candidates for the dissolution of cellulose and hemicellulose. This was further confirmed by the measurement of solid-liquid equilibria with cellulose and hemicellulose. The regenerated cellulose powder was then characterised by Fourier transform spectroscopy(FTIR), X-ray diffraction (XRD) and Thermal gravimetric analysis (TGA).     

Ultrasound-Assisted Surface-Modification of Wood Particulates for Improved Wood/Plastic Composites

The combined effects of alkali and ultrasound treatment of wood flour on the mechanical properties of polypropylene-based wood/plastic composites (WPCs) were examined. FT-IR measurements confirmed that the alkali treatment removed both hemicellulose and lignin from the wood, and there was an increase in the number of hydroxyl groups on the cellulose surface. This process was promoted by ultrasound treatment. Mechanical testing of injection-molded WPC samples revealed that alkali treatment improved both composite strength and modulus when polypropylene grafted with maleic acid was used as a coupling agent. The strength increase is due to improved adhesion between the fiber and matrix, while improved modulus is due to the removal of lignin and hemicellulose that are not as stiff as cellulose. Polarized optical microscopy showed the presence of well-defined polymer crystals on the surface of the modified wood, and this is also responsible for the improved mechanical properties. It is conclusively demonstrated that the combination of chemical treatment of wood and ultrasound assistance is more effective in improving the mechanical properties of the composites than the use of chemical treatment alone.     

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。     

NOx and N2O precursors (NH3 and HCN) from biomass pyrolysis: Co-pyrolysis of amino acids and cellulose, hemicellulose and lignin

Nitrogen in biomass is mainly in forms of proteins (amino acids). Glycine, glutamic acid, aspartic acid, leucine, phenylalanine and proline are the major amino acids in agricultural straw. The six amino acids were pyrolyzed individually at 800 °C in a tubular reactor in an argon atmosphere. Each amino acid sample was then pyrolyzed individually with cellulose, hemicellulose or lignin with 1:1 mixing ratio by weight under the same condition. The emissions of HCN and NH₃ were detected with a Fourier transform infrared (FTIR) spectrometer. The extent of interaction between the amino acids with cellulose, hemicellulose or lignin was determined by comparing the yields of HCN and NH₃ from co-pyrolysis with those from single amino acid pyrolysis under the same condition. The results indicate that the structure of the amino acid has a significant effect on the nitrogen transformation during pyrolysis. The mixtures undergo solid-state decomposition reactions during co-pyrolysis. The extent of interaction between the amino acids with cellulose, hemicellulose or lignin depends on the amino acid types and the components in biomass. Although single proline and leucine form no char, they give a significant amount of nitrogen-containing char when co-pyrolyzed with cellulose, hemicellulose and lignin. HCN and NH₃ yields and nitrogen conversion pathway from amino acid pyrolysis are influenced by cellulose, hemicellulose and lignin.     

13C CPMAS studies of plant cell wall materials and model systems using proton relaxation-induced spectral editing techniques

The solid state 13C CPMAS NMR spectra of plant cell walls are often complex owing to superposition of resonances from different polysaccharides and the heterogeneity of the cell wall assembly. In this paper, we describe the application of a set of proton relaxation-induced spectral editing (PRISE) experiments which combine 1H relaxation properties (T1, T1rho, T2) with 13C high resolution spectroscopy (CPMAS) to relate the dynamics of the plant cell walls and model systems to their domain structural details. With PRISE it has been found that in plant cell wall materials, cellulose is always associated with the long components of spin-lattice relaxation in both the laboratory and rotating frames whereas non-cellulose polysaccharides (pectin and hemicellulose) are associated with the short ones. For the proton T2 relaxation, cellulose is only associated with the short component (below 20 micros), pectin contributes to both the short component and the long one.     

Electron spectroscopy of graphite,graphite oxide and amorphous carbon

Core-level and valence-band photoelectron spectra and Auger spectra for the basal plane of highly ordered graphite, the edge plane of highly ordered graphite, the basal plane of graphite oxide, and for the basal plane of disordered graphite are compared in an effort to determine spectral features that may be used to identify these chemical species in carbon-rich specimens. The photoelectron spectra were recorded using 1253.6 eV X-ray excitation. The Auger spectra were obtained using both X-ray (1253.6 eV) and electron (3 keV) excitation. The differential X-ray excited C-KVV spectra were the most useful in distinguishing the different types of carbon. In particular, the plasmon structure and the energy separation between the two major excursions were very sensitive to changes in the surface chemistry and structure. Changes in peak position and peak width observed in the valence band and C(1s) photoelectron spectra were also very helpful in distinguishing the pristine, structurally damaged, and the oxidized graphite surfaces. Much of the structural and chemical information apparent in the X-ray excited C-KVV spectra was lost upon electron beam exposure. Differences in the C-KVV Auger lineshapes for X-ray and electron excitation were attributed to both structural and chemical changes induced by electron beam exposure.     

The experimental vibrational infrared spectrum of lemon peel and simulation of spectral properties of the plant cell wall

The experimental vibrational IR spectra of the outer part of lemon peel are recorded in the range of 3800–650 cm^–1. The effect of artificial and natural dehydration of the peel on its vibrational spectrum is studied. It is shown that the colored outer layer of lemon peel does not have a noticeable effect on the vibrational spectrum. Upon 28-day storage of a lemon under natural laboratory conditions, only sequential dehydration processes are reflected in the vibrational spectrum of the peel. Within the framework of the theoretical DFT/B3LYP/6-31G(d) method, a model of a plant cell wall is developed consisting of a number of polymeric molecules of dietary fibers like cellulose, hemicellulose, pectin, lignin, some polyphenolic compounds (hesperetin glycoside-flavonoid), and a free water cluster. Using a supermolecular approach, the spectral properties of the wall of a lemon peel cell was simulated, and a detailed theoretical interpretation of the recorded vibrational spectrum is given.

     

13C CPMAS NMR spectroscopic analysis applied to wood characterization

Solid-state nuclear magnetic resonance (NMR) spectroscopic analysis were carried out on recent and archaeological wood. Cross-polarization-magic-angle spinning¹³C NMR spectra obtained from samples of poplar (Populus sp.), oak (Quercus sp.), and silver fir (Abies alba) were examined in this study. The most relevant peaks were assigned according to the extensive literature in the area, and the differences observed discussed in terms of lignin and cellulose composition: by fixing a lignin reference signal intensity, the cellulose and hemicellulose moieties showed a strong depletion compared to the lignin signals in archaeological wood.     

X-ray radiation of poly-L-arginine hydrochloride and multilayered DNA-coatings

The aim of this work was to determine the chemical changes induced in thin films of the dry polypeptide poly-L-arginine hydrochloride and its mixture with calf thymus deoxyribonucleic acid (DNA) during 5 h of soft X-ray exposure. The physical and chemical effects of the soft X-ray irradiation were studied using X-ray Photoelectron Spectroscopy (XPS). Analysis of O1s, N1s and C1s features in XPS spectra reveals the existence of several routes of radiation-induced decomposition and shows quantitative and qualitative changes.     

Characterization of the structural and dynamic changes of cell wall obtained by ultrasound-water and ultrasound-alkali treatments

It is well-known that ultrasound has been studied for its cavitation, mechanical and thermal effects. As a pretreatment technology, ultrasonic alkali treatment has attracted much attention in the field of biomass biochemical transformation. In this study, the structural and dynamic changes of wood cell walls during ultrasound-water, alkali, and ultrasound-alkali treatments were investigated by stereoscopic microscopy, confocal Raman microscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction. The results indicated that the ultrasound-water, alkali, and ultrasound-alkali treatments had the effect of removing extractives from conduits. The uniform self-shrinking samples with shrinkage conduits were obtained by the alkali and ultrasound-alkali treatments. All of the treatments affected the relative content, structure and distribution of the chemical components in the wood cell walls. Compared with water-immersion samples, the relative content of hemicellulose of the treated samples reduced from 32.31% to 7.02% for ultrasound-8% NaOH treated samples. For the signal intensity of lignin, ultrasound-water treated and ultrasound-alkali treated samples displayed a more significant reductions than the alkali treated samples in the cell wall region. The crystal zone and amorphous zone of cellulose coexisted before and after the treatment, for all of the treated samples, and particularly for the ultrasound-assisted treated samples, the crystallinity increased from 38.15% for water-immersion samples to 57.42% for ultrasound-8% NaOH treated samples.     

软X射线辐照引起的铟锡氧化物表面光化学反应

利用XPS原位研究了Mg Kα X射线辐照对ITO表面的影响.结果表明,随着X射线辐射时间的延 长,表面辐照区域In,Sn相对含量增加,而O则逐渐减少,同时,In,Sn3d光电子峰随X射线 辐射的增强而变化.分析说明X射线的辐照导致了ITO表面光化学反应,氧的脱离使In,Sn有 被还原的趋势,受损较重的In明显存在亚氧化态.In,Sn俄歇参数的变化进一步证实ITO表面 发生了光化学反应.并讨论了X射线引起ITO表面光化学反应的机制. 关键词： X射线辐照 光电子能谱 光化学反应