松柏醇-β-D-葡萄糖苷-[α-^13C]与造纸废水中可溶性木素的聚合反应研究

研究了在木素氧化酶催化的体系下,木素前驱物松柏醇-β-D-葡萄糖苷-[α-13C]与废水中可溶性木素的聚合反应方法.应用了凝胶渗透色谱(GPC)测定了聚合产物的相对分子量,GPC测定的结果表明相对分子质量也明显增大,相对分子质量Mn由326提高到1 068.采用了13C同位素示踪技术,并结合红外光谱、核磁共振技术探讨了松柏醇葡萄糖苷与废水中木素的聚合产物的化学结构.碳-13同位素示踪结合13C NMR的测定结果表明:木素前驱物松柏醇-β-D-葡萄糖苷能与废水中木素形成聚合产物,主要连接方式有β-O-4、β-β、β-5和β-1等,产物中松柏醇结构含量也比较高,低分子水溶性木素聚合为相对分子质量较大的木素而沉淀析出,因而用在制浆造纸废水处理时,可以有效降低废水中可溶性难降解的木素含量,使废水的污染负荷降低,并提高可生化降解性.     

松柏醇-β-D-葡萄糖苷-[α-13C]与造纸废水中可溶性木素的聚合反应研究

研究了在木素氧化酶催化的体系下,木素前驱物松柏醇-β-D-葡萄糖苷-[α-¹³C]与废水中可溶性木素的聚合反应方法. 应用了凝胶渗透色谱(GPC)测定了聚合产物的相对分子量,GPC测定的结果表明相对分子质量也明显增大,相对分子质量Mn由326提高到1 068. 采用了¹³C同位素示踪技术,并结合红外光谱、核磁共振技术探讨了松柏醇葡萄糖苷与废水中木素的聚合产物的化学结构. 碳-13同位素示踪结合¹³C NMR的测定结果表明：木素前驱物松柏醇-β-D-葡萄糖苷能与废水中木素形成聚合产物,主要连接方式有β-O-4、β-β、β-5和β-1等,产物中松柏醇结构含量也比较高,低分子水溶性木素聚合为相对分子质量较大的木素而沉淀析出,因而用在制浆造纸废水处理时,可以有效降低废水中可溶性难降解的木素含量,使废水的污染负荷降低,并提高可生化降解性.     

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。     

基于TG-FTIR的杨木热解过程中脲醛树脂影响机理的模型物研究

热解是废弃人造板高效回收利用的方式,人造板中所含胶黏剂是其不同于生物质的主要特征。为了有效环保地利用热解技术处理废弃人造板,解明人造板热解过程中其所含脲醛树脂胶黏剂(UF)对木材热解特性的影响,深入探索UF对人造板中木材各组分的作用机制,以杨木及木材的三种主要组分(纤维素、半纤维素、木素)为研究对象,创新性地依据杨木的化学组成,以纤维素、木聚糖和木素配制成模型物,并加入UF模拟人造板的构成。利用热重红外光谱联用(TG-FTIR)分析法,对比分析了加入UF前后模型物以及杨木各主要组分的热失重特性及气相演变规律。热重及红外结果表明,UF促进了纤维素热解过程中水和羧酸类物质的生成。UF与木素结合生成热不稳定的含氮结构,释放大量氨气,并且在200～300 ℃区间内参与了木素的热解并直接影响木素热解产物的生成。由此推测,在人造板热解过程中,木材三种主要组分中与UF作用的主要成分是木素。     

红外光谱结合热重法对考古木材降解状况的分析

考古木材的保存保护需要基于其主要化学组分的降解状况,制定科学的保护方案,如加固剂的选用、处理时间与温度的控制等。选取徐州万达汉代墓群出土四个棺木作为样品;经鉴定,树种分别为硬松(Pinus subgen. Diploxylon sp.)、楠木(Phoebe sp.)、梓木(Catalpa sp.)和榉木(Zelkova sp.)。采用衰减全反射傅立叶红外光谱及热重分析,快速表征考古木材和对应现代材的化学性质和热解特性。研究结果表明:考古硬松、考古楠木、考古梓木以及考古榉木的红外光谱中1 730 cm~(-1)附近来自于半纤维素乙酰基上CO伸缩振动的吸收峰几乎消失,而1 500 cm~(-1)附近木素苯环骨架伸缩振动吸收峰的相对峰强提高,这反映出古木半纤维素降解严重,而木素留存较好。古木综纤维素样品中均未发现半纤维素中酰氧键(—COO)位于1 238 cm~(-1)附近的特征峰,而除现代楠木综纤维素外,其余现代材综纤维素红外谱图中均检测到此峰,这表明与纤维素相比,古木中半纤维素降解更严重,也说明楠木的半纤维素含有较少的酰氧键。与古木酸不溶木素样品相比,现代健康材酸不溶木素1 459 cm~(-1)附近甲基与亚甲基的C—H弯曲振动的吸收峰强度较高,说明现代健康材酸不溶木素中有更多的甲基与亚甲基,木素大分子中含有更多的侧链。古木酸不溶木素的红外谱中1 028 cm~(-1)附近的木素中仲醇与脂肪醚结构的吸收峰强度低于现代材,说明古木的酸不溶木素含有较少的C—O键。比较不同树种古木和现代材的热解行为,发现古木热解速率均减缓,快速热解段起始温度提前,残炭率提高。古木与现代材热解行为的差异,主要与古木综纤维素大量降解,木素相对含量的提高有关。在4个古木样品中,考古楠木的残炭率最低,这表明考古楠木木素相对含量较低,综纤维素保存较好,其天然耐久性在4个树种中最好。此外,由于古木酸不溶木素中含有较少的侧链以及甲氧基使得其热解速率变慢。以上结果表明,红外光谱与热重分析均可用于分析考古木材的降解状况,能为及时制定文物保护方案提供科学依据。     

纤维素拉曼光谱的单体仿真方法研究

纤维素是由葡萄糖组成的大分子多糖,是世界上最丰富、最便宜、最容易获得的天然聚合物。纤维素作为最古老最丰富的天然高分子在研究中备受关注,纤维素的可控性取决于其分子量、大小和结构,而拉曼光谱具有“指纹特性”,可以对不同的纤维素纤维进行鉴别,也能对历史老化的纺织纤维材料进行鉴别。然而纤维素作为大分子多糖对其做理论仿真较为困难,该研究提出采用基本单元模拟大分子光谱这一方案,使用纤维素单体仿真拉曼光谱来分析纤维素大分子的光谱性质。使用Gaussian 16软件基于密度泛函理论,在B3LYP/6-31g(d, p)的基组条件下,计算了不同外电场(-0.01～0.03 a.u.)下的纤维素单体的拉曼光谱,以及纤维素双链节的拉曼光谱。研究表明,在无外电场作用下,纤维素单体的拉曼光谱主要在449、 597、 842、 1 127、 1 361、 1 395和3 005 cm^-1处有特征峰,对其做振动分析,结果表明这些拉曼峰分别是由环(C6—C4—O20)伸缩振动、 C—C—H扭曲振动、环(C4—O20—C2)伸缩振动、糖苷键(C2—O1—C8)的伸缩振动、 CH₂     

多胺型纤维素基螯合纤维的合成和光谱学研究

将漂白化学桉木浆(BCEP)与甲基丙烯酸缩水甘油酯(GMA)的接枝共聚产物(CPGMA)与乙二胺(EDA)反应,合成了多胺型纤维素基螯合纤维CPGMA-EDA。利用傅里叶变换红外光谱(FTIR)、固体核磁共振碳谱(13C CP/MAS NMR)和X射线衍射(XRD)对产物进行了分析。FTIR和13C CP/MAS NMR的研究结果表明,与EDA反应后,CPGMA在904 cm-1波数处的环氧基特征吸收峰基本消失,3 200～3 500 cm-1处的吸收峰因新增N—H伸缩振动而明显增宽,说明大量氨基通过开环反应被接枝到了CPGMA表面;XRD结果表明所得纤维素基螯合纤维的结晶度为48.1%,相对于原漂白化学桉木浆的结晶度下降了31.0%,说明反应不仅发生在纤维素的非结晶区,同时也发生在结晶区。     

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。     

电子回旋共振等离子体增强化学气相沉积a-CF_x薄膜的化学键结构

使用CHF3 和C6H6混合气体做气源 ,在一个电子回旋共振等离子体增强化学气相沉积装置中制备了氟化非晶碳 (a CFx)薄膜 .利用发射光谱研究了等离子体中形成的各种碳 氟、碳 氢基团随放电宏观参量的变化规律 ,对薄膜做了傅里叶变换红外光谱和X射线光电子能谱分析 ,证实等离子体中的CF2 ,CF和CH基团是控制薄膜生长、碳 /氟成分比和化学键结构的主要前驱物     

棒状纳米纤维素仿生矿化及光谱分析

以棒状纳米纤维素为模板,采用仿生矿化的方法制备纳米纤维素/纳米羟基磷灰石复合材料。并利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜能谱分析(SEM-EDAX)对仿生矿化前后纳米纤维素中碳、氧、钙、磷元素的变化情况及分布状态进行了表征,并探讨了纳米羟基磷灰石的生长机理。结果表明纳米纤维素表面形成了纳米羟基磷灰石;纳米纤维素的碳氧比为1.81,仿生矿化后下降为1.54;仿生矿化后纳米纤维素的钙磷比nCa/nP=1.70;纳米羟基磷灰石成核是在纳米纤维素的羟基上,并且纳米纤维素表面羟基和纳米羟基磷灰石的钙离子之间发生了配位作用。纳米羟基磷灰石较为均一的形成在纳米纤维素的基体中。通过原子力显微镜(AFM)图片可以看出,直径为20nm左右的羟基磷灰石生长在纳米纤维素的表面。     

Effect of cellulose–lignin interactions on char structural changes during fast pyrolysis at 100–350 °C

This study investigates the cellulose–lignin interactions during fast pyrolysis at 100–350 °C for better understanding fundamental pyrolysis mechanism of lignocellulosic biomass. The results show that co-pyrolysis of cellulose and lignin (with a mass ratio of 1:1) at temperatures < 300 °C leads to a char yield lower than the calculated char yield based on the addition of individual cellulose and lignin pyrolysis. The difference between the experimental and calculated char yields increases with temperature, from ～2% 150 °C to ～6% at 250 °C. Such differences in char yields provide direct evidences on the existence of cellulose–lignin interactions during co-pyrolysis of cellulose and lignin. At temperatures below 300 °C, the reductions in both lignin functional groups and sugar structures within the char indicate that co-pyrolysis of cellulose and lignin enhances the release of volatiles from both cellulose and lignin. Such an observation could be attributed to two possible reasons: (1) the stabilization of lignin-derived reactive species by cellulose-derived reaction intermediates as hydrogen donors, and (2) the thermal ejection of cellulose-derived species due to micro-explosion of liquid intermediates from lignin. In contrast, at temperatures ≥ 300 °C, co-pyrolysis of cellulose and lignin increases char yields, i.e., with the difference between the experimental and calculated char yields increasing from ～1% at 300 °C to ～8% at 350 °C. The results indicate that the cellulose-derived volatiles are difficult to diffuse through the lignin-derived liquid intermediates into the vapor phase, leading to increased char formation from co-pyrolysis of cellulose and lignin as temperature increases. Such an observation is further supported by the increased retention of cellulose functional groups in the char from co-pyrolysis of cellulose and lignin.     

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。     

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。     

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。     

THERMAL CHARACTERIZATIONS OF WOOD FLOUR/STARCH CELLULOSE ACETATE COMPOUNDS

Thermogravity analysis (TGA) and differential scanning calorimetric (DSC) analysis, as well as dynamic thermal analysis (DMA), were carried out to study the interfacial interaction between wood flour (WF) and starch/cellulose acetate (SCA) blend. It was found that the main components in the compounds, namely, starch, cellulose, and cellulose acetate, started to decompose at around 330°C, a characteristic temperature for breaking glycoside-linked glucose units. Complexation of lignin in WF with amylose in SCA occurred during compounding, which gave rise to new crystallites that have a melting point of around 160°C. Hydrogen bonding is believed to play a key role in the crystallization. With increasing WF content, both the glass transition temperature and softening temperature increase as a result of the restricted molecular chain mobility imposed by rigid cellulose filaments. In addition, the DMA data revealed that amylose can occur as linkages in the crystallites. All these observations indicated that the interfacial adhesion between SCA and WF is relatively strong, even in absence of a coupling agent.     

Soft X-ray induced chemical modification of polysaccharides in vascular plant cell walls

Scanning transmission X-ray microscopy and micro carbon X-ray Absorption Near Edge Spectroscopy (C-XANES) can provide quantitative information regarding the distribution of the biopolymers cellulose, hemicellulose, and lignin in vascular plant cell walls. In the case of angiosperms, flowering plants, C-XANES may also be able to distinguish variations in lignin monomer distributions throughout the cell wall. Polysaccharides are susceptible to soft X-ray irradiation induced chemical transformations that may complicate spectral analysis. The stability of a model polysaccharide, cellulose acetate, to variable doses of soft X-rays under conditions optimized for high quality C-XANES spectroscopy was investigated. The primary chemical effect of soft X-ray irradiation on cellulose acetate involves mass loss coincident with de-acetylation. A lesser amount of vinyl ketone formation also occurs. Reduction in irradiation dose via defocusing does enable high quality pristine spectra to be obtained. Radiation induced chemical modification studies of oak cell wall reveals that cellulose and hemicellulose are less labile to chemical modification than cellulose acetate. Strategies for obtaining pristine C-XANES spectra of polysaccharides are presented.     

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.     

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.     

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.