Analysis of Lignin Aromatic Structure in Wood Based on the IR Spectrum

Abstract

A total of 17 softwoods and 48 hardwoods were analyzed by IR spectroscopy to examine if syringyl ratio (syringyl/(syringyl+guaiacyl)) calculated from nitrobenzene oxidation products can be precisely expressed by area ratios of characteristic peaks of lignin in IR spectrum. Area ratio of two peaks is referred to as that of two wavenumber domains, represented by “wavenumber 1/ wavenumber 2.” Examined peak area ratios were 1595/1509, 1509/1460, 1275/1220, 1130/1032, and 835/(855+815). Among these ratios, log(1595/1509) and log(1275/1220) showed significant linear relationship with the syringyl ratios with a correlation coefficient of 0.98 for all 65 woods. These two ratios could also be used to distinguish all the hardwoods from the softwoods.     

Hemicellulose Composition in Different Cell Wall Fractions Obtained using a DMSO/LiCl Wood Solvent System and Enzyme Hydrolysis

In our previous studies on the relationships between lignin structure and hemicellulose composition in a wide range of hardwood species, we showed that the higher the syringyl ratio, the higher the xylan/mannan ratio. In this study, the relationship of the syringyl ratio and xylan/mannan ratio was further studied using fractions obtained by stepwise extraction of finely milled beech wood by use of aqueous dioxane and subsequent dimethyl sulfoxide (DMSO)/LiCl solvents with increasing LiCl concentration. Each soluble fraction obtained with a different LiCl concentration was compared with the corresponding insoluble residue, and it was shown that both the syringyl ratio and xylan/mannan ratio were always higher in the insoluble fraction. To analyze polysaccharides closely located with lignin, milled wood lignin (MWL), and cellulolytic enzyme lignin (CEL) obtained by enzyme treatment after DMSO/LiCl swelling were investigated. Although the xylan/mannan ratio of MWL was higher, that of CEL with more than 80% lignin yield was lower.     

红外光谱法植物油脂分析研究进展

综述了红外光谱法在植物油脂油定性识别及定量分析中的应用。介绍了红外光谱法分析植物油脂的基本原理。论述了红外光谱法在油脂理化参数的定量分析的研究进展。展望了红外光谱法在油脂检测中的应用前景。提出多种方法联合运用的检测油脂的新思路,为红外光谱法油脂快速分析检以及定性识别分析提供参考。     

Polyoxometalate (POM) Oxidation of Milled Wood Lignin (MWL)

Abstract

The chemical structural changes of Lodgepole pine milled wood lignin (MWL) before and after polyoxometalate (POM) oxidation were investigated using gel permeation chromatography (GPC), Fourier Transform infrared spectroscopy (FTIR), and solution‐state nuclear magnetic resonance spectroscopy (NMR). ¹³C NMR spectroscopic data revealed an approximately 28% decrease in α‐OH/β‐O‐4 inter‐unit linkages after POM treatment. This was accompanied by an increase in carbonyl and phenolic hydroxyl content. These results suggest POM oxidation involved side chain (such as α‐OH/β‐O‐4) oxidation and/or degradation of some of the inter‐unit linkages. Quantitative ¹³C NMR along with GPC analysis revealed an increase in the degree of condensation of the MWL as a result of POM treatment, suggesting radical coupling as a major reaction pathway.     

重整生成油C8馏分中芳烯烃的分析

采用毛细管气相色谱-氢火焰离子化检测器(CGC-FID)和气相色谱-质谱法(CGC/MS)分析了重整生成油C8馏分中的芳烯烃。实验使用HP-FFAP毛细管色谱柱(50m×0.32mm×0.50μm)和ATTM-WAX毛细管色谱柱(50m×0.32mm×0.30μm),根据烃类化合物在这两种色谱柱上的保留规律,用CGC/MS联用技术和UOP方法744-06以及标准样品相结合的方法对重整生成油C8馏分中的芳烯烃进行了定性定量分析,从12O多种组分中鉴定出18种烯烃,对其中的15种烯烃组分进行了定量分析,对其它3种烯烃组分进行了半定量分析。本法操作简单、重复性好,适用于重整生成油C8馏分和二甲苯塔塔顶液的烯烃检测,也可用于芳烃厂同类产品质量控制分析。     

红外光谱法测定烷基硫酸盐中游离的脂肪醇

建立了用红外光谱法测定十二烷基硫酸钠中游离十二醇的方法,选用标准曲线法,选择 3660cm~(-1)吸收峰为分析谱带,并以四氯化碳为溶剂,在红外液体吸收池内记录其在3680～3050cm~(-1)的A值。方法准确、快速、简便,标准偏差为0.008％,变异系数0.51％,回收率99.8％。     

改性淀粉的交联度和红外光谱性质的研究

研究了以环氧氯丙烷为交联剂制备交链淀粉的方法，讨论了交联剂用量对淀粉交联度及产率的影响，并采用红外光谱分析及解析技术对淀粉在不同交联度下其分子结构与性质的特征作了进一步的分析。研究表明，随着交联度增大，波数为3390cm^-1峰越来越宽，而且越来越不对称；如果低交联度淀粉(理论交联度为0，2)在1250cm^-1～1269cm^-1带中波数较小，而高交联度淀粉(理论交联度为12，20)波数较高，则可以将红外峰由1250cm^-1向1269cm^-1的过渡视为交联淀粉构象上由B型向V型的转变；1047cm^-1和1022cm^-1峰高的比值表明，在交联度较低的时候，淀粉颗粒中有序分子迅速减少，无定形分子增多，而交联度继续增大时，有序分子与无定形分子的比值变化不大。     

The Reduction and Oxidation of Co Species in CoZSM-5 Zeolites Studied by IR Spectroscopy

The process of reducing Co ions in zeolite CoZSM-5 by NO, H₂ and CO, as well as of oxidizing them by O₂ was studied by IR spectroscopy with CO as the probe molecule for Co²⁺ and NO as the probe for Co³⁺. Two zeolites of different Co status were used: in the first, Co²⁺ ions were localized mostly in cation exchange positions, and in the second most of the Co²⁺ occurred in the form of CoO and oxide-like clusters. IR studies evidenced that NO reduced some Co³⁺ to Co²⁺ already at room temperature, and also reduced some Co²⁺ to lower oxidation states (probably Co⁺) at 670 and 1070 K. Only Co²⁺ in exchange positions could be reduced with NO. The treatment of zeolite CoZSM-5 with H₂ or with CO at 670 and 1070 K made the reduction of Co³⁺ to Co²⁺ (the contribution of Co³⁺ decreased and the contribution of Co²⁺ increased). IR studies illustrated that the most electron-acceptor Co³⁺ (characterized by a high frequency Co³⁺–NO band) were transformed, by reduction, into the most electron-acceptor Co²⁺ (characterized by a high frequency Co²⁺–CO band). The treatment of zeolite CoZSM-5 with oxygen at 670–1070 K resulted in the oxidation of Co²⁺ to Co³⁺ (the contribution of Co²⁺ decreased while the contribution of Co³⁺ increased).     

苯乙烯类嵌段共聚物对IR/CR共混物形态结构的影响

考察了苯乙烯类嵌段共聚物对ＩＲ／ＣＲ二元共混物相态结构及粒子尺寸的影响。结果表明，加入苯乙烯类嵌段共聚物可有效改善ＩＲ／ＣＲ共混物的分散状态，在任何组成下均可降低分散相粒子尺寸，促进体系均匀分散，其中苯乙烯－异戊二烯共聚物的效果最为理想，其最佳用量为３～７份。     

Separation and Structural Characterization of Lignin from Hybrid Poplar Based on Complete Dissolution in DMSO/LiCl

In this paper, the physicochemical properties and structural features of six lignin preparations separated with a total dissolution of ball-milled wood in dimethyl sulfoxide and lithium chloride (DMSO/LiCl) followed by extraction with ethanol/water were investigated. These isolated lignin fractions were characterized using wet chemical analysis, FT-IR, and ¹H and¹³C-NMR techniques. Experimental results showed that separated lignin preparations were relatively free of associated polysaccharides. These lignin fractions were classified as guaiacyl-syringyl lignin type: mainly composed of guaiacyl units with noticeable amounts of syringyl units and fewer p-hydroxyphenyl units. The molar ratio of non-condensed guaiacyl units to syringyl units (G/S) decreased as the ratio of LiCl to poplar weight increased. The results also showed that these lignin preparations consisted mainly of β-O-4 ether bonds combined with small quantities of β-β′ and β-5 carbon-carbon linkages. Furthermore, considerable amounts of esterified p-hydroxybenzoic acids and minor amounts of esterified p-coumaric acid were also detected in these lignin fractions.     

Synthesis,Spectroscopy, Single-Crystal Structure Analysis and Antibacterial Activity of Two Novel Complexes of Silver(I) with Miconazole Drug

In a previous article, we reported on the higher toxicity of silver(I) complexes of miconazole [Ag(MCZ)₂NO₃ (1)] and [Ag(MCZ)₂ClO₄ (2)] in HepG2 tumor cells compared to the corresponding salts of silver, miconazole and cisplatin. Here, we present the synthesis of two silver(I) complexes of miconazole containing two new counter ions in the form of Ag(MCZ)₂X (MCZ = 1-[2-(2,4-dichlorobenzyloxy)-2-(2,4-dichlorophenyl)ethyl]-1H-imidazole]; X = BF₄⁻ (3), SbF₆⁻ (4)). The novel silver(I) complexes were characterized by elemental analysis, ¹H NMR, ¹³C NMR and infrared (IR) spectroscopy, electrospray ionization (ESI)-MS spectrometry and X-ray-crystallography. In the present study, the antimicrobial activity of all obtained silver(I) complexes of miconazole against six strains of Gram-positive bacteria, five strains of Gram-negative bacteria and yeasts was evaluated. The results were compared with those of a silver sulfadiazine drug, the corresponding silver salts and the free ligand. Silver(I) complexes exhibited significant activity against Gram-positive bacteria, which was much better than that of silver sulfadiazine and silver salts. The highest antimicrobial activity was observed for the complex containing the nitrate counter ion. All Ag(I) complexes of miconazole resulted in much better inhibition of yeast growth than silver sulfadiazine, silver salts and miconazole. Moreover, the synthesized silver(I) complexes showed good or moderate activity against Gram-negative bacteria compared to the free ligand.     

基于电子束辅助固化的木塑复合材料的研究

在辐射剂量为56kGy的双面电子束辐照工艺条件下，制备了苯乙烯(St)、苯乙烯与不饱和聚酯树脂(St／UPE)混合物以及苯乙烯与环氧丙烯酸酯树脂(St／EA)混合物浸渍的冬瓜木和松木系列木塑复合材料，研究了木材和浸渍液体种类以及电子束辐射对浸渍液体的聚合和固化程度以及所得木塑复合材料性能的影响。结果表明在电子束辅助固化工艺条件下，浸入木材的St、St/UPE和St／EA的聚合率以及St／UPE和St／EA的固化率均可大于90％。木塑复合材料的硬度和压缩强度较原木材可提高2～6倍，其1昼夜吸水率则从原木材的64．6％和52．8％分别降低到8．9％～12．9％和7．0％～7．9％。     

Rapid Assessment of Quality Parameters in Cocoa Butter Using ATR-MIR Spectroscopy and Multivariate Analysis

The development of sensitive and robust screening tool(s) for assuring the quality of incoming raw materials would supplement the assurances provided by food manufacturer vendor auditing programs. Our aim was to evaluate the ability of attenuated total reflectance mid‐infrared (ATR‐MIR) spectroscopy in combination with multivariate analysis as a screening tool for the diverse cocoa butter supply. Forty different cocoa butter samples encompassing an acceptable range of compositional variability for the chocolate industry were included. Cocoa butters were characterized for their melt characteristics (melting heat), triacylglycerol content and fatty acid composition (GC‐FAME). Soft independent modeling of class analogy (SIMCA) and partial least squares regression (PLSR) were used for classification and quantification analysis. SIMCA classified all cocoa butters in distinct clusters in a 3‐dimensional space but no sample clustering patterns were associated with melt characteristics. Spectral differences responsible for the separation of classes were attributed to stretching vibrations of the ester (–C=O) linkage (1,660–1,720 cm^?1). PLSR models showed correlation coefficients >0.93 and prediction errors (SECV) of 1.5 units for melt characteristics, 0.2–0.3 and 0.4–0.8 % for major fatty acids and triacylglycerols, respectively. ATR‐MIR spectroscopy combined with pattern recognition analysis provides robust models for characterization and determination of cocoa butter composition.     

A Single-Cell Raman Spectroscopy Analysis of Bone Marrow Mesenchymal Stem/Stromal Cells to Identify Inter-Individual Diversity

The heterogeneity of stem cells represents the main challenge in regenerative medicine development. This issue is particularly pronounced when it comes to the use of primary mesenchymal stem/stromal cells (MSCs) due to a lack of identification markers. Considering the need for additional approaches in MSCs characterization, we applied Raman spectroscopy to investigate inter-individual differences between bone marrow MSCs (BM-MSCs). Based on standard biological tests, BM-MSCs of analyzed donors fulfill all conditions for their characterization, while no donor-related specifics were observed in terms of BM-MSCs morphology, phenotype, multilineage differentiation potential, colony-forming capacity, expression of pluripotency-associated markers or proliferative capacity. However, examination of BM-MSCs at a single-cell level by Raman spectroscopy revealed that despite similar biochemical background, fine differences in the Raman spectra of BM-MSCs of each donor can be detected. After extensive principal component analysis (PCA) of Raman spectra, our study revealed the possibility of this method to diversify BM-MSCs populations, whereby the grouping of cell populations was most prominent when cell populations were analyzed in pairs. These results indicate that Raman spectroscopy, as a label-free assay, could have a huge potential in understanding stem cell heterogeneity and sorting cell populations with a similar biochemical background that can be significant for the development of personalized therapy approaches.     

近红外水性墙面涂料常用乳液类型鉴定研究

采用近红透射光谱法建立一种无损、快速定性分析方法,鉴别三种水性墙面涂料常用乳液。218批样品采集近红外光谱,结合红外光谱法（IR）、热裂解气相色谱-质谱联用法（PyGC—MS）,采用近红外光谱结合主成分分析和模糊聚类分析法对三类乳液（纯丙、苯丙和醋丙）进行分类,建立近红外涂料乳液定性分析模型。18批未知样品用于验证模型校正集,校正集的纯丙乳液、苯丙乳液和醋丙乳液的马氏距离阈值分别为3．7、4．4和4．3。18批未知样品预测样品的准确率为100％,表明近红透射光谱法可以取代传统的鉴别方法对三种乳液进行定性分析。     

成膜助剂在高T_g乳液木器漆中的应用

针对高Tg乳液在木器漆(通常为家具漆)应用中所面临的可操作性问题,讨论了决定因素之一的成膜助剂的影响,基于测试结果提出建议配方.     

近红外光谱技术用于制浆原料分析的研究进展

对近红外光谱技术的原理、分析方法及特点等作了介绍,综述了当前将近红外光谱技术应用于制浆原料的快速分类,及其在制浆原料化学成分测定、水分含量测定、基本密度测定和纤维形态分析中的运用,并分析了实际投产应用面临的问题,最后对未来发展趋势进行了展望。     

Pharmaceutical Cocrystals of Ethenzamide: Molecular Structure Analysis Based on Vibrational Spectra and DFT Calculations

Pharmaceutical cocrystals can offer another advanced strategy for drug preparation and development and can facilitate improvements to the physicochemical properties of active pharmaceutical ingredients (APIs) without altering their chemical structures and corresponding pharmacological activities. Therefore, cocrystals show a great deal of potential in the development and research of drugs. In this work, pharmaceutical cocrystals of ethenzamide (ETZ) with 2,6-dihydroxybenzoic acid (26DHBA), 2,4-dihydroxybenzoic acid (24DHBA) and gallic acid (GA) were synthesized by the solvent evaporation method. In order to gain a deeper understanding of the structural changes after ETZ cocrystallization, terahertz time domain spectroscopy (THz-TDS) and Raman spectroscopy were used to characterize the single starting samples, corresponding physical mixtures and the cocrystals. In addition, the possible molecular structures of ETZ-GA, ETZ-26DHBA and ETZ-24DHBA cocrystals were optimized by density functional theory (DFT). The results of THz and Raman spectra with the DFT simulations for the three cocrystals revealed that the ETZ-GA cocrystal formed an O−H∙∙∙O hydrogen bond between the -OH of GA and oxygen of the amide group of the ETZ molecule, and it was also found that ETZ formed a dimer through a supramolecular amide–amide homosynthon; meanwhile, the ETZ-26DHBA cocrystal was formed by a powerful supramolecular acid–amide heterosynthon, and the ETZ-24DHBA cocrystal formed the O−H∙∙∙O hydrogen bond between the 4-hydroxy group of 24DHBA and oxygen of the amide group of the ETZ molecule. It could be seen that in the molecular structure analysis of the three cocrystals, the position and number of hydroxyl groups in the coformers play an essential role in guiding the formation of specific supramolecular synthons.     

Analysis of Among-Species Variability in Wood Fiber Surface Using DRIFTS and XPS: Effects on Esterification Efficiency

Abstract

Variability in the chemical composition of surface properties of various wood fibers (eastern white cedar, jack pine, black spruce, and bark) was investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray photoelectron spectroscopy (XPS). Both DRIFTS and XPS showed high variability in fiber surface composition between species and between fiber types (sapwood, heartwood, and bark). Fiber surface was modified by esterification reaction using a maleic anhydride polyethylene (MAPE) treatment. DRIFTS failed to assess surface modification, whereas XPS results showed that MAPE treatment increased the surface hydrocarbon concentration of jack pine wood fiber, indicated by a decrease in oxygen–carbon ratio and an increase in relative intensity of the C1 component in the C1s signal. Lignin concentration variability on the fiber surface was determined as the major factor that prevents esterification from taking place.     

近红外光谱技术在含能材料成分分析中的建模研究

近红外光谱法在对含能材料成分的分析中采用不同波数以及不同区间的变量，并用偏最小二乘法建立数学模型。建模结果说明模型精度较高，缩减后的自变量矩阵X中提取的主成分对原因变量有着更好的解释能力，并提高了计算速度。