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1.
Abstract The lignins from dewaxed oil palm trunk and empty fruit bunch (EFB) fibers were fractionated into 95% ethanol soluble, cold and hot water soluble, and 1% NaOH soluble lignins, respectively. The chemical and structural composition of the lignin preparations was determined by using UV, GPC, FT-IR, 13C-NMR spectroscopy and nitrobenzene oxidation. The alkali soluble and 95% ethanol soluble lignin fractions were found to contain low amounts of chemically linked polysaccharides, 2.9-3.9% and 7.5-8.0%, respectively, while the water soluble lignin fractions showed significant amounts of bound polysaccharides (16.2-23.3%). All of the lignin fractions contained a high proportion of non-condensed syringyl units, together with small amounts of non-condensed guaiacyl and fewer p-hydroxyphenyl units. The lignin from oil palm EFB fiber contained a significant amount of esterified p-hydroxybenzoic acid and a minor quantity of esterified glucuronic acid. Trace of ferulic acids was both esterified and etherified to lignin side chains in the EFB fiber cell walls. 相似文献
2.
The posttreatment of various organosolvs pretreated wheat straw with cyanamide-activated hydrogen peroxide was studied. About 44–80% of the total residual lignin and 38–85% of the total residual hemicelluloses were released or degraded during the posttreatment with 1.8% H2O2–0.18% cyanamide at 50°C under pH 10.0 for 4 h from different aqueous organic acids or alcohols pretreated straw. The seven degraded residual lignin preparations were subjected to a comprehensive physicochemical and structural characterization by UV, FTIR, and 1H and 13NMR spectroscopy, and GPC. The nitrobenzene oxidation method was also applied to the in situ lignins. It was found that the seven residual lignin preparations contained large amounts of noncondensed syringyl and guaiacyl units, together with fewer noncondensed p-hydroxyphenyl units, esterified p-coumaric acid, and mainly etherified ferulic acid. All of the lignin fractions are free of associated polysaccharides and had molecular-average weights ranging between 2980 and 3820 g mol−1. Analysis of these low molecular weight degradation products revealed an oxidation of residual lignin had occurred. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
3.
《分离科学与技术》2012,47(8):1809-1829
Abstract One chlorophyll rich fraction and two lignin preparations were separated from perennial grass and cocksfoot grass by sequential three‐stage treatments with 80% ethanol containing 0.2% NaOH, 2.5% H2O2?0.2% EDTA containing 1.5% NaOH, and 2.5% H2O2?0.2% TAED containing 1.0% NaOH at 75°C for 3 h, respectively, which released 4.6 and 3.6% chlorophyll rich fraction, 2.3 and 5.8%, and 0.9 and 1.0% lignin preparations, except for releasing 8.0 and 10.4%, 79.1 and 77.0%, and 12.9 and 12.5% of the original hemicelluloses, respectively. The lignin fractions obtained from the two different grasses had very similar molecular weights and structural composition. The NMR spectra of the lignin preparations revealed the presence of p‐hydroxyphenyl, guaiacyl, and syringyl structures, and the lignin in chlorophyll rich fraction contained more guaiacyl and syringyl units than p‐hydroxyphenyl unit, whereas the reverse trend was found in the two lignin preparations. The lignin preparations are distinguished with straw and wood lignins by relatively higher contents of p‐hydroxyphenyl unit and lower amounts of condensed units (β‐5 and 5‐5′) and resinol units (β‐β). This difference in distribution of structural units indicated some structural heterogeneity between grass and straw/or wood lignin. 相似文献
4.
Nine lignin fractions from bamboo (Dendrocalamus brandisii) were sequentially isolated with hot water at 80, 100, and 120°C for 3 h and 60% aqueous ethanol containing 0.25, 0.5, 1.0, 2.0, 3.0, and 5.0% NaOH at 80°C for 3 h. Molecular weight and purity analysis revealed that the lignin fractions isolated by hot water (L1, L2, and L3) had lower weight-average molecular weights (between 1350 and 1490 g mol−1) and contained much higher amounts of associated hemicelluloses (between 9.26 and 22.29%), while the lignin fractions isolated by alkaline aqueous ethanol (L4, L5, L6, L7, L8, and L9) had higher weight-average molecular weights (between 2830 and 3170 g mol−1) and contained lower amounts of associated hemicelluloses (between 0.63 and 1.66%). Spectroscopy (UV, FTIR, 13C-NMR, and HSQC) analysis showed that the bamboo (Dendrocalamus brandisii) lignin was typical grass lignin, consisting of p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) units. The major interunit linkages presented in the alkaline aqueous ethanol extractable bamboo lignin were β-O-4′ aryl ether linkages (about 74.3%), followed by β-β′ resinol-type linkages and β-1′ spirodienone-type linkages (both for 7.8%), together with small amounts of β-5′ phenylcoumaran (6.8%) and p-hydroxycinnamyl alcohols end groups (3.1%). In addition, a small percentage (1.0%) of the lignin side-chain was found to be acetylated at the γ-carbon, predominantly over syringyl units. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
5.
《分离科学与技术》2012,47(8):1272-1279
Dewaxed Calamagrostis angustifolia Kom was pretreated with hot water at 60 and 90°C for 3 h, and then the residue obtained was successively treated with 70% ethanol, and 70% ethanol containing 0.2%, 1.0%, 2.0%, 4.0%, and 8.0% NaOH at 80°C for 3 h. The dissolved components were subjected to further separation to get eight lignin fractions, which were characterized by gel permeation chromatography, Fourier transform infrared, and sugar analysis. All the lignin fractions had small weight-average molecular weights between 810 and 2580 g/mol. Two typical lignins, L3 (prepared with 70% ethanol) and L5 (prepared with 70% ethanol containing 1.0% NaOH), were further analyzed using 1H, 13C NMR and HSQC spectroscopy. Signals from guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H) units observed in aromatic/olefinic region of HSQC spectra indicated that the lignin from Calamagrostis angustifolia Kom could be classified as “GSH” lignin. In aliphatic-oxygenated region, β-O-4′ together with small amounts of β-5′, β-β′, and p-hydroxycinnamyl alcohol end group were the main interunit linkages observed. Aqueous ethanol, which could avoid the cleavage of ether bonds in lignin at neutral condition, was more effective than water on lignin extraction. 相似文献
6.
The content and structure of lignin have been considered as important factors that affect both pretreatment and enzymatic hydrolysis of lignocellulosic biomass. In this work, wheat stems (WS) were pretreated using mild alkali including green liquor (GL) and sodium carbonate (SC). The results indicate that GL pretreatment exhibits better delignification selectivity and higher enzymatic digestibility than SC pretreatment. Analysis of 1H–13C HSQC NMR and FTIR on cellulolytic enzyme lignin (CEL) preparations isolated from untreated and pretreated WS also proves that a certain amount of lignin degrades which leads to a decrease of β-O-4′ linkages. Under mild alkaline conditions, more guaiacyl units in lignin are removed than syringyl units, which results in a higher condensation degree and S/G ratio of CELs isolated from GL- and SC-pretreated stems. Compared with p-coumarate structures, ferulates in lignin are more stable under mild alkaline conditions. 相似文献
7.
This study aimed to clarify why the β-O-4 bond cleavage of syringyl lignin is more rapid than that of guaiacyl lignin under alkaline pulping conditions. We examined whether or not three chemical factors, acidity of the α-hydroxy group, nucleophilicity of the generated α-alkoxide, and leaving ability of the leaving phenoxide, are different between syringyl and guaiacyl lignins and control the rate of the alkaline-induced β-O-4 bond cleavage, employing dimeric non-phenolic β-O-4-type lignin model compounds (LMCs) and novel methods for estimating these three factors. The results indicated that the α-hydroxy groups of syringyl-type LMCs are relatively more acidic than those of guaiacyl-type and that syringyl nucleus is a better leaving group than guaiacyl nucleus in the β-O-4 bond cleavage. These factors result in the β-O-4 bond of syringyl lignin being more prone to the alkaline-induced cleavage than that of guaiacyl lignin. 相似文献
8.
Abstract Substituent effects on the chemical shifts of aromatic carbons in lignin model compounds have been elucidated from 13C NMR spectra of guaiacyl and syringyl type monomerio and β-O-4 model compounds and guaiacyl type β-5 model compounds. Evaluation of the observed values of substituent chemical shift (SCS) for the aromatic carbons leads to elucidation of a generalized SCS additivity rule, for estimation of the chemical shifts of aromatic carbons in ring A of β-O-4 and β-5 type substructures in model compounds and in ring B of β-O-4 substructures in lignin preparations, with errors of less than 1 ppm. The rule is applicable to substructures of both guaiacyl and syringyl types, using an appropriate parent compound as reference instead of benzene. Signals in the aromatic region of the 13C NMR spectra of β-O-4 and β-5 type model compounds are reassigned on the basis of the observed SCS's as well as APT spectra of the compounds. 相似文献
9.
Deded Sarip Nawawi Wasrin Syafii Iori Tomoda Yosuke Uchida Takuya Akiyama Tomoya Yokoyama 《木材化学与工艺学杂志》2017,37(4):273-282
The chemical characteristics of lignin, including the Klason lignin content, acid-soluble lignin content, proportion of the aromatic ring types [syringyl ratio = syringyl/(syringyl + guaiacyl)], and proportion of the diastereomeric forms for the β-O-4 structure [erythro ratio = erythro/(erythro + threo)], and pulpability were investigated for 28 wood samples belonging to the genera Acacia and Eucalyptus. Although the lignin characteristics of these 28 woods varied widely, the chemical characteristics of the two genera could be categorized in two clearly distinguished groups on the basis of the syringyl ratio. Clear negative correlations were observed between both the syringyl and erythro ratios and the total lignin content (sum of the Klason and acid-soluble lignin contents) within each genus. In addition, the syringyl ratio correlated positively with the erythro ratio and acid-soluble lignin content, regardless of the genus. The existence of a clear, high correlation between the syringyl and erythro ratios supports the hypothesis that the aromatic ring type (syringyl ratio) is a decisive factor for controlling the diastereomeric forms of the β-O-4 structure (erythro ratio). Each of the wood samples was also subjected to Kraft pulping, and it was demonstrated that the woods with higher syringyl ratios were easier to delignify. This tendency is reasonably attributed to the high reactivity of the erythro-rich and syringyl-rich β-O-4 structures, and the low lignin content of these syringyl-rich woods. 相似文献
10.
R. Krishna Mohan Rao Kallury Thomas T. Tidwell Foster A. Agblevor David C. B. Boocock Martin Holysh 《木材化学与工艺学杂志》2013,33(3):353-371
Abstract Rapid hydrothermolysis at 350°C of poplar sapwood, heartwood and bark, as well as the lignin extracted from the sapwood and heartwood, gives oil and water soluble fractions whose chemical analysis is correlated with the nature of the feed stock. Results from cellulose and Douglas fir are included, and the poplar bark and heartwood lignin are shown to give an ether soluble oil that consists mainly of guaiacyl units while the sapwood product is mainly syringyl. However, the chloroform soluble oil from both sapwood and heartwood was mainly syringyl with the additional presence of carbohydrate derived material in the heartwood oil. The acetone-only soluble residue from sapwood was shown by pyrolysis mass spectrometry to be mainly cellulose derived while that from heartwood was mainly from lignin. Thus there is a fundamental difference in the behaviour of the poplar sapwood and heartwood that may arise from different distributions of the guaiacyl and syringyl units, and of the binding to the cellulose. The origin of the rapid hydrothermolysis products with respect to the major wood components is discussed. An empirical approach to the calculation of the lignin content based on the rapid hydrothermolysis fractions is presented. 相似文献
11.
A new rapid method of two step precipitation for isolation of alkali-soluble lignins with relatively free of polysaccharides from wheat straw was proposed in this study. The isolated alkali-soluble lignin fractions LA contained rather low amounts of neutral sugars (0.7–1.0%) and had low average molecular weights (960–1440 Da). The isolated lignin fractions LA contained roughly equal amounts of guaiacyl (G) and syringly (S) units with relatively fewer p-hydroxyphenyl (H) units, and appeared to be closely associated to phenolic acids and glucuronic acid or 4-O-methylglucuronic acid. The chemical compositions in each of the fractions are reported. The physico-chemical properties and structure features of these lignin fractions LA were characterized by UV-, IR-, 13C-NMR-spectroscopy, and alkaline nitrobenzene oxidation. © 1996 John Wiley & Sons, Inc. 相似文献
12.
Lignin fractions obtained by steam explosion pretreatment and subsequent alkaline ethanol solution post‐treatment from Lespedeza cyrtobotrya stalks were studied in terms of chemical characteristics, to reflect the influence of elevating steam pressure from 15 to 25 kg/m2. Because of the remarkable selectivity with respect to lignin, the post‐treatment with 60% ethanol solution containing 1% NaOH yielded 8.3, 13.0, 16.0, 16.4, and 17.8% lignin fractions from the samples steam‐exploded at 15, 17.5, 20, 22.5, and 25 kg/m2 for 4 min, respectively, comparing to 7.7% lignin removal from the raw material. Steam explosion pretreatment, not only obviously cleaved the linkage between carbohydrates and lignin resulting in the significantly decrease of the associated hemicelluloses in lignin fractions, but also broke the β‐O‐4 bond between lignins to some degrees. In particular, slightly more guaiacyl moieties than syringyl units were affected. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
13.
以蔗渣为原料,经脱蜡后依次用H2O、1% NaOH和3% NaOH进行抽提,分别得到水溶性木质素L1和碱溶性木质素L2、L3,并对其理化性质和结构特征进行分析。通过硝基苯氧化法、高效液相色谱检测来确定蔗渣木质素的组分,通过凝胶渗透色谱检测蔗渣木质素的分子质量,利用紫外分光光度计和二维核磁共振推导出蔗渣木质素的结构单元和连接方式。结果表明,L1、L2和L3的得率(以绝干原料计)分别为0.4%、5.7%和3.7%,占蔗渣木质素总量的54.1%,而且水溶性木质素分子质量大于碱溶性木质素。L2和L3主要来自于蔗渣次生壁,富含紫丁香基单元和大量的非缩合醚结构。蔗渣木质素的结构单元间的主要连接方式是β-O-4'醚键,还有β-β'、β-5'和β-1'等碳碳结构。蔗渣木质素是由紫丁香基、愈创木基和少量对羟苯基结构单元组成的GSH型木质素,此外,还含有对香豆酸和阿魏酸,通过酯键与木质素相连。 相似文献
14.
Acetosolv lignins obtained under a variety of pulping conditions as regards acetic acid concentration, catalyst concentration, temperature and pulping time were characterized structurally by elemental analysis, FTIR and 1H and 13C NMR spectroscopy, and determination of methoxyl group content. Increasing catalyst concentration and pulping time favours both the dissolution of lignin (by cleavage of α and β-O-4 bonds) and the occurrence of condensation reactions. Increasing temperature favours the degradation of syringyl units more than of guaiacyl units. 相似文献
15.
Heterogeneity of sugarcane lignin with respect to the composition of structural units in different morphological regions was studied by microautoradiography and some degradative analyses. Structure of the lignin differs among fiber, vessel and parenchyma. The lignin in the secondary wall of fiber is composed of syringyl (S)-, guaiacyl (G)- and p-hydroxyphenyl (H)-propane units with accompanying phenolic acid residues, and the proportion of these monolignols is S > G > H. The lignin in vessels of protoxylem contains more G and H units than S units, and that in vessels of metaxylem is similar to that in fibers. Phenolic acid constituent in sugarcane cell wall includes sinapic acid in addition to p-coumaric and ferulic acids. Ferulic acid deposits at the very early stage of lignification, and p-coumaric and sinapic acids increasingly deposit with the progress of lignification. Therefore, the ratio of p-coumaric acid or sinapic acid to ferulic acid increases with lignification. Parenchyma wall involves larger amount of phenolic acids than vascular bundle does. The lignin in parenchyma is difficult to isolate by Björkman procedure, because there is greater possibility to form cross-linkage among cell wall polymers through phenolic acids. The cross linkages involving phenolic acid ester also explains why the sugarcane lignin is easily degraded. 相似文献
16.
Kraft-AQ pulping lignin was sequentially fractionated by organic solvent extractions and the molecular properties of each fraction were characterized by chemical degradation, GPC, UV, FT-IR, (13)C-NMR and thermal analysis. The average molecular weight and polydispersity of each lignin fraction increased with its hydrogen-bonding capacity (Hildebrand solubility parameter). In addition, the ratio of the non-condensed guaiacyl/syringyl units and the content of β-O-4 linkages increased with the increment of the lignin fractions extracted successively with hexane, diethylether, methylene chloride, methanol, and dioxane. Furthermore, the presence of the condensation reaction products was contributed to the higher thermal stability of the larger molecules. 相似文献
17.
Xing-Ping Guo 《木材化学与工艺学杂志》2015,35(1):43-51
Wood lignin contains significant amounts of acid-labile aryl ether units, which play a significant role in lignin modification or delignification processes. We have evaluated the rate and reaction kinetics on the acid-catalyzed cleavages of aryl ether structures for wood lignin in situ based on the formation of phenolic hydroxyl groups. The content of acid-labile aryl ether units was quite uniform for a variety of softwood wood lignins (~4% per C9 unit) and it varied appreciably among hardwood species, ranging from 4% for aspen to 9% for beech wood lignin. These variations, however, appear to be related to the content of syringyl units in wood lignin. The reactivity of these reactive aryl ether structures was noticeably higher for the spruce than for the aspen wood lignin. This difference in reactivity, based on the behavior of lignin model compound reactions, can be attributed to the influence of syringyl moieties in aspen wood lignin. It appears that most of the acid-labile aryl ether units in hardwood were associated with the syringy moiety being present as a benzyl unit, which is much less reactive than the corresponding guaiacyl moiety. 相似文献
18.
Abstract The fractionation of wood cell wall components was achieved by the application of the LiCl/DMSO solvent system developed in our previous study. Various soluble and insoluble fractions were prepared from beech milled wood by extractions with DMSO containing different amounts of lithium chloride (LiCl) for the study of a lignin-carbohydrate complex (LCC). Nitrobenzene oxidation (NO) analyses demonstrated that the lignin in the soluble fractions always has lower yields of NO products consisting of syringaldehyde + syringic acid (Sy) and vanillin + vanillic acid (Va). The syringyl ratios, Sy/(Sy+Va), were also lower than in insoluble fractions. Accordingly, lignins with lower syringyl ratios are better soluble than those with higher syringyl ratios. The former is typical in the primary wall and the latter in the secondary wall. Solubilization of glucan is significantly dependent on the LiCl concentration in DMSO. In the absence of LiCl, only about 6% of glucan was found in the soluble fraction, but about 40% of lignin and xylan were solubilized. The additional 40% of lignin and xylan became soluble together with glucan solubilization, which increased at 3% LiCl concentration. However, a fraction amounting to 13% (based on the whole wood) still remained as a residue under these conditions. Glucan solubilization could not be the reason for this observation as ball-milled cellulose is soluble in 3% LiCl/DMSO. It is likely that strong interactions between lignin and carbohydrates prevent solubilization of this fraction, which has never been isolated and analyzed in previous studies. 相似文献
19.
Ball-milled and enzyme lignins were extracted with 90 and 50% dioxane–water from 6 days ball-milled wheat straw, and subsequently cellulase-treated straw residues, respectively. The crude lignin preparations were purified using a two-step precipitation method instead of the traditional ether precipitation procedure, and fractionated into pure milled lignin (PML), pure enzyme lignin (PEL), hemicellulose-rich milled lignin (HRML), lignin-rich enzyme lignin (LREL), and solubilized lignin during enzyme treatment (SLET) fractions. The five lignin fraction were studied using spectroscopic and degradative tecyhniques. The PML and PEL fractions showed very low content of associated polysaccharides (2.36–2.86%). The PML is mainly composed of β-O-4 ether bonds in the lignin structural units. The less common β-5 and β-β carbon–carbon linkages are also present. The results obtained also indicated that the lignins in wheat straw cell walls appeared to be very closely associated to p-coumaric and ferulic acid, and glucuronic acid or 4-O-methylglucuronic acid. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1633–1641, 1998 相似文献
20.
Oxidation of a lignin model disyringyl dimer with nitrogen dioxide (NO2) in the presence of air and N-hydroxysuccinimide led to C1-Cαcleavage with the formation of approximately equal amounts of 2,6-dimethoxy-p-benzoquinone (DMBQ) and glyceraldehyde-2-syringyl ether type structures. The result indicates that only the phenolic end syringyl units of a lignin polymer will be converted to DMBQ upon treatment with the current NO2 reaction conditions. Internal (non-phenolic) lignin units, bonded by β-O-4 linkages, will resist oxidation. 相似文献