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.     

Fractional Isolation and Structural Characterization of Lignins from Oil Palm Trunk and Empty Fruit Bunch Fibers

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.     

水溶性和碱溶性蔗渣木质素的分离与表征

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。     

Fractional Separation and Structural Characterization of Chlorophyll and Lignin from Perennial Ryegrass (L. perenne) and Cocksfoot Grass (D. glomerata)

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.     

Fractionation and Characterization of Wood Cell Wall Components of Fagus crenata Blume Using LiCl/DMSO Solvent System

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 (S_y) and vanillin + vanillic acid (V_a). The syringyl ratios, S_y/(S_y+V_a), 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.     

Chemical Factors Underlying the More Rapid β-O-4 Bond Cleavage of Syringyl than Guaiacyl Lignin under Alkaline Delignification Conditions

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.     

Pulping Yield and Delignification Kinetics of Heartwood and Sapwood of Maritime Pine

Abstract

In maritime pine (Pinus pinaster Ait.), heartwood represents a substantial part of the tree stem at final harvest age (80 years) corresponding to 42% at the base of the stem wood diameter and decreasing upward. The rate of heartwood formation was estimated at 0.35 rings/year, beginning at 18 years of age. Differences in the chemical composition between heartwood and sapwood were mainly in the extractives, 19.7% and 5.8%, respectively. The lignin content was 23.1% and 24.5% in the heartwood and sapwood, respectively. Pulping yield of the heartwood was lower than that of the sapwood (40.0% vs. 49.7%) and was negatively correlated with the extractives content. Extraction of heartwood prior to pulping increased the pulp yield and the delignification (lower residual lignin in pulps). Pulping kinetics showed lower yields for heartwood at all pulping stages, the difference occurring especially in the initial reaction phase. However, delignification rate constants were similar for heartwood and sapwood (3.1×10^?2 min^?1 and 2.7×10^?2 min^?1 for the main delignification phase for sapwood and heartwood, respectively), with a lower activation energy for sapwood (68.3 vs. 90.0 kJ · mol^?1). The presence of heartwood decreases the raw‐material quality for pulping and this should be taken into account when harvesting trees for pulping processes.     

Condensation Reactions of Softwood and Hardwood Lignin Model Compounds Under Organic Acid Cooking Conditions

In order to examine the condensation reactions of softwood and hardwood lignin during organic acid cooking, mixtures of benzyl alcohol type lignin model compounds with guaiacyl and syringyl units as the sources of benzyl cations and creosol and 5-methoxycreosol as the sources of electron-rich aromatic carbons were cooked under acidic pulping conditions.

From the yield of the condensation products in the initial reactions, it was shown that the carbonium cations of guaiacyl nuclei were more reactive than those of syringyl nuclei.

Syringyl type aromatic ring carbons had higher reactivities than guaiacyl type ones.

The cleavage of the benzyl ether bond in syringyl compounds was slower than that of guaiacyl compounds.

The diphenylmethane structures formed by the condensation reaction between veratryl alcohol and 5-methoxycreosol were found to be unstable under the strong acidic cooking conditions.

It is concluded that the condensation reactions between benzylic cations from the guaiacyl compounds and the electron rich aromatic ring carbons of syringyl ones are very fast, but the condensation products are unstable under the strong acidic pulping conditions.

When the guaiacyl nuclei react as an electron-rich aromatic carbon, the reaction is slower but the condensation product is much more stable.

These differences in reactivities, and the stabilities of the condensation products, may contribute to the resistance of softwood toward complete delignification on acid pulping.     

Characterization of Lignins Isolated from Alkali Treated Prehydrolysate of Corn Stover

Lignins were isolated and purified from alkali treated prehydrolysate of corn stover. The paper presents the structural features of lignins in a series purification processes. Fourier transform infrared spectroscopy, ultraviolet-vis spectroscopy and proton nuclear magnetic resonance spectroscopy were used to analyze the chemical structure. Thermogravimetric analysis was applied to follow the thermal degradation, and wet chemical method was used to determine the sugar content. The results showed that the crude lignin from the prehydrolysate of corn stover was a heterogeneous material of syringyl, guaiacyl and p-hydroxyphenyl units, containing associated polysaccharides, lipids, and melted salts. Some of the crude lignin was chemically linked to hemicelluloses （mainly xylan）. The lipids in crude lignin were probably composed of saturated and/or unsaturated long carbon chains, fatty acids, tdterpenols, waxes, and derivatives of aromatic. The sugar content of purified lignin was less than 2.11%, mainly composed of guaiacyl units. DTGmax of purified lignin was 359 ℃. The majority of the hydroxyl groups were phenolic hydroxyl groups. The main type of linkages in purified lignin was β-O-4. Other types of linkages included β-5, β-β and α-O-4.     

Influence of steaming pressure on steam explosion pretreatment of Lespedeza stalks (Lespedeza cyrtobotrya). II. Characteristics of degraded lignin

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     

Molecular Characteristics of Kraft-AQ Pulping Lignin Fractionated by Sequential Organic Solvent Extraction

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.     

Characterization of pyrolytic lignins with different activities obtained from bio-oil

Pyrolytic lignin, the water-insoluble fraction in bio-oil, often shows a high content and has strong intermolecular interactions with other compounds in bio-oil. In order to obtain pure pyrolytic lignin and facilitate the utilization of aqueous phase obtained from water extraction of bio-oil, methanol–water extraction method was employed to further separate the bio-oil water-insoluble phase in this paper. Different technologies, including Fourier transform infrared spectroscopy, gel permeation chromatography, and nuclear magnetic resonance, were adopted to characterize the structures of pyrolytic lignins with different activities obtained through this method. Both the heating value and the polymerization degree of high-molecular-weight pyrolytic lignin were higher than those of low-molecular-weight pyrolytic lignin. The molecular weight distribution of high-molecular-weight pyrolytic lignin was relatively wider, among which the contents of dimers to pentamers all accounted for 12% –18%,while the low-molecular-weight pyrolytic lignin mainly consisted of trimers(75.38%). The pyrolytic lignins had similar basic structures, both of which contained syringyl and guaiacyl units, whereas the low-molecular-weight pyrolytic lignin had more abundant syringyl units, reactive carbonyl groups and hydroxyl groups. Meanwhile,thermogravimetric study revealed that the final char residue yield of low-molecular-weight pyrolytic lignin was lower than that of high-molecular-weight pyrolytic lignin.     

The Characteristics and Reactivity of Acid-Labile Aryl Ether Units in Wood Lignin

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.     

Insoluble Lignin Models (4): Condensation Reactions of a Polymer-Bound Guaiacylpropanol Model

The reactions of syringyl alcohol with itself and with either a soluble phenol, 3-methoxy-4-hydroxyphenylpropane (guaiacylpropane, 13) or an insoluble polymer-bound phenol, guaiacylpropanol (14)¹, led to dimeric products. The low (11%), but significant yield of C5-Cα dimer 16 in the reaction of polymer-bound phenol with syringyl alcohol suggests that soluble lignin units are able to condense with insoluble lignin gels during the course of soda pulping. The yield of the C5-Cα dimer 15 in the soluble system was four times greater than that of the analogous heterogeneous dimer 16. Reactions of the polymer model 14 were not mass transfer limited.     

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.     

白腐菌Panus conchatus降解稻草木素机理研究──(二)木素降解产物高分子部分的结构特征

用定量(13)C－NMR技术研究了稻草经白腐菌Panusconchatus降解后木素的高分子部分的结构特征变化。与未经生物作用的木素相比较,发现发酵稻草木素的13C－NMR谱图出现新的吸收峰以及某些吸收峰的强度有明显变化。这些变化证实了在生物作用过程木素大分子中形成了醌类以及α-羟基酸的结构,这些类型的结构特别有利于木素进一步降解。并同时证实木素生物降解过程中发生β-O－4;Cα-Cβ及Cβ-Cγ键的断裂及Cγ的氧化。定量分析结果表明,经生物降解后木素大分子的甲氧基和羧基含量增加,愈疮木基和对羟基苯基结构单元优先降解,推断出此白腐菌对稻草的作用首先进攻纤维胞间层,其结果与电子显微镜所得的结果相一致。分析结果同时表明,生物降解优先发生于木索非缩聚结构单元。     

Structural characterization of residual lignins isolated with cyanamide-activated hydrogen peroxide from various organosolvs pretreated wheat straw

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     

碱-氧-蒽醌蒸煮麦草脱木素

引　言木素、纤维素和半纤维素是构成麦草的主要成分 ,是自然界中较为丰富的可再生资源 .木素在制浆造纸过程中生成碱木素 ,溶于黑液 ,排入江河后 ,不仅污染了环境 ,而且浪费了大量的木素资源 ,因此寻求对可再生资源的工业化应用途径越来越受到人们的重视 .通常 ,脱木素的方法有亚硫酸盐法和碱法 ,后来许多研究者对其进行了改进 ,不过这些研究的目是为了提高纸浆得率 ,在不破坏纤维素的条件下得到白度好、易漂白、易成浆的纸浆 ,这些方法只考虑了对纤维素进行造纸的利用 ,而没有考虑对纤维素的其他利用途径以及对木素资源的利用[1～ 8] .纤…     

Determination of Sugarcane Bagasse Lignin S/G/H Ratio by Pyrolysis GC/MS

Abstract

In this work, analytical pyrolysis (Py-GC-MS) was employed to identify lignin markers derived from H, S, and G phenylpropanoid units in sugarcane bagasse. Temperatures of 450 and 500°C allowed the detection of key products that were informative on the bagasse lignin composition. The method was validated by comparing the S/G ratio as determined by the nitrobenzene oxidation (NBO) standard method for five sugarcane varieties. The S/G ratio as determined by Py-GC-MS, taking into consideration all known lignin markers in the analysis, resulted in a correlation coefficient of 0.85 with a linear regression coefficient of 0.74. When a group of selected markers (M2) was used, the correlation coefficient between methods was improved to 0.95 and the linear regression coefficient was adjusted to 0.92. M2 markers consisted of five syringyl markers (syringol, 4-methylsyringol, 4-ethylsyringol, 4-vinylsyringol, and trans-4-propenylsyringol) and four guaiacyl markers (guaiacol, 4-vinylguaiacol, 4-methylguaiacol, and vanillin). Importantly, Py-GC-MS allowed for the study of lignin composition in sugarcane bagasse without the need to remove the extractives, minimizing the work with sample preparations.     

Substituent Effects on 13C Chemical Shifts of Aromatic Carbons in β-O-4 and β-5 type Lignin Model Compounds

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.