定量~(13)C-NMR谱表征蔗渣碱木素结构

从蔗渣纸浆黑液中制出纯蔗渣碱木素，然后测定其定量13C-NMR谱．图谱分析表明，蔗渣碱木素主要由紫丁香基，愈创木基和对羟苯基三种丙烷结构单元组成，其中未绩合的紫丁香基、愈创木基和对羟羊基含量比为2.2：1．0：1．4．蔗渣碱术素结构单元间主要以β-O－4烷基芳基醚键连接，也有一定量的非环状α-醚键存在．蔗渣碱木素中，相当部分对香豆酸类结构并非通过酯键而是通过醚键或碳双键连接于芳核上．     

Absolute Configuration of β- and α-Asymmetric Carbons within β-O-4-Structures in Hardwood Lignin

In this study, we investigated the proportion of erythro- and threo-forms of β-O-4-ether structures and their enantiomeric compositions in hardwood lignin by applying the ozonation method to birch wood meal. Optical activity was not substantially observed in either the erythronic or threonic acids obtained as the ozonation products of β-O-4-structures in birch wood meal. The proportions of the four stereoisomeric forms {(αS,βR)-erythro, (αR,βR)-threo, (αS,βS)-threo, and (αR,βS)-erythro forms} were estimated to be 37-38%, 13-14%, 12-13%, and 36-37% based on the yields of erythronic and threonic acids, and on their optical activities. The proportions suggest that the entire components of β-O-4-ether structures in birch wood lignin have R- and S-configurations at the β-carbon in approximately the same quantities {(βR)-β-O-4-structure: (βS)-β-O-4-structure = 50–52:48–50}; i.e., that the β-ether structures are essentially racemic. This estimation implies that, during lignin biosynthesis, an equal number of enantiomeric forms of β-O-4-bonded quinone methides were formed by radical coupling reactions.     

Characteristics and Reactivity of Lignin in Acacia and Eucalyptus Woods

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.     

麦草烧碱—蒽醌—乙二胺制浆的研究

在麦草烧碱-蒽醌蒸煮液中加入少量乙二胺可以减少筛渣率和降低纸浆的卡伯值、使纤维分离点提前、提高纸浆的粘度和纤维结晶度,改善纸浆的可漂性及提高纸浆的机械强度(尤其是撕裂强度)。用SEM研究了烧碱-AQ-EDA纸浆的纤维发现;乙二胺加入烧碱-AQ液中能加速胞间层木素的脱除。     

Characteristics of Dioxane Lignins Isolated at Different Ages of Nalita Wood (Trema orientalis)

Abstract

Nalita (Trema orientalis) is one of the fastest growing trees in the tropical countries. The structural characteristics of lignin isolated at different ages of Nalita wood (Trema orientalis) by acidolytic dioxane method were examined by UV, FTIR, ¹H‐NMR and ¹³C‐NMR spectroscopy, alkaline nitrobenzene oxidation, molecular weight determination, elemental and methoxyl analysis. The data were compared with aspen lignin. The structural analysis revealed that Nalita wood lignin is syringyl‐guaiacyl type. The methoxyl content in Nalita wood lignin was lower than aspen lignin. The C₉ formulas for 30‐months‐old Nalita was C₉H_9.31O_3.13(OCH₃)_1.27, whereas that of aspen was C₉H_8.94O_3.15(OCH₃)_1.47. The weight average molecular weight of Nalita wood lignin was decreased from 36,500 to 25,500 with increasing tree age from 12 to 30 months, whereas weight average molecular weight of aspen was 20,000. Both alcoholic and phenolic hydroxyl group in Nalita wood lignin is lower than aspen lignin.     

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.     

Sunflower as a biofuels crop: An analysis of lignocellulosic chemical properties

Four accessions of cultivated sunflower (Helianthus annuus) and silverleaf sunflower (Helianthus argophyllus), were each grown in three locations (Georgia, British Columbia, and Iowa) at different planting densities and phenotyped for biomass-related traits and wood biochemistry. In most environments, H. argophyllus produced significantly more biomass than H. annuus. Cell wall chemistry for a subset of plants grown in Georgia and Iowa was assessed using analytical wet chemistry methods to measure lignin and sugar content/composition. The analysis of lignin and the S/G-lignin ratios for a larger number of samples (n > 250) was also assessed by high-throughput pyrolysis Molecular Beam Mass Spectrometry. Average pyMBMS estimated lignin content (i.e., dry weight fraction) for 60 °C dried basal stem samples of H. annuus and H. argophyllus was 29.6% (range, 24.0%–34.6%) and 28.6% (range, 24.6%–33.3%), respectively when averaged across all environments. The average S/G lignin mass ratio was 1.5 (range, 1.0–2.0) for H. annuus and 1.7 (range, 1.0–2.4) in H. argophyllus. Stem samples from these two species only differed statistically for a few cell wall chemistry traits; however, accession level differences within each species were apparent. Cell wall chemistry in both species was significantly affected by both location and planting density, thus demonstrating the need to select for these traits in the environment for which the crop will be produced. Overall, these results show that cultivated sunflower and silverleaf sunflower both possess the necessary phenotypic diversity to facilitate the development of a hybrid sunflower with improved lignocellulosic biofuels traits, namely increased biomass, decreased lignin, and increased glucan.     

Impact of lignin composition on cell‐wall degradability in an Arabidopsis mutant

An Arabidopsis mutant that does not deposit syringyl‐type lignin was used to test the hypothesis that lignin composition impacts cell‐wall degradability. Two lines of the ferulate‐5‐hydroxylase‐deficient fah1 mutant and the wild‐type control line were grown in the greenhouse. In Experiment 1, the plants were harvested at the mature seed stage. For Experiment 2, plants were harvested 5, 6, 7 and 8 weeks after sowing. In both experiments stems were collected and analysed for cell‐wall concentration and composition, and in vitro degradability of cell‐wall polysaccharide components by rumen micro‐organisms. The absence of syringyl‐type lignin was confirmed for the mutant lines by nitrobenzene oxidation and pyrolysis‐GC‐MS. Lignin concentration was the same for all three Arabidopsis lines, at all stages of maturity. The Arabidopsis stems were similar to forage legumes in that the potentially degradable cell‐wall fraction was very quickly degraded. Cell‐wall polysaccharide degradability did not differ among the Arabidopsis lines in the first experiment after 24‐h fermentations, but the cell‐wall polysaccharides of the fah1‐2 mutant line were less degradable after 96‐h than either the wild‐type or the fah1‐5 mutant. In contrast, in Experiment 2 no differences among lines were found for cell‐wall polysaccharide degradability after either 24‐ or 96‐h fermentations; however, signficantly higher levels of ester‐bound ferulic acid were found in the walls of the fah1 mutant lines. As expected, increasing stem maturity was correlated with reduced degradation of cell‐wall polysaccharides. These experiments indicate that either lignin composition, as measured by syringyl‐to‐guaiacyl ratio, does not alter cell‐wall degradability in Arabidopsis, or that the fah1 mutation has other effects on the cell walls of these mutants such that the impact of the change in syringyl‐to‐guaiacyl ratio is masked. © 1999 Society of Chemical Industry     

Characterisation of Lignin from CAD and OMT Deficient Bm Mutants of Maize

Internodes of the maize cell line W401 and bm₁ and bm₃ mutants expressed in W401 were harvested 5 days after anthesis (A5) and at silage (S) stage. The normal maize had a higher total phenolic (TP) content (80·5–90·5 g kg^-1 cell wall DM) than both bm₁ and bm₃ mutants (74·4–86·4 and 66·0– 84·2 g kg^-1 cell wall DM, respectively). TP were inversely related to cellulase digestibility with values of 85·4–91·5, 89·3–92·1 and 91·3–94·1% for normal, bm₁ and bm₃. Marked differences in p-coumaric acid concentrations were found ranging from 20·9 to 26·3 g kg^-1 cell wall DM for normal, 14·9 to 15·3 g kg^-1 for bm₁ to 10·1 to 14·4 g kg^-1 for bm₃. The ferulate pattern was entirely different with the bm₁ genotype providing the lowest total (9·1–10·7 g kg^-1) and etherified (1·9–2·3 g kg^-1) values. Although the bm₃ contained more total ferulate (11·5–13·1 vs 10·9–11·7 g kg^-1), the normal variety had a significantly greater amount of etherified ferulate (2·8–3·4 vs 3·2–4.1 g kg^-1) implying a greater extent of cross-linking between wall polymers. Recovery of guaiacyl and syringyl residues was greatest in the normal maize with the bm₁ occupying the middle position between the two extremes. Calculated S: G ratios from 4 M NaOH digestion and NMR were in good agreement with the normal line giving the highest ratio, bm₁ intermediate and bm₃ the lowest. Colorimetric analysis revealed a large increase in the aldehyde content of the in situ bm₁ lignin compared to normal and bm₃ genotypes although NMR failed to reveal significant numbers of aldehydic resonances. © 1997 SCI.     

Characterisation of Lignin from Parenchyma and Sclerenchyma Cell Walls of the Maize Internode

Internodes of maize (Zea mays L, Co125), harvested 5 days after anthesis, were sectioned into five equal parts and samples of sclerenchyma and parenchyma cells mechanically isolated from each section. Phenolic acids and syringyl and guaiacyl degradation products of lignin were released from the walls of the two cell types by microwave digestion with 4 M NaOH. Aryl ether bonded units were selectively released by thioacidolysis. Total phenolic content of cell walls from the youngest (basal) sections were approximately two-thirds of those of the oldest, topmost sections (parenchyma 70·8–99·0 and sclerenchyma 72·5–114·1 mg g^-1) indicating that the process of lignification was already well advanced amongst most of the cell walls of the youngest section. The total phenolic content was marginally, but significantly, greater (P<0·05) in sclerenchyma walls than in parenchyma walls at all stages of maturity. There was no significant difference in phenolic acid concentrations between cell types from the same section but p-coumaric acid concentration increased with maturity (P<0·001) in walls from both cell types. The increase in p-coumarate with age was matched by an increased recovery of syringyl units resulting in a constant coumaroyl: syringyl molar ratio. Recovery of acetosyringone was significantly greater (P<0·001) from sclerenchyma than parenchyma walls and, in sclerenchyma, acetosyringone as a proportion of total syringyl recovery, increased significantly with age (P=0·015). Digestion with NaOH and thioacidolysis released comparable amounts of guaiacyl residues but NaOH digestion released approximately twice the amount of syringyl residues. This difference may be explained by the retention of the ester-bond between p-coumaric acid and syringyl units during thioacidolysis but not during digestion with 4 M alkali. The similarity in phenolic composition suggested that both cell types, despite their considerable anatomical differences, were exposed to a common flux of lignin precursors during the later stages of lignification as illustrated by the internode sections. Differences between cell walls arose because of differences in the regiochemistry of precursor incorporation. © 1997 SCI.