Milled Wood Lignin Research Articles

Lignin Depolymerization in Hydrogen-Donor Solvents

Summary The conversion of different types of lignin to monophenolic compounds has been studied between 500 and 650 K, under typical coal liquefaction conditions using 9,10-dihydroanthracene (AnH2) and 7H-benz[de]anthracene (BzH) as the hydrogen-donor solvents. The yield of phenolic compounds was found to increase with the capacity of the hydrogen donor. The application of a polar cosolvent appeared to be beneficial as well. The differences in product distribution could be related to the origin of lignin. The maximum yield amounted to 11 % after 4 h at 625 K using milled wood lignin in AnH2. It has been found that lignin itself is a hydrogen-donating substance and capable of cleaving aromatic ketones such as α-phenoxyacetophenone.

Analytical pyrolysis products derived from cinnamyl alcohol-end groups in lignins

The contributions of cinnamyl alcohol-end groups to lignin-derived pyrolysis products were studied using coniferyl alcohol benzyl ether I, a model compound for cinnamyl alcohol-end groups. The profile of the pyrolysis product distribution of I demonstrated that cinnamyl alcohol-end groups are greatly responsible for the formation of propenylphenols, and cinnamyl compounds (dihydrocinnamyl alcohols, cinnamaldehydes, and cinnamyl alcohols), but play a small role in the formation of the products with a short side-chain (<C3). The contributions of coniferyl alcohol-end groups were examined in pyrolyses of reference lignins, a bulk dehydrogenative polymer of coniferyl alcohol (DHP), a Japanese cedar ( Cryptomeria japonica D. Don) wood and its milled wood lignin. Large similarity of the distribution profile of the cinnamyl compounds in the DHP pyrolyzate to that in the I pyrolyzate showed that coniferyl alcohol-end groups play a large role in the DHP pyrolyzate. The distribution profiles of the cinnamyl compounds in the cedar wood and its lignin pyrolyzates were greatly differed from that of the I pyrolyzate.

Solid-state spectroscopic analysis of lignins from several Austral hardwoods

In order to gain information about lignin molecular characteristics with a direct bearing on the remarkable susceptibility of some Austral hardwoods to biological delignification, milled-wood lignins were isolated and analyzed by spectroscopic techniques in the solid state. Cross polarization and magic-angle spinning 13 C nuclear magnetic resonance ( 13 C CPMAS NMR) and Fourier-transform infrared (FTIR) spectra of the lignin preparations were obtained. The most diagnostic peaks were assigned and quantified as percentages of the total spectral area, and the differences observed discussed in terms of lignin composition. The spectral patterns obtained revealed that the woods from Gevuina avellana, Eucryphia cordifolia and Nothofagus dombeyii have lignin with high syringyl/guaiacyl ratio, as evidenced by relative areas of 13 C NMR signals at 153 and 148 ppm, and FTIR bands at 1335 and 1275 cm −1. The presence of syringyl-rich lignins, characterized by lower redox potential and condensation degree than guaiacyl-rich lignins, could be a structural factor contributing to the ease of extensive delignification of these woods by white-rot fungi.

Lignin-Polyphenol Interaction in Azobe (Lophira alata) Heartwood. A Study on Milled Wood Lignin (MWL) and Klason Residues

Summary Findings about anomalous high Klason residues of azobe (Lophira alata) heartwood prompted a search for methods of determination of non lignin-type polyphenols in lignin preparations. A four step procedure was performed: (1) ethylation of milled wood lignins (MWLs) from azobe and beech heartwood, (2) permanganate oxidation, (3) methylation, and (4) GC analysis of the oxidation products. Besides the well known degradation products of hemipinic, iso-hemipinic, and meta-hemipinic acid type, methyl-3,4-diethoxy-benzoate (compound I) has also been detected among the oxidation products. The oxidation of beech MWL gave rise only to 0.4 mol % of I but azobe MWL yielded the remarkably high amount of 10.7 mol % of I. As lignins do not contain two adjacent aromatic hydroxyl groups, we concluded that I is of polyflavonoid origin. Hence the extraordinarily high Klason residues of azobe heartwood can be rationalized with large amounts of acid insoluble polyphenols which are an integral part of the azobe cell wall and which is also closely associated to MWLs. Ethylation followed by KMnO4 oxidation is an effective tool to detect polyflavonoids in lignins.

Determination of Phenolic Hydroxyl Groups in Lignin by Combined Use of 1H NMR and UV Spectroscopy

Summary Two independent spectroscopic methods are presented and compared for the quantitation of the phenolic hydroxyl groups in lignins. The combined information is used to further elucidate the character of the lignin samples examined. The UV method is based on the difference of the spectroscopic properties of the ionised and the nonionised phenol. The method using 1H NMR spectroscopy is based on the exchange of phenolic protons in D2O. The difference in integrated proton intensities in the sample dissolved in DMSO and the sample with additional 20% D2O is proportional to the phenolic protons. The method based on UV spectroscopy uses differences in the maxima close to 300 nm and 350 nm of the sample dissolved in alkali and the neutral sample. The results using the two independent methods are in agreement for milled wood lignin, for kraft lignin and for model compounds carrying one aromatic hydroxyl group. For modified lignins and for model compounds with more than one aromatic hydroxyl group, the UV method gives too low values for phenolic hydroxyl groups. The combined results obtained by the two methods however provide information of the total amount of the phenolic groups and of the nature of the phenolic structure formed by the lignin refining.

Characterization of soluble lignin released from alfalfa by sheep digestion

A faecal soluble lignin fraction (FSL) extracted with 90% dioxane from the faeces of sheep fed on alfalfa hay was characterized by chemical analysis, nitrobenzene oxidation, fourier transform infrared spectroscopy and gel permeation chromatography, and compared with milled wood lignin (MWL) isolated from the alfalfa hay. The amount of FSL in the faeces was low, accounting for only 1% of the lignin present in the alfalfa hay. FSL and MWL consisted mostly of lignin components and contained a small amount of carbohydrate. FSL had a much higher proportion of syringylpropane units than MWL and showed a wide molecular size distribution. The results indicate the selective and limited solubilization of syringyl-rich lignin from alfalfa by sheep digestion.

Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.

Modified Lignin and Delignification with a CAD-Deficient Loblolly Pine

Summary Lignin composition and lignin removal were investigated in loblolly pines (Pinus taeda L.) deficient in the monolignol biosynthesis enzyme, cinnamyl alcohol dehydrogenase (CAD). The CAD-deficient pines were homozygous for the cad-n1 allele, a mutant form of the gene encoding CAD. We show that lignin from CAD-deficient seedlings is more easily removed by mild alkali at room temperature. The nature of the phenolics recovered from this treatment link the increased lignin solubility to a build up of aromatic aldehyde lignin subunits. We carried out a retrospective genetic analysis to identify a 12 year-old CAD-deficient tree from which we isolated Milled Wood Lignin (MWL) and obtained wood chips for pulping studies. The UV absorption spectra of MWL and the effect of sodium borohydride reduction of MWL showed that the CAD-deficient tree had substantially higher incorporation of aldehyde subunits. The CAD-deficient wood was delignified more extensively than the wild type in soda pulping but not in kraft conditions. More extensive lignin removal, both in mild alkali treatment and in soda pulping, indicate that suppression of CAD in softwood trees may hold promise to produce woods well suited for “milder” pulping conditions that consume less chemicals and generate less waste.

Pyrolysis‐gas chromatography/Mass spectrometry analysis of phenolic and etherified units in natural and industrial lignins

Milled-wood lignin (MWL) from Carpinus betulus, Eucryphia cordifolia, Picea abies, Pinus sp. and Bambusa sp., Kraft lignin from Fagus sylvatica and Eucalyptus globulus, and alkali lignin and hemicellulose-linked lignin from Triticum aestivum, were investigated with respect to their composition in phenolic and etherified phenylpropanoid H (p-hydroxyphenyl), G (guaiacyl) and S (syringyl) units. For this purpose, a methodology based on lignin permethylation, followed by pyrolysis-gas chromatography/mass spectrometry, and quantitation of marker compounds (H-, G- and S-type vinylphenols and their methylated derivatives) in single-ion chromatograms, was developed. The phenolic content in the samples analyzed ranged from 2% of total units in hemicellulose-linked lignin to near 70% in Kraft lignins. Softwood MWL showed higher amounts of phenolic units than MWL from annual plants and hardwoods. It was found that the phenolic content of MWL from the Austral tree species E. cordifolia was unexpectedly high for a hardwood lignin. The significance of this finding in terms of lignin degradability by white-rot fungi, of biotechnological interest, is discussed. Copyright © 1999 John Wiley & Sons, Ltd.

Pyrolysis-gas chromatography/Mass spectrometry analysis of phenolic and etherified units in natural and industrial lignins

Milled-wood lignin (MWL) from Carpinus betulus, Eucryphia cordifolia, Picea abies, Pinus sp. and Bambusa sp., Kraft lignin from Fagus sylvatica and Eucalyptus globulus, and alkali lignin and hemicellulose-linked lignin from Triticum aestivum, were investigated with respect to their composition in phenolic and etherified phenylpropanoid H (p-hydroxyphenyl), G (guaiacyl) and S (syringyl) units. For this purpose, a methodology based on lignin permethylation, followed by pyrolysis-gas chromatography/mass spectrometry, and quantitation of marker compounds (H-, G- and S-type vinylphenols and their methylated derivatives) in single-ion chromatograms, was developed. The phenolic content in the samples analyzed ranged from 2% of total units in hemicellulose-linked lignin to near 70% in Kraft lignins. Softwood MWL showed higher amounts of phenolic units than MWL from annual plants and hardwoods. It was found that the phenolic content of MWL from the Austral tree species E. cordifolia was unexpectedly high for a hardwood lignin. The significance of this finding in terms of lignin degradability by white-rot fungi, of biotechnological interest, is discussed. Copyright # 1999 John Wiley & Sons, Ltd.

Structural Characterization of Cork Lignin by Thioacidolysis and Permanganate Oxidation

Summary Quercus suber L. milled cork lignins obtained from extractive-free cork (MCL) and from saponified cork (MCLsap) were characterized by thioacidolysis and KMnO4 oxidation. These techniques and the previously used analytical pyrolysis revealed that cork contains a guaiacyl lignin (G lignin) with 94–96% guaiacyl-, ca. 3% syringyl-, and 2–3% of 4-hydroxyphenyl-propane units. The total yields of degradation products in thioacidolysis and KMnO4 oxidation experiments were lower in comparison to those of a spruce milled wood lignin (MWLspruce) suggesting a higher cross-linking in the G-lignin of cork. The higher frequency of “condensed” structures (having C-C or C-O-C linkages to aromatic rings) in cork lignin was also manifested in the relative abundance of various aromatic acids obtained by KMnO4 oxidation. The cork lignin (MCLsap) contains only low amounts (ca. 2%) of covalently bonded suberinic acids. Numerous free aliphatic suberinic acids were detected and identified in the ether soluble part of MCLsap. Ferulic acid was not liberated by thioacidolysis, pointing at an in situ acylation. We suggest that the major part of the aromatic domain in cork is a G-lignin but that it includes also another structural moiety with higher H-unit content and linked by thioacidolysis resistant bonds.

Isochroman lignin trimers from DFRC-degraded Pinus taeda1Part 5 in the series “The DFRC Method for Lignin Analysis”. Previous paper: Peng, J., Lu, F., &amp; Ralph, J. (1998). “Part 4. Lignin Dimers Isolated from DFRC-Degraded Loblolly Pine Wood” J. Agric. Food Chem., 46, 553–560.1

A pair of new aryl isochroman lignin trimers, 7-acetoxy-1-{2-acetoxy-1-[4-(3-acetoxyprop-2-enyl)]-2-methoxyphenoxy}-3-(4-acetoxy-3-methoxyphenyl)-4-acetoxymethyl-6-methoxy-isochromans, along with three related dimers were isolated from DFRC degraded loblolly pine (Pinus taeda L.) wood following gel permeation and reversed-phase TLC and HPLC. Their structures were elucidated by means of 2D–NMR, FAB–MS and GC–MS analyses. These two trimers contained a unique β–1 inter-unit linkage with a 6-membered di-α-ether ring and with the original sidechain migrated. The mechanistic plausibility of the lignification pathway, the isolation of expected DFRC degradation dimers and trimers, and the tentative identification of the aryl isochroman structure in pine milled wood lignins by NMR spectroscopy, all suggest that such structures, or their precursors, are present in native lignins (in their unacetylated forms). An unrelated trimer possessing 5–5/β–β interunit linkages was also isolated and characterized.

A New Approach Towards the Yellowing Inhibition of Mechanical Pulps. Part I: Selective Removal of α-Hydroxyl and α-Carbonyl Groups in Lignin Model Compounds

Summary The α-hydroxyl group in lignin model compounds 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol (1) and 1-(4-hydroxy-3-methoxyphenyl)ethanol (3), and the α-carbonyl group in 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)ethan-1-one (5) are removed by treatment of the model compounds with trifluoroacetic acid (CF3CO OH) and triethylsilane (Et3sih) in methylene chloride. The reaction is highly chemoselective and it tolerates the lignin γ-hydroxyl group, phenol and β-O-4-aryl ether linkage. The α-hydroxyl group in 1 has also been removed with triethylsilane in aqueous trifluoroacetic acid (CF3CO OH : H2o = 75 : 25). The combination of trifluoroacetic acid and sodium borohydride, or sodium triacetoxyborohydride, is also effective in removing the α-carbonyl group in 5 and the α-hydroxyl group in lignin model compound 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)ethanol (7) and in milled wood lignin. The selective removal of the lignin α-hydroxyl and α-carbonyl groups may potentially be used, in conjunction with the protection of the lignin phenol, to inhibit the light and/or heat-induced yellowing of mechanical pulps.

Acid Reactions of Lignin Models of β-5 Type

Summary Refluxing of trans–2-(3,4-dimethoxyphenyl)-3-hydroxymethyl-7-methoxy-2,3-dihydrobenzo[b]furan with dioxane-water (9 : 1) in the presence of various acid catalysts led to the formation of 2-(3,4-dimethoxyphenyl)- 7-methoxy-3-methylbenzo[b]furan, the trans and cis forms of 2-hydroxy-3,3′4′-trimethoxystilbene and cis–2-(3,4-dimethoxyphenyl)-3-hydroxymethyl-7-methoxy-2,3-dihydrobenzo[b]furan. The proportions of the products were strongly dependent on the particular acid used as catalyst. HCl and to a greater extent HBr favored the formation of the 2-arylbenzofuran (phenylcoumarone) while the trans-stilbene derivative predominated in reaction products from the experiments with trifluoromethane sulfonic acid as the catalyst. Isomerization of the starting material occurred, regardless of the nature of the catalyst (small amounts of the cis-isomer formed). The number of phenylpropane units in spruce lignin attached to an adjacent unit by a β−5 linkage was estimated to be 6–9% on the basis of 1H NMR spectrometric measurements of the formation of phenylcoumarone structures on refluxing of milled wood lignin from spruce with 0.1M HBr in dioxane-water (9 : 1).

Article

3,5-Di-tert-butyl-ortho-quinone, 6, and 1-(3,4-dimethoxyphenyl-2-(2-methoxyphenoxy)-1-propanone, 7, models for oxidized lignin and for lignin, were used as sensitizers of photo-oxidation. Product studies by HPLC from oxidation of methyl linoleate in solution sensitized by 6 or 7, and in sodium dodecyl sulfate (SDS) sensitized by 6, showed a product distribution of six hydroperoxides, the four conjugated 9- and 13-hydroperoxides of the geometrical isomers: trans-10, cis-12 (2), cis-9, trans-11 (3), trans-10, trans-12 (4), and trans-9, trans-11 (5)-octadecadienoates plus two nonconjugated hydroperoxides. The higher cis/trans to trans/trans (ct/tt) of geometrical isomers (2 + 3//4 + 5) compared to ct/tt from known thermal free-radical peroxidations (Type 1) indicate that singlet oxygen (Type 2) oxidation occurs in reactions sensitized by 6 or 7. Kinetic studies by oxygen uptake are reported on oxidations of hydrocarbons 1-phenyl-2-methylpropene,8, and trans-stilbene,9, sensitized by the quinone, 6, or by a dye, Rose Bengal. Quenching studies imply singlet oxygen reactions. Milled wood lignin undergoes self-initiated photo-oxidation in water, and oxygen uptake was quenched by sodium azide. Cellobiose, a cellulose model, undergoes sensitized photo-oxidation using model quinone, 6, in a mixture of tert-butyl alcohol and water or using the sensitizers benzophenone or the lignin model, 7, delivered on a solid support, silica gel, and these oxidations were quenched with sodium azide. These results implicate singlet oxygen in the photo-yellowing of high lignin content wood pulps.Key words: lignin models, ortho-quinone, photo-oxidation, singlet oxygen, lignin, cellobiose.

Structural Characterization of the Bark and Core Lignins from Kenaf (Hibiscus cannabinus)

Dioxane and milled wood lignins were isolated from the core and bark of kenaf (Hibiscus cannabinus), variety Salvador. These lignins were characterized by 13C and 1H NMR, FTIR, and UV spectroscopies, permanganate oxidation, and alkaline hydrolysis followed by GC and GC-MS analysis of the released products and by functional groups analysis. The permanganate oxidation and alkaline hydrolysis was also applied to “in situ” lignins. Isolated and “in situ” lignins showed significant differences in composition and structure. Strong structural differences were observed between bark and core lignins, suggesting their different biosynthetic routes. The β-O-4 type linkages are the main interunit linkages and are more abundant in bark than in core lignin. The core lignin is more “condensed” and shows higher contents of β-β plus β-5 linkages than those in the bark lignin. Permanganate oxidation showed that both core and bark “in situ” lignins are HGS-type lignins with HGS proportions of 15:66:19 and 12:56:32, respectively (H including coumarate structures in the case of core lignin). Coumarates represent about 50% of the H units of core lignin and are absent in bark lignins. The presence of suberin-like aliphatic chains covalently bound to lignin was suggested for bark lignin. Keywords: Lignin; kenaf; Hibiscus cannabinus; 13C NMR; 1H NMR; UV spectroscopy; FTIR spectroscopy; permanganate oxidation; phenolic acids

Chemical characterization of lignin preparations of fresh and decomposing Spartina anglica by pyrolysis mass spectrometry

In order to determine terrestrial contributions to the organic matter pool in the marine environment, a reliable chemical tracer is required. Lignin, an abundant component of vascular plant tissue is often used as such. In this study the lignin moiety of both fresh and degraded tissue of the model halophyte Spartina anglica was purified and chemically characterized to investigate its suitability as tracer. The study can be split into three parts. In the first part several enzymatic lignin purifications of fresh S. anglica tissue were compared with each other. In the second part pyrolysis gas chromatography mass spectrometry was applied to analyse untreated and on-line methylated milled wood lignin preparations. The previous characterizations of the lignin moiety of S. anglica were used in the third part to monitor modifications in the chemical composition induced by natural aerobic decomposition in the field. The temperature at which lipids were extracted from the original tissue was not critical, although low temperatures improved the purification to some extent. For enzymatic purification of lignin the use of a polysaccharidase turned out to be the most important prerequisite. The use of a protease did not have much influence on the lignin residue. After 2 yr of aerobic decomposition, the lignin character of untreated S. anglica tissue was no longer identifiable with direct temperature-resolved mass spectrometry, but it still could be retrieved in the residue obtained after enzyme treatment. With continuing decomposition the chemical structure of the lignin moieties became partly modified. The very complicated spectra obtained after longer decomposition periods suggest the formation of a heterogeneous organic fraction, probably representing “humic substances”. The gradual loss of lignin characteristics in the litter makes its suitability as tracer for terrestrial material in a complex mixture of substances doubtful, at least with the analytical technique applied in this study.

On the formation of diphenylmethane structures in lignin under kraft, EMCC®, and soda pulping conditions

This paper describes our efforts focused at defining the formation of diphenylmethane moieties in lignin during conventional kraft and soda pulping conditions. This objective was realized by confirming, initially, the assignment of a 31P NMR signal as being due exclusively to the presence of phosphitylated diphenylmethane (DPM) phenolic hydroxyl groups. More specifically, softwood milled wood lignin (Picea mariana) was subjected to kraft pulping conditions in the presence and absence of varying amounts of formaldehyde. After quantitative recovery of the lignin, the 31P NMR spectra were recorded and the spectra revealed selective signal growth in the region confined between 142.8 and 144.3 ppm, in accordance with previous model compound work and detailed calculations based on the Hammett principles. To further substantiate our conclusions we also carried out two series of isothermal (120°C) kraft and soda pulping experiments followed by quantitative determinations of the DPM moieties, and correlated our findings with the differences in chemistry known to occur between the two processes. Finally, diphenylmethane phenolic moieties were determined in isolated residual lignins from two western hemlock kraft pulp samples produced via an EMCC® mill protocol and a laboratory batch digester, respectively. These structures prevailed amongst the condensed phenolic units of the conventional pulp, providing additional evidence to support the fact that modern modified pulping technologies beneficially alter the structure of residual kraft lignin.Key words: phenyl groups, kraft pulping, modified kraft process, nuclear magnetic resonance (NMR), phosphorus spectroscopy.

Peroxidations initiated by lignin model compounds: investigating the role of singlet oxygen in photo-yellowing

3,5-Di-tert-butyl-ortho-quinone, 6, and 1-(3,4-dimethoxyphenyl–2-(2-methoxyphenoxy)-1-propanone, 7, models for oxidized lignin and for lignin, were used as sensitizers of photo-oxidation. Product studies by HPLC from oxidation of methyl linoleate in solution sensitized by 6 or 7, and in sodium dodecyl sulfate (SDS) sensitized by 6, showed a product distribution of six hydroperoxides, the four conjugated 9and 13-hydroperoxides of the geometrical isomers: trans-10, cis-12 (2), cis-9, trans-11 (3), trans-10, trans-12 (4), and trans-9, trans-11 (5)-octadecadienoates plus two nonconjugated hydroperoxides. The higher cis/trans to trans/trans (ct/tt) of geometrical isomers (2 + 3//4 + 5) compared to ct/tt from known thermal free-radical peroxidations (Type 1) indicate that singlet oxygen (Type 2) oxidation occurs in reactions sensitized by 6 or 7. Kinetic studies by oxygen uptake are reported on oxidations of hydrocarbons 1-phenyl-2-methylpropene, 8, and trans-stilbene, 9, sensitized by the quinone, 6, or by a dye, Rose Bengal. Quenching studies imply singlet oxygen reactions. Milled wood lignin undergoes self-initiated photo-oxidation in water, and oxygen uptake was quenched by sodium azide. Cellobiose, a cellulose model, undergoes sensitized photooxidation using model quinone, 6, in a mixture of tert-butyl alcohol and water or using the sensitizers benzophenone or the lignin model, 7, delivered on a solid support, silica gel, and these oxidations were quenched with sodium azide. These results implicate singlet oxygen in the photo-yellowing of high lignin content wood pulps.

13C NMR Characterization of Guaiacyl, Guaiacyl/Syringyl and Syringyl Dehydrogenation Polymers

Summary Dehydrogenation polymers (DHPs) were prepared from coniferyl alcohol (CA), sinapyl alcohol (SA), and a mixture of coniferyl and sinapyl alcohol. The polymers were fully acetylated and their carbon NMR spectra were compared. Comparison of the 13C NMR spectra of the DHPs with those of authentic tri- and tetralignols facilitated the assignment of about 85% of the 117 reported signals. Most of the unassigned signals were those from syringyl units. Major differences between the DHP prepared from CA and a pine milled wood lignin were: a relative deficiency of s-O-4 linkages and a predominance of s-5, s-s, and CA end units in the DHP. In contrast, there was no significant quantity of SA end units in a DHP prepared from SA. A major conclusion of the study confirmed that DHPs prepared from CA are relatively poor models of natural lignins isolated from gymnosperms.