Lignin Side Chains Research Articles

Styrene-Spaced Copolymers Including Anthraquinone and β-O-4 Lignin Model Units: Synthesis, Characterization and Reactivity Under Alkaline Pulping Conditions

A series of random copoly(styrene)s has been synthesized via radical polymerization of functionalized anthraquinone (AQ) and β-O-4 lignin model monomers. The copolymers were designed to have a different number of styrene spacer groups between the AQ and β-O-4 lignin side chains aiming at investigating the distance effects on AQ/β-O-4 electron transfer mechanisms. A detailed molecular characterization, including techniques such as size exclusion chromatography, MALDI-TOF mass spectrometry, and (1)H, (13)C, (31)P NMR and UV-vis spectroscopies, afforded quantitative information about the composition of the copolymers as well as the average distribution of the AQ and β-O-4 groups in the macromolecular structures. TGA and DSC thermal analysis have indicated that the copolymers were thermally stable under regular pulping conditions, revealing the inertness of the styrene polymer backbone in the investigation of electron transfer mechanisms. Alkaline pulping experiments showed that close contact between the redox active side chains in the copolymers was fundamental for an efficient degradation of the β-O-4 lignin model units, highlighting the importance of electron transfer reactions in the lignin degradation mechanisms catalyzed by AQ. In the absence of glucose, AQ units oxidized phenolic β-O-4 lignin model parts, mainly by electron transfer leading to vanillin as major product. By contrast, in presence of glucose, anthrahydroquinone units (formed by reduction of AQ) reduced the quinone-methide units (issued by dehydration of phenolic β-O-4 lignin model part) mainly by electron transfer leading to guaiacol as major product. Both processes were distance dependent.

A comparative study of bamboo (Phyllostachys incarnata Wen) milled wood lignin and the successively alkali-fractionated lignins

The chemical composition and structural characterization of the milled wood lignin (MWL) and successively alkali-fractionated lignins from bamboo (Phyllostachys incarnata Wen) were comparatively investigated using Fourier transform infrared (FT-IR), gel permeation chromatography (GPC), 2D heteronuclear single quantum coherence (HSQC), and alkaline nitrobenzene oxidation. It was found that bamboo MWL (S/G ~ 1.3) is of SGH type with a considerable amount of esterified p-coumaric acid and etherified ferulic acid. Molecular weights of 3,320 g/mol for MWL and varying weights between 970 and 3,430 g/mol for the alkali-fractionated lignins were obtained. Moreover, 2D HSQC of MWL showed a predominance of β-O-4′ linkages (65%), followed by β–β′ linkages (15%) and lower amounts of β-5′ (7%), β-1′ (4%), 5–5′ (4%) linkages, and cinnamyl acetate end groups (5%). In addition, a percentage (~45%) of the lignin side chain was found to be acylated at the γ-carbon. However, the alkali-fractionated lignins lost parts of these linkages during successive alkaline fractionation processes.

Thermal characterization of softwood lignin modification by termite Coptotermes formosanus (Shiraki)

Abstract Wood-feeding termites (WFT) pretreat wood cell walls to achieve efficient cellulose utilization by modifying the protecting lignin polymers. An analytical protocol consisting of three-stage-pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetry (TG/DTG) was employed along with attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy to investigate softwood degradation by the lower termite Coptotermes formosanus . The results revealed that softwood-lignin moieties were altered during termite digestion. This was characterized by preferential ring demethoxylation, dehydroxylation, and methylation, side chain carboxylation and oxidation, methylation, and oxidation on the ring hydroxyl group, as well as depolymerization and ring destruction. The TG/DTG data demonstrated remarkable changes in the thermal behavior of the processed softwood and also in termite feces, showing decreased activation energy and pre-exponential factor at the second stage (330–400 °C) of lignin pyrolysis. Meanwhile, ATR-FTIR analysis suggested aromatic ring destruction, methoxyl and hydroxyl group modification, C–H deformations in –CH 3 and –CH 2 groups, splitting/modification of aliphatic side chains in lignin, and conformation changes of lignin. Such modifications induced changes in pyrolysis products and bond energies in lignin, and provided information on softwood digestion by termite.

Origin of the acetylated structures present in white birch (Betula pendula Roth) milled wood lignin

The occurrence and nature of acetate groups in the milled wood lignin (MWL) isolated from birch (Betula pendula Roth) has been addressed by spectroscopic (2D-NMR) and chemical degradative (derivatization followed by reductive cleavage, DFRC) methods. Considerable amounts of acetate groups were present in the MWL preparation. However, 2D-NMR analysis indicated that the lignin polymer is not extensively acetylated and that the major part of the acetate groups is attached to the xylan moieties present in the MWL preparation. Nevertheless, evidence of the presence of minor acetylation of the γ-carbon of the lignin side chain (<3% of both syringyl and guaiacyl lignin units) was provided by DFRC analysis.

Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 2. Non-catalyzed reactions with the wood cell wall

Abstract Solution-state NMR provides a powerful tool to observe the presence or absence of covalent bonds between wood and adhesives. Finely ground wood can be dissolved in an NMR-compatible solvent system containing dimethylsulfoxide-d 6 and N-methylimidazole-d 6 , in which the wood polymers remain largely intact. High-resolution solution-state two-dimensional NMR correlation experiments, based on 13C–1H one-bond heteronuclear single quantum coherence, allow structural analysis of the major cell wall components. This technique was applied to loblolly pine that was treated with polymeric methylene diphenyl diisocyanate (pMDI) related model compounds under controlled moisture and temperature conditions. Chemical shifts of carbamates formed between the pMDI model compounds and loblolly pine were determined. The results show that: (a) under dry conditions and a high concentration of isocyanate, carbamates will form preferentially with side-chain hydroxyl groups on β-aryl ether and phenylcoumaran-linked lignin units in a swelling solvent; (b) phenyl isocyanate is more capable of derivatization in the cell wall than the bulkier 4-benzylphenyl isocyanate; (c) at 5% and 14% moisture content, detectable carbamates on lignin side-chains dramatically decrease; and (d) under typical conditions of industrial oriented strand-board production in a hot press at 5% and 14% moisture content, no carbamate formation was detected.

NMR Structural Characterization of Quercus alba (White Oak) Degraded by the Brown Rot Fungus, Laetiporus sulphureus

High resolution magic angle spinning (HRMAS) is utilized here to characterize the structure of solid lignin from Quercus alba (white oak) wood that has been biodegraded by the brown rot (BR) fungus Laetiporus sulphureus. The ground wood sample is swelled in deuterated solvent, allowing an enhanced molecular motion that is required for obtaining 2D HRMAS spectra. This technique provides for direct, non-invasive analysis of solid biodegraded lignin. Emphasis is placed on the characterization of the lignin side chains in an effort to elucidate the types of linkages connecting the various monomers. The HRMAS spectra obtained provide evidence for the presence of structures in this biodegraded lignin that have been commonly found in chemically extracted lignins and model compounds. This information supports the existence of several of the six major types of lignin linkages (β-O-4, β-5, β-1, 5-5, 4-O-5, and β-β) as well as three other structures: dibenzodioxocin, isochroman, and spirodienone.

Structural Characterization of the Lignin from Jute (Corchorus capsularis) Fibers

The structural characteristics of the lignin from jute (Corchorus capsularis ) fibers, which are used for high-quality paper pulp production, were studied. The lignin content (13.3% Klason lignin) was high compared to other nonwoody bast fibers used for pulp production. The lignin structure was characterized by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), 2D-NMR, and thioacidolysis. Upon Py-GC/MS, jute fibers released predominantly products from syringylpropanoid units with the S/G ratio being 2.1 and a H/G/S composition of 2:33:65. 2D-NMR of the milled wood lignin (MWL) isolated from jute fibers showed a predominance of beta-O-4' aryl ether linkages (72% of total side chains), followed by beta-beta' resinol-type linkages (16% of total side chains) and lower amounts of beta-5' phenylcoumaran (4%) and beta-1' spirodienone-type (4%) linkages and cinnamyl end groups (4%). The high predominance of the S-lignin units, together with the high proportion of beta-O-4' aryl ether linkages, which are easily cleaved during alkaline cooking, are advantageous for pulping. On the other hand, a small percentage (ca. 4%) of the lignin side chain was found to be acetylated at the gamma-carbon, predominantly over syringyl units. The analysis of desulphurated thioacidolysis dimers provided additional information on the relative abundances of the various carbon-carbon and diaryl ether bonds and the type of units (syringyl or guaiacyl) involved in each of the above linkage types. Interestingly, the major part of the beta-beta' dimers included two syringyl units, indicating that most of the beta-beta' substructures identified in the HSQC spectra were of the syringaresinol type (pinoresinol being absent), as already observed in the lignin of other angiosperms.

HSQC-NMR analysis of lignin in woody (Eucalyptus globulus and Picea abies) and non-woody (Agave sisalana) ball-milled plant materials at the gel state 10th EWLP, Stockholm, Sweden, August 25–28, 2008

Abstract In situ analysis of lignin by 2D NMR of whole plant material was carried out by swelling finely ball-milled samples in deuterated dimethylsulfoxide (DMSO-d6 ) and sonicated so that a gel was formed in the NMR analysis tube. Solution HSQC NMR spectra of different plant materials representative for hardwood (Eucalyptus globulus), softwood (Picea abies), and non-woody plants (Agave sisalana) are presented here. The spectra show signals corresponding to those of the main plant constituents, such as lignin and polysaccharides. The lignin signals were assigned by comparing the HSQC spectra of the whole plant materials with the HSQC spectra of their respective milled-wood lignins (MWLs). In general terms, the major lignin structural features, such as the relative abundances of the main lignin substructures, the syringyl/guaiacyl ratios and the extent of γ-acetylation of the lignin side-chain observed in the HSQC spectra of the whole plant materials, matched those obtained from the HSQC spectra of the isolated MWLs. Therefore, this technique, which needs only minor amounts of lignocellulosic material and minimal sample preparation, can be useful for the rapid screening of plant lignins without the need for tedious and time-consuming lignin isolation procedures.

Early maturation processes in coal. Part 2: Reactive dynamics simulations using the ReaxFF reactive force field on Morwell Brown coal structures

This paper reports reactive dynamics (RD) simulations of a macro-model of Morwell Brown coal using the ReaxFF reactive force field. We find that these reactive MD simulations successfully reproduce thermal decomposition processes of defunctionalization, depolymerization and rearrangement of the residual structure observed in various experimental studies. For example, our simulations indicate that the decarboxylation and dehydroxylation of the lignin side chain of the Morwell model involves the formation of double bonds conjugated with the aromatic rings. The process of defunctionalization of the methoxy functions involving the formation of phenolic structures in the residue has been confirmed. We also observe that gaseous hydrocarbons are generated by cleavage of C–C bonds of the lignin side chain. The success in using ReaxFF RD to describe the molecular processes underlying the kinetics in pyrolysis of this model of coal plus the success of a similar previous study on the algaenan of Botryococcus braunii race L biopolymer model of kerogens suggests that such computation can be useful in providing molecular based kinetic models for other pyrolysis processes underlying the organic transformations in sedimentary materials.

Native Lignin Structure of Miscanthus x giganteus and Its Changes during Acetic and Formic Acid Fractionation

Milled wood lignin (MWL) and acetic and formic acid lignin (AL and FL) from Miscanthus x giganteus bark were produced, respectively, before and after organosolv fractionations under optimal conditions, in terms of organic and hydrochloric acid concentrations, liquid/wood ratio, and reaction time. In order to study the M. x giganteus native lignin structure and its modifications during the fractionation process, the lignins were studied by two-dimensional heteronuclear single quantum coherence (2D-(HSQC)), (13)C- and (31)P nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR), size-exclusion chromatography (SEC) both before and after thioacidolysis, and elemental analysis. In addition, chemical composition analysis was performed on ash, Klason lignin, and carbohydrate content. The analyses demonstrated that M. x giganteus native lignin (MWL) is highly acylated at the C(gamma) of the lignin side chain (46%), possibly with p-coumarate and/or acetate groups. This is newsworthy since several earlier studies showed that acylation at the gamma-carbon commonly occurs in C(3) and CAM grasses, whereas M. x giganteus is a C(4) grass. Furthermore, M. x giganteus showed a low S/G ratio (0.7) and a predominance of beta-O-4' linkages (up to 93% of all linkages). AL and FL lose part of these linkages during organosolv fractionation (up to 21 and 32%, respectively). The p-coumarate groups resist fractionation processes and are still present in high quantities in AL and FL. During the fractionation process, lignin is acetylated (acetic acid process) and condensed, with the G units condensing more than S units. M. x giganteus MWL contains a high content of carbohydrates (22.8%), suggesting that it is a lignin-carbohydrate complex (LCC). AL and FL showed low carbohydrate contents because of the breaking down of the LCC structures. AL and FL have high molecular weights and low polydispersities, and are high in phenolic content, qualities that make these suitable for different applications. These results suggest that refinement of M. x giganteus via organosolv processes could potentially turn this grass into a valuable source of both fiber and lignin.

The Effects on Lignin Structure of Overexpression of Ferulate 5-Hydroxylase in Hybrid Poplar1

Poplar (Populus tremula x alba) lignins with exceedingly high syringyl monomer levels are produced by overexpression of the ferulate 5-hydroxylase (F5H) gene driven by a cinnamate 4-hydroxylase (C4H) promoter. Compositional data derived from both standard degradative methods and NMR analyses of the entire lignin component (as well as isolated lignin fraction) indicated that the C4HF5H transgenic's lignin was comprised of as much as 97.5% syringyl units (derived from sinapyl alcohol), the remainder being guaiacyl units (derived from coniferyl alcohol); the syringyl level in the wild-type control was 68%. The resultant transgenic lignins are more linear and display a lower degree of polymerization. Although the crucial beta-ether content is similar, the distribution of other interunit linkages in the lignin polymer is markedly different, with higher resinol (beta-beta) and spirodienone (beta-1) contents, but with virtually no phenylcoumarans (beta-5, which can only be formed from guaiacyl units). p-Hydroxybenzoates, acylating the gamma-positions of lignin side chains, were reduced by >50%, suggesting consequent impacts on related pathways. A model depicting the putative structure of the transgenic lignin resulting from the overexpression of F5H is presented. The altered structural features in the transgenic lignin polymer, as revealed here, support the contention that there are significant opportunities to improve biomass utilization by exploiting the malleability of plant lignification processes.

Early maturation processes in coal. Part 1: Pyrolysis mass balance and structural evolution of coalified wood from the Morwell Brown Coal seam

We have developed a theoretical approach for evaluating the maturation of kerogen-like material, involving molecular dynamic reactive modelling with a reactive force field to simulate thermal stress. Morwell Brown Coal was selected to study the thermal evolution of terrestrial organic matter (OM). To achieve this, a structural model is first constructed on the basis of literature models and analytical characterization of our samples using modern 1and 2D nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy and elemental analysis. Then, artificial maturation of the coal is performed at low conversion in order to obtain quantitative and qualitative detailed evidence for the structural evolution of the kerogen upon maturation. The chemical changes include defunctionalization of carboxyl, carbonyl and methoxy functional groups, coupled with an increase in cross linking in the residual matured kerogen. Gaseous and liquid hydrocarbons, essentially CH 4, C 4H 8 and C 14+ hydrocarbons, are generated in low amount, merely via cleavage of the lignin side chain.

Highly Acylated (Acetylated and/or p-Coumaroylated) Native Lignins from Diverse Herbaceous Plants

The structure of lignins isolated from the herbaceous plants sisal ( Agave sisalana), kenaf ( Hibiscus cannabinus), abaca ( Musa textilis) and curaua ( Ananas erectifolius) has been studied upon spectroscopic (2D-NMR) and chemical degradative (derivatization followed by reductive cleavage) methods. The analyses demonstrate that the structure of the lignins from these plants is highly remarkable, being extensively acylated at the gamma-carbon of the lignin side chain (up to 80% acylation) with acetate and/or p-coumarate groups and preferentially over syringyl units. Whereas the lignins from sisal and kenaf are gamma-acylated exclusively with acetate groups, the lignins from abaca and curaua are esterified with acetate and p-coumarate groups. The structures of all these highly acylated lignins are characterized by a very high syringyl/guaiacyl ratio, a large predominance of beta- O-4' linkages (up to 94% of all linkages), and a strikingly low proportion of traditional beta-beta' linkages, which indeed are completely absent in the lignins from abaca and curaua. The occurrence of beta-beta' homocoupling and cross-coupling products of sinapyl acetate in the lignins from sisal and kenaf indicates that sinapyl alcohol is acetylated at the monomer stage and that, therefore, sinapyl acetate should be considered as a real monolignol involved in the lignification reactions.

Occurrence of Naturally Acetylated Lignin Units

This work examines the occurrence of native acetylated lignin in a large set of vascular plants, including both angiosperms and gymnosperms, by a modification of the so-called Derivatization Followed by Reductive Cleavage (DFRC) method. Acetylated lignin units were found in the milled wood lignins of all angiosperms selected for this study, including mono- and eudicotyledons, but were absent in the gymnosperms analyzed. In some plants (e.g., abaca, sisal, kenaf, or hornbeam), lignin acetylation occurred at a very high extent, exceeding 45% of the uncondensed (alkyl-aryl ether linked) syringyl lignin units. Acetylation was observed exclusively at the gamma-carbon of the lignin side chain and predominantly on syringyl units, although a predominance of acetylated guaiacyl over syringyl units was observed in some plants. In all cases, acetylation appears to occur at the monomer stage, and sinapyl and coniferyl acetates seem to behave as real lignin monomers participating in lignification.

Biochemical origin and refractory properties of humic acid extracted from maize plants: the contribution of lignin

The soil organic carbon (SOC) pool is the largest terrestrial reservoir of carbon and plant residues play an important role in its maintenance. Up to 70–80% of SOC in arable soil is composed of humic substances (HS). In these soils post-harvested residues, left in arable soil after harvesting the crops, are the basic source of humus. Previous research indicated that maize plants residue contain a humic acid (HA) fraction possessing recalcitrant compounds that contributed to soil-HA fraction. This study presents updated results obtained using Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) to provide an indication of the contribution of the lignin to the soil HA. Results obtained indicated that the HAs from maize plants were mainly composed of lignin-derived moieties that were likely derived from the partial hydrolysis of p-coumaric and ferulic acid that are linked to lignin, polysaccharides or other biopolymers of the cell wall. Lignin composing the HAs derived from plants and incubated in soil was substantially preserved. Nevertheless the modification of the syringyl/guaiacyl ratio and the oxidation of the side-chains of lignin, suggested a turnover of lignin-derived molecules in soil-HA fraction. This fact indicated an involvement of the alkali insoluble fraction of maize plant residue (humin) in the soil-HA formation, up-dating our previous knowledge.

Studies on the dehydrogenative polymerizations of monolignol β-glycosides. Part 2: Horseradish peroxidase-catalyzed dehydrogenative polymerization of isoconiferin

AbstractDehydrogenative polymerization of isoconiferin (IC; coniferyl alcohol γ-O-β-D-glucopyranoside) catalyzed by horseradish peroxidase (HRP) was carried out. The polymerization of IC proceeded in a homogeneous system, resulting in a water-soluble dehydrogenation polymer (IC-DHP). The degree of polymerization (DP) of IC-DHP was significantly higher than that of a standard dehydrogenative polymer (CA-DHP) obtained from coniferyl alcohol (CA) in a heterogeneous system. Under optimum conditions, the DP of IC-DHP was 44 (Mn=1.5×104), whereas that for CA-DHP was only 11 (Mn=3.0×103, as acetate). Spectroscopic analyses confirmed that IC-DHP has a lignin-like structure containing D-glucose moieties attached to the lignin side-chains. The D-glucose unit introduced into γ-O position of CA essentially influenced the water solubility and molecular mass of the resulting DHP.

Structural characterization of fulvic acids, extracted from sewage sludge during composting, by thermochemolysis–gas chromatography–mass spectrometry

Thermochemolysis coupled with gas chromatography and mass spectrometry were applied to determine the chemical structure of fulvic acids (FA) extracted from a sewage sludge and straw mixture at different steps of composting. The FA starting structures were composed mainly of mono-, di- and tri-methoxy (alkyl) benzoic acids representing lignin derivatives in an advanced stage of oxidation, as well as of methylated polyphenols and a series of fatty acids saturated C15, C16, C18, unsaturated and branched C18:1. Besides, there are many unidentified structures suspected to be N-containing compounds. During the composting process, the fate of the three structural typical monomer units of lignin was followed. The p-hydroxyphenyl units showed a strong relative decrease especially at the beginning of composting. The guiaicyl units showed a steady increase in course of composting. A relative decrease of syringyl units was noted at the beginning of composting, but they then relatively increased towards the end of composting. These changes support the formation during composting of more oxidized units. All subunits composing the fulvic acid structures have been subdivided into main five groups of similar chemical structure. The lignin-like C6–C3 subunits showed a relative decrease during composting attributed to microbial oxidation, but there was a relative increase during the intermediate step of composting related probably of an enhancing of lignin solubility. The C6–C1 subunits were reduced at the beginning of composting, which mainly attributed to the oxidation of 4-methoxybenzaldehyde to hydroquinones derivatives under the composting conditions. Although, the relative increase of these subunits (C6–C1) at the end of composting originates from oxidation of C6–C3 lignin side-chains or could be partly attributed to microbial neosynthesis. The unidentified N-containing compounds increased strongly during course of composting. The rise in the level of fatty acids at the beginning of composting is attributed to an increase of branched-chain fatty acids such as C18:1 commonly used as bacterial biomarkers. Their amounts were greatly reduced at the end of composting. Both the Shannon–Weaver and similitude indices show a relative increase in structural diversity at the start of composting conditions following the appearance of hydroquinone derivatives and unidentified nitrogen compounds in the FA network. But, the produced FA structure reaches a certain level of homogeneity at the end of composting through self-polycondensation or recombination of C6–C1 subunits and hydroquinones derivatives with N-containing compounds.

Structural characterization of humic acids, extracted from sewage sludge during composting, by thermochemolysis–gas chromatography–mass spectrometry

Thermochemolysis coupled with gas chromatography and mass spectrometry were applied to determine the structure of humic acids (HA) extracted from a sewage sludge and straw mixture at different steps of composting. The HA extracted from sludge mixture released various compounds, such as mono-, di-, tri-methoxy (alkyl) benzene and (alkyl) benzoic acids, which originated from lignin like derivatives of p-hydroxyphenyl, guiaicyl and syringyl units. In addition, other aromatic non-lignin derived structures were found along with series of branched C15, linear C16, C18 fatty acid methyl esters. The follow-up of various lignin-derived units during composting shows a decrease in p-hydroxyphenyl type-compounds (C) after the stabilisation phase. In parallel the more oxidized units, derived from guaiacyl (G) and syringyl (S) units, corresponding mainly to methylated derivatives of cafeic acids, protocatechuic acids, gallic acids and aldehydes, significantly increased in comparison with the other aromatic structures. Various ratios commonly used as parameters to determine the degree of lignin decomposition during humification were followed to monitor the chemical structure changes of the HA extracted from sludge mixture during composting. In the present case, the S/G ratio did not present significant changes during composting. The acid/aldehyde ratio was supervised using the ratio of gallic acids to gallic aldehyde methylated derivatives and showed an increase from 0.73 to 2.13 after the stabilisation phase but a decrease to 0.93 at the end of composting. This evolution may be explained by the increase of acid-containing derivatives following the intense oxidation of lignin side-chains during the stabilisation phase. But, the decrease of the acid/aldehyde ratio during the maturation phase could be attributed to a decrease in acid units by polymerisation of benzoic acid type-compounds through ester/ether linkages. The follow up of six families of compounds of similar chemical structures during composting showed a decrease of lignin-type compounds C6 C3 and that C6 C1 units predominated in the humic acid isolated from end compost sludge. The fatty acid methyl esters showed an increase in the intermediate phase of composting probably originating from the activities and tissues of microorganisms, which are numerous during the process. The final decrease in the amount of fatty acids may be explained by the death of most of the microbial population at the end of composting typified by a low respiratory rate. The index of Shannon-Weaver (Ish) remained constant at about 3 in course of composting indicating the neoformation of HA from subunits of similar chemical nature. A similitude index ( S ij , S ′ i j ) showed a split between 30 and 90 days of composting indicating a change in the rate of neoformation of HA after a stabilisation phase. Afterwards, the rate of HA neoformation varied linearly with the duration of composting.

Characterization of Low Molecular Weight Organic Acids from Beech Wood Treated in Supercritical Water

Japanese beech (Fagus crenata Blume), its cell wall components, and model compounds were treated by supercritical water (380 degrees C, 100 MPa) for 5 s using a batch-type reactor to investigate the production behavior of low molecular weight organic acids. It was found that cellulose and hemicellulose were decomposed to formic acid, pyruvic acid, glycolic acid, acetic acid, and lactic acid, whereas lignin was barely decomposed to such organic acids under the given conditions. However, after prolonged treatment (380 degrees C, 100 MPa, 4 min) of lignin, some organic acids were recovered owing perhaps to the decomposition of the propyl side chain of lignin. It was additionally revealed that the predominant organic acid recovered was acetic acid, which might be derived from the acetyl group of hemicellulose in Japanese beech.

Poly(Ethylene Oxide)/Organosolv Lignin Blends: Relationship between Thermal Properties, Chemical Structure, and Blend Behavior

Blends of poly(ethylene oxide) with organosolv lignin (Alcell) were prepared by thermal blending. Excellent fiber spinning was achieved over the entire blend ratio. The good thermal properties of the Alcell lignin arise from its unique chemical structure. HMQC 2D NMR analysis revealed the presence of alkoxyl chains at the Cα and Cγ positions of the Alcell lignin side chain structure acting as internal plasticizers and enhancing the thermal mobility of the lignin. The addition of a small amount of Alcell lignin to PEO resulted in an increase of the PEO crystalline domain size. However, both PEO crystallinity and crystalline domain size decreased with lignin incorporation beyond 25 wt %. A negative polymer−polymer interaction energy density “B” was calculated on the basis of the melting point depression of PEO and a negative deviation of Tg from the weighted average values observed. Good prediction of the Tg-composition behavior was obtained indicating the presence of favorable interactions between blend components. FT-IR analysis revealed the formation of a strong hydrogen-bonding system between Alcell lignin and PEO, supporting that hydrogen-bonding interactions are an important factor in the formation of miscible lignin-based polymer blends.