Destruction of aspen wood by the fungusPhanerochaete sanguinea quantitative1H and13C NMR spectroscopies of biologically degraded lignin

The lignin of mechanically ground aspen wood and lignins isolated from aspen wood attacked by the fungusPhanerochaete sanguinea have been investigated by quantitative¹H and¹³C NMR spectroscopies. It has been shown that the biodestruction of the lignin takes place through the cleavage of alkyl-aryl and aryl-aryl bonds and is accompanied by demethylation (demethoxylation) reactions, and the oxidation of C and C atoms. In addition to reactions in which the C—C bonds are cleaved, the formation of ether bonds has been observed. An interconnection has been shown between the variations in the amount of functional groups, fragments, and the bonds in biolignins and the loss in mass of the wood. A method is proposed for evaluating the carbohydrate content in lignin preparations using the NMR method.Wood Chemistry Branch of the Institute of Organic Chemistry, Siberian Division of the Russian Academy of Sciences, Irkutsk. Irkutsk State University. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 547–557, July–August, 1994.     

Chemical transformations of lignin during the biodegradation and organosolv pulping of deciduous wood

The lignins from the liquors in the organosolv pulping of aspen wood treated with wood-destroying fungi have been investigated using quantitative¹H and¹³C NMR spectroscopy and exclusion liquid chromatography. It has been shown that the biodegradation of lignin takes place in different ways according to the complex of enzymes produced by the fungi. Phanerochaete sanguinea causes degradation through predominant cleavage at alkyl-phenyl bonds, and Trametes villosus at the C-C bonds of the aliphatic chain. In addition to degradation reactions, polymerization (condensation) reactions also take place with the appearance of new C_ar-O-C and C_ar-C bonds. It has been established that the biological pretreatment of aspen wood ensuring partial degradation of the lignin leads to its more ready extraction in the process of organosolv pulping.Wood Chemistry Division of the Irkutsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 603–610, July–August, 1995. Original article submitted May 23, 1994.     

Biotransformation of Aspen Lignin by the Fungus Trametes villosus

Quantitative ¹ H and ¹³ C NMR spectroscopies demonstrate that biotransformation of aspen wood by the fungusTrametes villosusresults in oxidation and destruction of lignin with cleavage of C-C alkyl-alkyl bonds in side chains and partial demethoxylation in addition to cleavage of lignocarbohydrate bonds. New C _ar -O-C bonds form while lignin is being destroyed at alkyl-alkyl bonds. Cleavage of rings and destruction of C _ar -C bonds was not observed.     

Quantitative1H and13C NMR spectroscopy of lignins from an aqueous ethanolic cook of aspen wood

General and comparative characteristics obtained by¹H and¹³C NMR spectroscopy of the lignins from aqueous ethanolic cooks are presented. It is shown that degradation of the lignin macromolecule takes place during the digestion of aspen wood. The mean length of the lignin side chains decreases and ether bonds are cleaved, while the degree of condensation of the substances increases.Irkutsk State University. Irkutsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 277–285, March–April, 1993.     

Effects of process severity on the chemical structure of Miscanthus ethanol organosolv lignin

Ethanol organosolv lignin extracted from Miscanthus × giganteus with differing levels of severity (1.75 < CS<2.8) were subjected to comprehensive structural characterization by ¹³C, ³¹P NMR, FTIR spectroscopy and gel permeation chromatography. The results were compared to those from milled wood lignin from the same feedstock. The results showed that an increase in the severity of the treatment enhanced the dehydration reactions on the side chain and the condensation of lignin, increased the concentration of phenol groups and decreased the molecular mass of lignin fragments. It appeared that for the experimental conditions generally employed the cleavage of α-aryl ether bonds is primarily reaction responsible for lignin depolymerization under the organosolv conditions examined.     

Investigation of structure of milled wood and dioxane lignins of Populus nigra and Cupressus sempervirens using the DFRC method

In this study, derivatisation followed by reductive cleavage (DFRC) were used to investigate milled wood lignin (MWL) and dioxane lignin (DL) structures of Populus nigra and Cupressus sempervirens. After the DFRC reactions, the constituents obtained from these two kinds of lignin were recognised structurally using several chromatographic and spectral methods such as ¹³C NMR, GC-MS, and GPC. Comparative results showed that the dominant structural components of the two kinds of lignin are obtained from the cleavage of ??-O-4 bonds. The main component of DL and MWL of P. nigra is 4-hydroxy-3,5-dimethoxy-1-phenyl-??-hydroxypropene (syringyl structures). Also, some guaiacyl structures were observed. The dominant component identified in both lignins of C. sempervirens is 4-hydroxy-3-methoxy-1-phenyl-??-hydroxypropene (guaiacyl structures). The cleavage method has a good performance for both P. nigra and C. sempervirens and the results obtained are in good agreement with previously published data.     

Investigation of the chemical modifications of beech wood lignin during heat treatment

Holocellulose, Klason lignin and milled wood lignin (MWL) of beech wood were extracted before and after heat treatment and analysed using CP MAS ¹³C NMR, ¹³C NMR, ³¹P NMR and size exclusion chromatography (SEC). Experimental results showed that the thermal treatment degrades hemicelluloses and affects lignin polymer through depolymerisation due mainly to cleavage of β-aryl-ether linkages and recondensation reactions. The spectroscopic analysis of MWL demonstrated that these recondensation reactions involved mainly guaiacyl units through formation of 5,5′-biphenolic and diarylmethane structures.Analysis of molecular weight distribution of MWL by SEC indicated that average molecular weights of heat treated milled wood lignin were lower than those of native milled wood lignin.     

The chemistry and kinetic behavior of Cu-Cr-As/B wood preservatives. II. Fixation of the Cu/Cr system on wood

The kinetic behavior of a Cr⁶⁺/Cu²⁺ system in its reaction with wood has been elucidated. The same reactions with carbohydrates and lignin of wood for Cr^VI alone are still present. Approximately 20% of the copper is fixed to the guaiacyl units of lignin in the form of copper chromate; the remaining copper forms complexes with cellulose and mainly with the guaiacyl units of lignin. The Cr^VI/lignin guaiacyl unit complexes already found for the treatment of wood with CrO₃ are still the main Cr^VI complexes formed. Copper chromate is present as [Cu(H₂O)₂(guaiacol)]CrO₄(guaiacol) complexes, and CuCrO₄ bridges between different guaiacyl units of the lignin network appear to be likely. Substantial interference of the Cu²⁺ ions in the second-zone reactions of Cr^VI with wood occurs. The amount of Cr^VI and Cr^III fixed onto lignin and cellulose compares well with experimental values. Rate constants, energies of activation, and Arrhenius equations of the various reactions have been obtained. The amount of Cu²⁺ interference in the reaction has also been calculated.     

Separation and characteristic analysis of steam-exploded lignin from cornstalk residue

Steam-exploded lignin (SEL) was separated from cornstalk residue, which came from steam-exploded cornstalk after enzymatic hydrolysis. There are two methods to acquire SEL, the alkali solution and the organic solvent method. SEL was analyzed with respect to the elementary composition, molecular weight, IR spectrum, and ¹³C NMR spectra. The C₉-formula of SEL was calculated from the experiment data. According to ¹³C NMR, SEL can be classified as a “GSH” type of lignin, and it is composed mainly of β-O-4 ether bonds together with β-5 and β-1 carbon-carbon linkages between the lignin structural units.     

The chemistry and kinetic behavior of Cu-Cr-As/B wood preservatives. IV. Fixation of CCA to wood

The kinetic behavior of copper–chromium–arsenic (CCA) wood preservatives in their reaction with wood, lignin, cellulose, and their respective simple model compounds, guaiacol and D(+)-glucose, has been elucidated. Copper chromates^VI/lignin guaiacyl units and chromium^III arsenates/lignin guaiacyl units, which are stable and insoluble complexes formed during the reaction, have been characterized. No copper arsenates were formed during the reactions (which were carried out using a CCA of type C). The sequence, nature, and combined effect of the reactions of CCA with wood, lignin, and cellulose are similar to that already described for the “CrO₃ alone,”¹ Cu/Cr², and Cr/As³ systems. Rate constants, energies of activation, and Arrhenius equations have been obtained and reported. The distribution of Cr^VI, Cr^III, As^v, and Cu²⁺ in CCA-C-treated wood has been calculated. The results obtained have allowed meaningful comparisons of several commercial CCA formulations.     

Chemical Characterization of Kraft Lignin Prepared from Mixed Hardwoods

Chemical characterization of kraft lignin (KL) from mixed hardwoods (Acacia spp. from Vietnam and mixed hardwoods (mainly Quercus spp.) from Korea) was conducted for its future applications. To compare the structural changes that occurred in KL, two milled wood lignins (MWLs) were prepared from the same hardwood samples used in the production of KL. Elemental analysis showed that the MWL from acacia (MWL-aca) and mixed hardwood (MWL-mhw) had almost similar carbon content, methoxyl content, and C₉ formula. KL had high carbon content but low oxygen and methoxyl contents compared to MWLs. The C₉ formula of KL was determined to be C₉H_7.29O_2.26N_0.07S_0.12(OCH₃)_1.24. The M_w of KL and MWLs was about 3000 Da and 12,000–13,000 Da, respectively. The structural features of KL and MWLs were investigated by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectrometry (¹H, ¹³C NMR). The analyses indicated that KL underwent severe structural modifications, such as γ-carbon cleavage, demethylation, and polycondensation reactions during kraft pulping, which resulted in increased aromatic content and decreased aliphatic content. The main linkages in lignin, β-O-4 moieties, were hardly detected in the analysis as these linkages were extensively cleaved by nucleophilic attack of SH^- and OH^- during pulping.     

The chemistry and kinetic behavior of Cu-Cr-As/B wood preservatives. I. Fixation of chromium on wood

The kinetic behavior of CrO₃ in its reaction with wood has been elucidated. Various reactions take place between CrO₃ and the lignin and cellulose in wood. CrO₃ reacts with cellulose in a two-step reaction: the first step is an adsorption of Cr^VI onto the cellulose to form Cr^VI/cellulose activated complexes. The second step is a Cr^VI → Cr^III reduction taking place on the cellulose surface. The Cr^III formed is only physically adsorbed to the cellulose or very weakly bound as small amounts of Cr^III can be released into the reaction medium. The Cr^VI adsorbed by cellulose appears mainly to be reduced to Cr^III. The reaction of Cr^VI with lignin has been shown to be the composition of the three successive reaction of Cr₂O₇^2?, HCrO₄^?, and CrO₄^2? with the guaiacyl units of lignin. Insoluble and stable Cr^VI/lignin complexes in which chromium maintains its hexavalent oxidation state are formed. Rate constants and energies of activation for all the reactions have been determined. The fixation of CrO₃-derived compounds on wood has been explained as the combination of the various reactions investigated. The results indicate that 60% of Cr is fixed irreversibly to the lignin of wood as Cr^VI and 40% is weakly bound, probably just precipitated, on the cellulose surface as Cr^III of which small amounts can be released in a water medium. The complex Cr^VI and Cr^III species forming complexes with the guaiacyl units have been identified.     

A 19F NMR study of the transmission of electronic effects in triarylantimony and triarylbismuth compounds. A comparison with the nitrogen- and carbon-containing analogues

A ¹⁹F NMR study of the transmission of electronic effects has been made for the systems Ar₂EC₆H₄F-4 (E = Sb, Bi, CH, N). The fluorine chemical shifts obtained are correlated with the polar constants (Σσ^o and Σσ) of the substituents, suggesting that electronic effects are transmitted through the SbC_ar, BiC_ar and CC_ar bonds predominantly by an inductive mechanism, whereas the transmission through the NC_ar bonds is contributed to significantly by classical resonance effects due to competitive conjugation of the lone pair with the aromatic rings, and the substituents therein. A dual parameter correlation of the fluorine chemical shifts with the inductive (σ_I) and resonance (σ^o_R and σ_R) parameters of the substituents in the aromatic rings has led to similar conclusions. The inductive transmission through the bridging Sb and Bi atoms has been assigned to the absence of conjugation of lone pair and vacant d-orbitals of the metals with π-electron systems of the aromatic rings. On the basis of the values of the ? coefficients for the correlation equations obtained it has been established that the transmitting ability of the BiC_ar bonds is close to that of the C_alC_ar bonds and considerably lower than the transmitting ability of the NC_ar bonds.     

Adsorption of phenol on wood surfaces

Adsorption of phenol on aspen and pine wood is investigated. It is shown that adsorption isotherms are described by the Langmuir model. The woods’ specific surface areas and adsorption interaction constants are determined. It is found that the sorption of phenol on surfaces of aspen and pine is due to Van der Waals interactions (S_sp = 45 m²/g_odw for aspen and 85 m²/g_odw for pine). The difference between the adsorption characteristics is explained by properties of the wood samples’ microstructures.     

Untersuchungen zum elektronischen einfluss von organylliganden: IV. 13C-NMR-spektroskopische untersuchung der gegenseitigen beeinflussung von organylliganden in triethylzinnorganylverbindungen

By means of ¹³C NMR spectroscopy, the coupling constants ¹J(¹¹⁹Sn¹³C_Et) of 18 compounds of the SnEt₃R type (R = organo group) have been measured. These coupling constants have been shown to reflect the change induced by R in the s-content of the tin hybrid orbitals of the SnCEt bonds. The series of the influence of R obtained on the basis of the coupling constant mentioned as a parameter is compared with a trans-influence series of R obtained on organo-mercury compounds. Occurring differences are attributed to different modes of bonding of the group R at the central atom.     

Urchin-like Nb2O5 hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions

Selective cleavage of robust C?C bonds to harvest value-added aromatic oxygenates is an intriguing but challenging task in lignin depolymerization. Photocatalysis is a promising technology with the advantages of mild reaction conditions and strong sustainability. Herein, we show a novel urchin-like Nb₂O₅ hollow microsphere (U-Nb₂O₅ HM), prepared by one-pot hydrothermal method, are highly active and selective for Cα?C_β bond cleavage of lignin β-O-4 model compounds under mild conditions, achieving 94% substrate conversion and 96% C?C bond cleavage selectivity. Systematic experimental studies and density functional theory (DFT) calculations revealed that the superior performance of U-Nb₂O₅ HMs arises from more exposed active sites, more efficient free charge separation and the active (001) facet, which facilitates the activation of C_β?H bond of lignin models and generate key C_β radical intermediates by photogenerated holes, further inducing the C_α?C_β bond cleavage to produce aromatic oxygenates. This work could provide some suggestions for the fabrication of hierarchical photocatalysts in the lignin depolymerization system.     

Preparation and some reactions of organogermylmercuryplatinum complexes and related compounds

A single-crystal X-ray diffraction study of tetracarbonyl-ferra-3-cyclopentene-2,5-dione has been made. Formally the compound can be derived from maleic anhydride by substitution of the bridging oxygen by Fe(CO)₄. Accordingly the bonding character is similar to that of maleic anhydride. The ironcarbon distances in the ring indicate partial double bonds. The octahedrally coordinated iron atom is linked to four terminal carbon monoxide ligands, with a longer bond distance to the equatorial than to the axial ones (FeC_ax 1.809 Å, FeC_eq 1.854 Å). The axial CO groups are strongly inclined towards the ring (C_axFeC_ax 164°). The latter effect is explained by electronic repulsion of the CO groups.IR, ¹H NMR, and ¹³C NMR data are reported. Crystal data: space groupPnama:α  12.708(10),b  10.058(7),c  7.527(5) Å;Z  4. With 625 reflections [F_o > 3o(F_o)] the structure has been refined anisotropically (hydrogen isotropically) to R0.022.     

Organic amine mediated cleavage of Caromatic–Cα bonds in lignin and its platform molecules

The activation and cleavage of C–C bonds remains a critical scientific issue in many organic reactions and is an unmet challenge due to their intrinsic inertness and ubiquity. Meanwhile, it is crucial for the valorization of lignin into high-value chemicals. Here, we proposed a novel strategy to enhance the C_aromatic–C_α bond cleavage by pre-functionalization with amine sources, in which an active amine intermediate is first formed through Markovnikov hydroamination to reduce the dissociation energy of the C_aromatic–C_α bond which is then cleaved to form target chemicals. More importantly, this strategy provides a method to achieve the maximum utilization of the aromatic nucleus and side chains in lignin or its platform molecules. Phenols and N,N-dimethylethylamine compounds with high yields were produced from herbaceous lignin or the p-coumaric acid monomer in the presence of industrially available dimethylamine (DMA).

Pre-functionalization with amine sources mediated the cleavage of C_aromatic–C_α bonds to produce two valuable chemicals with high yields, for the full utilization of the aromatic rings and side-chains in lignin and its platform molecules.     

Characterization of milled wood lignin and ethanol organosolv lignin from miscanthus

Ethanol organosolv lignin extracted from Miscanthus × giganteus (using the following conditions: T = 190 °C, t = 60 min, sulfuric acid = 1.2% w/w, EtOH/H₂O = 0.65) and milled wood lignin from Miscanthus × giganteus were subjected to a comprehensive structural characterization by ¹³C, ³¹P NMR, FTIR, UV spectroscopies and size exclusion chromatography. The results showed that Miscanthus lignin is an H/G/S type (4%, 52%, 44% respectively) with ∼0.41 β-O-4 linkage per aromatic ring and contains coumarylate linkages (0.1/Ar). It was shown that during organosolv treatment, cleavage of β-O-4 linkages and of ester bond (acetyl and coumaryl residues) was the major mechanisms of lignin breakdown but the process did not significantly change the core of the lignin structure.     

CP-MAS C NMR and FT-IR investigation of the degradation reactions of polymer constituents in wood welding

The essential chemical modifications involving the polymeric constituents of wood in friction welding occur in the first 5-6 s slowing down or even stopping afterwards. FT-IR and CP-MAS ¹³C NMR of the welded area of wood have shown dehydration and an apparent increase in the crystallinity of cellulose. A certain level of hemicelluloses degradation occurs, accompanied by the generation of some furfural. Cellulose degradation is instead very slight. Both analytical techniques show an increase in the proportion of lignin in the welding interphase. A proportion of methoxy groups of lignin is de-etherified to phenolic hydroxy groups. Self-condensation of lignin occurs by internal rearrangement with the formation of Ar-Ar and Ar-CH₂-Ar bridges. This progresses throughout the whole process of welding. The formation of C-O-C bridges, although stopping after 6 s welding, at the start of wood carbonisation, also appears to contribute to the increase in cross-linking of the lignin network.