Spectra Of Lignin Research Articles

Effects of Solvation and Ionization on 13C NMR Spectra of Lignin Model Compounds, Spruce Milled Wood Lignin and Kraft Lignin

The effects of alkali and polar aprotic solvent on the aromatic carbons signals in 13C NMR (Carbon-13 nuclear magnetic resonance) spectra of lignin model compounds and spruce milled wood lignin (MWL) were studied. It was found that in 1 M aqueous NaOH signal shifts of C-1 and C-4 carbon atoms in the aromatic ring were the most noticeable in lignin models with free phenolic hydroxyl groups, which are ionized under the conditions. A similar effect in the spectra of the studied model compounds was observed in 0.5 M aqueous NaOD-deuterated dimethyl sulfoxide (DMSO) mixture (DMSO: water ratio 3:7 v/v). The model data help explaining changes in the 13C NMR spectra of MWL and lignin in situ dissolved in spruce kraft black liquor caused by ionization. In the 13C NMR spectra of spruce black liquor the signals of phenolic and non-phenolic lignin units are clearly separated and do not overlap with the signals of the carbon atoms of carbohydrates and other aliphatic products of wood degradation. The data obtained are useful in understanding the important role of solvation and ionization processes leading to lignin solubilization.

Valorization of Lignin to Simple Phenolic Compounds over Tungsten Carbide: Impact of Lignin Structure.

Lignins isolated from representative hardwood, softwood, and grass materials were effectively hydrocracked to aromatics catalyzed by tungsten carbide over activated carbon (W2 C/AC). The effects of botanical species and fractionation methods on lignin structure and the activity of W2 C/AC were studied in detail. Gas permeation chromatography (GPC), FTIR, elemental analysis, and 2 D HSQC NMR showed that all the extracted samples shared the basic skeleton of lignin, whereas the fractionation method significantly affected the structure. The organosolv process provided lignin with a structure more similar to the native lignin, which was labile to be depolymerized by W2 C/AC. Softwood lignins (i.e., spruce and pine) possessed higher molecular weights than hardwood lignins (i.e., poplar and basswood); whereas corn stalk lignin that has noncanonical subunits and exhibited the lowest molecular weight owing to its shorter growth period. β-O-4 bonds were the major linkages in all lignin samples, whereas softwood lignins contained more resistant linkages of β-5 and less β-β than corn stalk and hardwood lignins; as a result, lowest hydrocracking efficiency was obtained in softwood lignins, followed by corn stalk and hardwood lignins. 2 D HSQC NMR spectra of lignin and the liquid oil as well as the solid residue showed that W2 C/AC exhibited high activity not only in β-O-4 cleavage, but also in deconstruction of other ether linkages between aromatic units, so that high yield of liquid oil was obtained from lignin.

Calculation of IR-spectra of structural fragments of lignins

To study structure of softwood lignins the experimental and theoretical IR-spectra in middle IR-diapason were analyzed. To interpret these data the quantum chemical calculations of IR-spectra of general dimmer fragments of softwood lignins by method of density functional theory (DFT/B3LYP) with 6-31G(d,p) as basis set were carried out. These calculations showed that frequencies of normal vibrations of fragment with β-alkyl-aryl linkage are close to the experimental values of the IR absorption bands of lignin, and infrared spectrum of this structure is similar to the experimental spectrum of lignin. The calculations with accounting for the solvent showed a strong increase in the intensity of the majority of the bands and the solvent effect on the frequencies of vibrations.

Introduction of soft X-ray spectromicroscopy as an advanced technique for plant biopolymers research.

Soft X-ray absorption spectroscopy coupled with nano-scale microscopy has been widely used in material science, environmental science, and physical sciences. In this work, the advantages of soft X-ray absorption spectromicroscopy for plant biopolymer research were demonstrated by determining the chemical sensitivity of the technique to identify common plant biopolymers and to map the distributions of biopolymers in plant samples. The chemical sensitivity of soft X-ray spectroscopy to study biopolymers was determined by recording the spectra of common plant biopolymers using soft X-ray and Fourier Transform mid Infrared (FT-IR) spectroscopy techniques. The soft X-ray spectra of lignin, cellulose, and polygalacturonic acid have distinct spectral features. However, there were no distinct differences between cellulose and hemicellulose spectra. Mid infrared spectra of all biopolymers were unique and there were differences between the spectra of water soluble and insoluble xylans. The advantage of nano-scale spatial resolution exploited using soft X-ray spectromicroscopy for plant biopolymer research was demonstrated by mapping plant cell wall biopolymers in a lentil stem section and compared with the FT-IR spectromicroscopy data from the same sample. The soft X-ray spectromicroscopy enables mapping of biopolymers at the sub-cellular (~30 nm) resolution whereas, the limited spatial resolution in the micron scale range in the FT-IR spectromicroscopy made it difficult to identify the localized distribution of biopolymers. The advantages and limitations of soft X-ray and FT-IR spectromicroscopy techniques for biopolymer research are also discussed.

Identification of the best DFT functionals for a reliable prediction of lignin vibrational properties

Lignin is the most abundant aromatic plant polymer on earth. Useful information on its structure and interactions is gained by vibrational spectroscopy and relies on the quality of band assignments. B3LYP predictions were recently shown to support band assignments. Further progress calls for a comprehensive study of the quality of available theoretical methods in relation to the task of predicting lignin vibrational properties. The present study examined more than 50 functionals for prediction of IR vibrations of an appropriate lignin model. Based on a basis set incompleteness study, the pc-2 basis set was used. B98, X3LYP and B97-1 were the overall best-performing functionals, and “fingerprint” band positions were predicted by single-factor scaling of harmonic frequencies to an average error of ±3 cm−1 by optimized scaling factors of 1.017, 1.021 and 1.016, respectively. Their performance using instead explicit anharmonic correction was slightly worse giving an error of ca. ±5 cm−1. The X3LYP and B97-1 functionals offer also good description of hydrogen bonding. Error compensation from, e.g., insufficient treatment of solvation is likely to affect these results, and thus at this stage no single functional stands out. These results provide a needed basis for further theoretical developments in relation to vibrational assignments of Infrared and Raman spectra of lignin.

SINTESIS DAN KARAKTERISASI SUPERABSORBEN DARI SELULOSA JERAMI PADI (Superabsorbent Synthesis and Characterization of Rice Straw Cellulose)

Copolymerization of cellulose from rice straw with acrylic acid and acrylamide produce biopolymer superabsorbent. Cellulose was purified from fat content by extraction with toluene:ethanol (2:1). Hemicelluloses and lignin were removal by using potassium hydroxide 5% and hydrogen peroxide 2% at alkaline pH. Cellulose yield obtained was 21.56%. FTIR spectra of lignin showed a loss of absorption at 1728 cm-1. Copolymerization was carried out at 65 C under nitrogen athmosphere. Initiator and cross linking agent used were potassium peroxodisulfate and N'N-methylene bis acrylamide. Superbasorben resulted from this experiment showed the water swelling capacity after 24 hour for the water, solution of 100 ppm of ammonium chloride, and urea respectively 387,11 g/g ; 193,47 g/g and 400,17 g/g.Keywords : superabsorbent, rice straw, swelling capacity

Assessment of covalent bond formation between coupling agents and wood by FTIR spectroscopy and pull strength tests

Abstract In the focus was the question whether metal alkoxide coupling agents – titanium, silane, and zirconium – form covalent bonds to wood and how they improve coating adhesion. In a previous work, a downshift of the lignin infrared (IR) band ∼1600 cm-1 was shown to be consistent with the formation of ether linkages between lignin and titanium coupling agent. In the present work, changes were found in the attenuated total reflectance-Fourier transform IR (ATR-FTIR) spectra of lignin and wood mixed with silane, and titanium coupling agents, and to a lesser extent for a zirconium coupling agent. This was seen as evidence for covalent bonds between lignin phenolics and the coupling agents. No spectral changes were observed when the coupling agents were mixed with the wood constituents cellulose and hemicellulose. For verification of the results, a modified EN 311 wet adhesion pull strength test was performed with softwood panels painted with a solvent-borne alkyd/acrylic coating. The results revealed an improved adhesion for all tested coupling agents compared to the untreated reference. The spectroscopic and pull test results underline that the presence of the lignin moiety in wood is of central importance for improved wood coating adhesion.

Treatment of Sugarcane Bagasse Lignin Employing Atmospheric Pressure Microplasma Jet in Argon

AbstractAn atmospheric argon rf microplasma jet was employed to treat lignin samples. The treatment time was carried out from 30 min to 4 h resulting in a strong degradation of the lignin structure. The most important degradation was observed in functional groups having asymmetric in‐phase ring stretching as well as in CC and CO stretching vibrations. Simple calculations may help us explain the OH bond breakings by electron collisions inside the microplasma. In the afterglow condition, it was not observed any change on the lignin spectra.

Low-energy electron scattering by cellulose and hemicellulose components

We report elastic integral, differential and momentum transfer cross sections for low-energy electron scattering by the cellulose components β-D-glucose and cellobiose (β(1 → 4) linked glucose dimer), and the hemicellulose component β-D-xylose. For comparison with the β forms, we also obtain results for the amylose subunits α-D-glucose and maltose (α(1 → 4) linked glucose dimer). The integral cross sections show double peaked broad structures between 8 eV and 20 eV similar to previously reported results for tetrahydrofuran and 2-deoxyribose, suggesting a general feature of molecules containing furanose and pyranose rings. These broad structures would reflect OH, CO and/or CC σ* resonances, where inspection of low-lying virtual orbitals suggests significant contribution from anion states. Though we do not examine dissociation pathways, these anion states could play a role in dissociative electron attachment mechanisms, in case they were coupled to the long-lived π* anions found in lignin subunits [de Oliveira et al., Phys. Rev. A, 2012, 86, 020701(R)]. Altogether, the resonance spectra of lignin, cellulose and hemicellulose components establish a physical-chemical basis for electron-induced biomass pretreatment that could be applied to biofuel production.

Raman-spectroscopy-based noninvasive microanalysis of native lignin structure

A new robust, noninvasive, Raman microspectroscopic method is introduced to analyze the structure of native lignin. Lignin spectra of poplar, Arabidopsis, and Miscanthus were recovered and structural differences were unambiguously detected. Compositional analysis of 4-coumarate-CoA ligase suppressed transgenic poplar showed that the syringyl-to-guaiacyl ratio decreased by 35% upon the mutation. A cell-specific compositional analysis of basal stems of Arabidopsis showed similar distributions of S and G monolignols in xylary fiber cells and interfascicular cells.

Blind image analysis for the compositional and structural characterization of plant cell walls

A new image analysis strategy is introduced to determine the composition and the structural characteristics of plant cell walls by combining Raman microspectroscopy and unsupervised data mining methods. The proposed method consists of three main steps: spectral preprocessing, spatial clustering of the image and finally estimation of spectral profiles of pure components and their weights. Point spectra of Raman maps of cell walls were preprocessed to remove noise and fluorescence contributions and compressed with PCA. Processed spectra were then subjected to k-means clustering to identify spatial segregations in the images. Cell wall images were reconstructed with cluster identities and each cluster was represented by the average spectrum of all the pixels in the cluster. Pure components spectra were estimated by spectral entropy minimization criteria with simulated annealing optimization. Two pure spectral estimates that represent lignin and carbohydrates were recovered and their spatial distributions were calculated. Our approach partitioned the cell walls into many sublayers, based on their composition, thus enabling composition analysis at subcellular levels. It also overcame the well known problem that native lignin spectra in lignocellulosics have high spectral overlap with contributions from cellulose and hemicelluloses, thus opening up new avenues for microanalyses of monolignol composition of native lignin and carbohydrates without chemical or mechanical extraction of the cell wall materials.

Study on Chemical Compositions of Manihot Esculenta Crantz(<i>M. utilissima</i> Pohl)Stalks

The chemical compositions of Manihot esculenta crantz(M. utilissima Pohl)stalks were investigated, the contents of phenolic hydroxyl group and UV spectra of lignin were determined by ultraviolet-visible spectrophotometer. The result showed that the chemical compositions of Manihot esculenta crantz(M. utilissima Pohl)stalks were as follows: ashes 4.97%, cold water extraction 12.04%, hot water extraction 12.57%, 1% sodium hydroxide solution extraction 34.16%, benzene-alcohol solution extraction 4.20%, nitric acid-alcohol cellulose 35.86%, holo-cellulose 72.62%, pentosan 19.20%, acid-soluble lignin 2.51%, acid-insoluble lignin 26.10%, organic solvent-soluble lignin 1.07%, pectin content is 0.02%; it can be used as a non-wood renewable source of natural products.Phenolic hydroxyl content of organic solvent-soluble lignin and acid-insoluble lignin are 1.245 mmol·g-1 and 0.261mmol·g-1 respectively; the maximum absorption wavelength of organic solvent-soluble lignin and acid-soluble lignin in the UV region is near to 205 nm and 280 nm, but shifts to long wavelength or short wavelength with the nature of the different solvents.

The Effect of Microwave Treatment on the Hydrogen Peroxide Bleaching of Soda-AQ Wheat Straw Pulp

In this paper, the effect of microwave treatment on the hydrogen peroxide bleaching of Soda-AQ wheat-straw pulp was investigated. The results showed that microwave treatment could increase the brightness of the hydrogen peroxide bleached pulp. The fiber coarseness of microwave enhancing peroxide bleached pulp was higher than that of the peroxide bleached pulp. However, the arithmetic average fiber length, the length weighted average fiber length and weight weighted average fiber length of the former was lower than that of the latter. Fourier transform infra-red spectroscopy (FTIR) and X-ray diffraction (XRD) spectra showed that CrI(%) crystallinity of microwave enhancing peroxide bleached pulp was similar as that of the peroxide bleached pulp but all higher than that of the Soda-AQ wheat-straw pulp. N·O′KI infra-red crystalline index of microwave enhancing peroxide bleached pulp were lower than that of the peroxide bleached pulp. The FTIR spectra of lignin showed that the microwave treatment had some influences on the methoxyl and phenolic group in lignin.

Acetylation of wood causes photobleaching

This paper deals with the photobleaching of acetylated wood. The acetylated spruce wood was irradiated by artificial sunlight emitted from xenon lamp with covering several kinds of band-pass filter. The lightness ( L *) of acetylated wood increased with integral irradiance. The chroma (Δ C *) decreased by light-irradiation with wavelength from 430 nm to 500 nm. However, the light-irradiation including ultraviolet ray region made it decrease after increase with integral irradiance. The visible light made hue angle ( h°) increase, however, the ultraviolet ray made it decrease. The lignin degradation and the production of carbonyl groups were observed by light-irradiation including ultraviolet ray. However, no remarkable changes in IR spectra were observed by visible light-irradiation. Photobleaching of acetylated wood was caused by mainly visible light without modifying the IR spectra of lignin.

Dual role of lignin in plant litter decomposition in terrestrial ecosystems

Plant litter decomposition is a critical step in the formation of soil organic matter, the mineralization of organic nutrients, and the carbon balance in terrestrial ecosystems. Biotic decomposition in mesic ecosystems is generally negatively correlated with the concentration of lignin, a group of complex aromatic polymers present in plant cell walls that is recalcitrant to enzymatic degradation and serves as a structural barrier impeding microbial access to labile carbon compounds. Although photochemical mineralization of carbon has recently been shown to be important in semiarid ecosystems, litter chemistry controls on photodegradative losses are not understood. We evaluated the importance of litter chemistry on photodegradation of grass litter and cellulose substrates with varying levels of lignin [cellulose-lignin (CL) substrates] under field conditions. Using wavelength-specific light attenuation filters, we found that light-driven mass loss was promoted by both UV and visible radiation. The spectral dependence of photodegradation correlated with the absorption spectrum of lignin but not of cellulose. Field incubations demonstrated that increasing lignin concentration reduced biotic decomposition, as expected, but linearly increased photodegradation. In addition, lignin content in CL substrates consistently decreased in photodegradative incubations. We conclude that lignin has a dual role affecting litter decomposition, depending on the dominant driver (biotic or abiotic) controlling carbon turnover. Under photodegradative conditions, lignin is preferentially degraded because it acts as an effective light-absorbing compound over a wide range of wavelengths. This mechanistic understanding of the role of lignin in plant litter decomposition will allow for more accurate predictions of carbon dynamics in terrestrial ecosystems.

Characterization of spectra of lignin from midribs of tobacco at THz frequencies

The functions of the chemicals are closely related with their compositions and structures. In this paper, we report the characterization of different lignin in the midribs of tobacco leaves using terahertz (THz) time-domain spectroscopy in the frequency range of 0.3 to 2 THz. These lignins are extracted from tobacco leaves grown in different regions. Lignin in midribs of tobacco leaves from the south region and the north region show distinctively different refractive indexes and absorption coefficients at THz frequency. The differences at THz range are found to be correlated with their chemical compositions, which are obtained by way of X-ray microanalysis. This clearly verifies that it is possible to employ THz time-domain spectroscopy as a tool for identifying the functions of the chemicals and analyzing their chemical compositions.

Colour in thermally modified wood of beech, Norway spruce and Scots pine. Part 1: Colour evolution and colour changes

Abstract Colour evolution and colour changes were analysed from surface images of small specimens of three thermally-modified timber species using the CIEL*a*b* colour space. Upon heat exposure, the wood substance became orange and then approached grey irrespective of species; this was accompanied by a steady reduction in lightness. Colour changes were similar in the three woods at any given level of heat-induced weight loss (WL), whilst changes in the three coordinates of the CIEL*a*b* space in function of WL were different regardless of the wood species. For ΔL*, the profile was curvilinear and monotonous, while Δa* and Δb* bear a complex, non-linear profile. In turn, ΔE* was found to be highly influenced by the behaviour of ΔL*. It is proposed that ΔE* in thermally modified wood originates from chemical changes in the main wood polymers, more so in lignin than in polysaccharides, due to the darkening of the lignin itself. This was associated with the generation of chromophoric groups, mainly the increase in carbonyl groups appearing in the Fourier transform infrared spectra of lignin between 1710 and 1600 cm-1, particularly the emergence of quinone species.

Near‐IR surface‐enhanced Raman spectrum of lignin

AbstractCompacted powders of commercially available nano‐ and microparticles of silver were used to successfully induce the surface‐enhanced Raman scattering (SERS) effect in spruce milled‐wood lignin (MWL). For the two silver particle sizes used in this investigation, the spectra were mostly similar. Some general characteristics of the lignin SERS spectrum are described. The SERS technique was found to be sensitive for detecting lignin. Significant spectral changes were present between the SERS and normal Raman spectra of MWL. The SERS spectrum was assigned on the basis of literature‐reported vibrational assignments of lignin and its models. Based on significant changes in Raman features, we propose that the lignin is strongly adsorbed on silver. To determine whether SERS of lignin can be obtained directly from wood without its isolation, Wiley‐milled spruce wood (WMW) adsorbed on silver was studied. The results indicated that not only the surface‐enhancement effect was successfully induced in the WMW, but that its spectrum was similar to MWL SERS. Moreover, for WMW, no signals from the carbohydrate components were observed, and therefore, lignin was detected selectively. This nano‐ and microparticle‐based molecularly specific method is expected to make a significant contribution in identifying and investigating lignin in various lignin‐containing materials. Published in 2009 by John Wiley & Sons, Ltd.

Changes in the infrared attenuated total reflectance (ATR) spectra of lignins from alfalfa stem with growth and development

Lignin is a poorly characterized polymer and its exact properties vary depending on both the species of the plant and its location within the plant. Three classes of lignins taken from alfalfa stem were examined. The investigation was concentrated on the determination of chemical changes in the lignins during growth and development by the attenuated total reflectance (ATR) infrared (IR) spectrometric technique. The spectrum of permanganate lignin was comparable to that of acid detergent lignin. The main differences were in the different relative absorbance of the peaks. The predominant component of acid detergent lignin and permanganate lignin was guaiacyl-type lignin. The predominant component of Klason lignin was syringyl-type lignin. A comparison between the signals from lignin in different development stages revealed the appearance of new peaks, which are indications of new bonds and changes in the structure of the lignins.

The oxidative destruction of lignin in the ozonation of wood

The oxidative destruction of lignin in the ozonation of aspen wood was studied. The kinetic curves of ozone consumption for samples with different contents of water were obtained. The consumption of ozone increased as the content of water grew. The second derivatives of the UV absorption spectra of lignin were obtained to show that the principal direction of lignin transformations under the action of ozone was the destruction of its aromatic constituents with the formation of carboxyl- and carbonyl-containing compounds. Measurements of the UV diffuse reflectance and EPR spectra of wood showed that the ozonation of wood caused the destruction of lignin quinoid structures. Part of lignin remained unchanged under the action of ozone. A key role in the destruction of wood lignin was played by ozone dissolved in water. Varying the content of water in wood samples allows various lignin transformation products to be obtained through ozonation.