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Sample records for nonphenolic lignin structures

  1. Manganese-dependent cleavage of nonphenolic lignin structures by Ceriporiopsis subvermispora in the absence of lignin peroxidase

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, K.A. Jr.; Bao, W.; Kawai, S. [USDA Forest Products Lab., Madison, WI (United States)] [and others

    1996-10-01

    Many ligninolytic fungi appear to lack lignin peroxidase (LiP), the enzyme generally thought to cleave nonphenolic structures in lignin. However, the fungus, Ceriporiopsis subvermispora, is able to degrade these nonphenolic structures. Experiments showed wood block cultures and defined liquid medium cultures of C. subvermispora rapidly deploymerized and mineralized a {sup 14}C-labeled, polyethylene glycol-linked, high-molecular-weight {beta}-O-4 lignin model compound (model I) that represents the major nonphenolic structure of lignin. The fungus cleaved model I between C{sub {alpha}} and C{sub {beta}} to release benzylic fragments, which were shown in isotope trapping experiments to be major products of model I metabolism. The C{sub {alpha}}-C{sub {beta}} cleavage of {beta}-O-4 lignin structures to release benzylic fragments is characteristic of LiP catalysis, but no detectable LiP activity. Three results pointed, instead, to the participation of a different enzyme, manganese peroxidase (MnP), in the degradation of nonphenolic lignin structures by C. subvermispora. (1) The degradation of model I and of exhaustively methylated (nonphenolic), {sup 14}C-labeled, synthetic lignin by the fungus in liquid cultures was almost completely inhibited when the Mn concentration of the medium was decreased from 35 {mu}M to approximately 5 {mu}M. (2) The fungus degraded model I and methylated lignin significantly faster in the presence of Tween 80, a source of unsaturated fatty acids, than it did in the presence of Tween 20, which contains only saturated fatty acids. Previous work has shown that nonphenolic lignin structures are degraded during the MnP-mediated peroxidation of unsaturated lipids. (3) In experiments with MnP, Mn(II), and unsaturated lipid in vitro, this system mimicked intact C. subvermispora cultures in that it cleaved nonphenolic {beta}-O-4 lignin model compounds between C{sub {alpha}} and C{sub {beta}} to release a benzylic fragment. 41 refs., 7 figs., 2 tabs.

  2. Oxidizability of unsaturated fatty acids and of a non-phenolic lignin structure in the manganese peroxidase-dependent lipid peroxidation system

    Science.gov (United States)

    Alexander N. Kapich; Tatyana V. Korneichik; Annele Hatakka; Kenneth E. Hammel

    2010-01-01

    Unsaturated fatty acids have been proposed to mediate the oxidation of recalcitrant, non-phenolic lignin structures by fungal manganese peroxidases (MnP), but their precise role remains unknown. We investigated the oxidizability of three fatty acids with varying degrees of polyunsaturation (linoleic, linolenic, and arachidonic acids) by measuring conjugated dienes...

  3. Unravelling lignin formation and structure

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, N.G. (Washington State Univ., Pullman, WA (United States). Inst. of Biological Chemistry)

    1991-01-01

    During this study, we established that the Fagaceae exclusively accumulate Z-monolignois/glucosides, and not the E-isomers. Evidence for the presence of a novel E{yields}Z isomerse has been obtained. Our pioneering work in lignin biosynthesis and structure in situ has also progressed smoothly. We established the bonding environments of a woody angiosperm, Leucanea leucocephala, as well as wheat (T. aestivum) and tobacco (N. tabacum). A cell culture system from Pinus taeda was developed which seems ideal for investigating the early stages of lignification. These cultures excrete peroxidase isozymes, considered to be specifically involved in lignin deposition. We also studied the effect of the putative lignin-degrading enzyme, lignin peroxidase, on monolignols and dehydropolymerisates therefrom. In all cases, polymerization was observed, and not degradation; these polymers are identical to that obtained with horseradish peroxidases/H{sub 2}O{sub 2}. It seems inconceivable that these enzymes can be considered as being primarily responsible for lignin biodegradation.

  4. Structural elucidation of inhomogeneous lignins from bamboo.

    Science.gov (United States)

    Wen, Jia-Long; Sun, Shao-Long; Xue, Bai-Liang; Sun, Run-Cang

    2015-01-01

    A better understanding of the inhomogeneous molecular structure of lignin from bamboo is a prerequisite for promoting the "biorefinery" technologies of the bamboo feedstock. A mild and successive method for fractionating native lignin from bamboo species was proposed in the present study. The molecular structure and structural inhomogeneity of the isolated lignin polymers were comprehensively investigated by elemental analysis, carbohydrate analysis, state-of-the-art NMR and analytical pyrolysis techniques (quantitative (13)C NMR, (13)C-DEPT 135 NMR, 2D-HSQC NMR, (31)P NMR, and pyrolysis-GC-MS). The results showed that the proposed method is effective for extracting lignin from bamboo. NMR results showed that syringyl (S) was the predominant unit in bamboo lignin over guaiacyl (G) and p-hydroxyphenyl (H) units. In addition, the lignin was associated with p-coumarates and ferulates via ester and ether bonds, respectively. Moreover, various substructures, such as β-O-4, β-β, β-5, β-1, and α,β-diaryl ether linkages, were identified and quantified by NMR techniques. Based on the results obtained, a proposed schematic diagram of structural heterogeneity of the lignin polymers extracted from the bamboo is presented. In short, well-defined inhomogeneous structures of native lignin from bamboo will facilitate further applications of bamboo in current biorefineries.

  5. Lignin degradation by a white-rot fungus lacking lignin peroxidase and manganese peroxidase

    Energy Technology Data Exchange (ETDEWEB)

    Eggert, C.B.; Eriksson, K.E.L. [Univ. of Georgia, Athens, GA (United States)

    1996-10-01

    Phanerochaete chrysosporium has been the organism of choice for studies of lignin degradation and much of this work has focused on two phenol oxidases, lignin peroxidase (LiP) and manganese peroxidase (MnP), secreted by the fungus under ligninolytic conditions. However, many white-rot fungi, including a number of aggressive lignin degraders, seem to operate without expressing LiP activity. Laccase is another phenol oxidase that white-rot fungi often produce. However, the role played by laccase in lignin degradation has remained obscured since its low redox potential appeared to make it incapable of oxidizing non-phenolic lignin constituents. We have identified, Pychnoporus cinnabarinus lacking both LiP and MnP, but a high producer of laccase, to degrade lignin as efficiently as UP producing fungi. We have found that P. cinnabarinus, to overcome the redox potential barrier for laccase, produces a mediator for oxidation of non-phenolic lignin structures. This is the first description of how laccase may be used in a biological system for the degradation of lignin.

  6. Oxidation of wheat straw lignin by fungal lignin peroxidase, manganese peroxidase and laccase: A comparative study

    Energy Technology Data Exchange (ETDEWEB)

    Martinez-Ingo, M.J.; Kurek, B. [Laboratorie de Chimie Biologique, Thiverval-Grignon (France)

    1996-10-01

    Lignin peroxidase (LiP), manganese peroxidase (MnP) from Phanerochaete chrysosporium and laccase from Pleurotus eryngii were separately used to degrade alkali wheat straw lignin (AL). In order to characterize the catalytic action of the different enzymes, the chemical structure and the hydrodynamic properties of the treated lignin were analyzed by thioacidolysis-gas chromatography and molecular size exclusion chromatography. The results confirmed that only LiP was able to degrade guiacyl (G) and syringyl (S) structures in non-phenolic methylated lignins. However, provided that some phenolic terminal structures are present, MnP and laccase were able to degrade the non-phenolic portion of the polymer linked by {beta}-O-4 alkyl aryl ether bonds. This suggested that the oxidative reactions catalyzed in alkali straw lignin could progress through bond cleavages generating phenoxy radicals. The molecular size distribution of both thioacidolysis products and the oxidized polymer showed that AL underwent condensation side-reactions regardless of the enzyme treatment, but only LiP oxidation led to the increase in the hydrodynamic volume of the recovered lignin. This indicated that modification of enzymes by bonding patterns in lignin is not always associated with alterations in the spatial network of the polymer.

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

    Science.gov (United States)

    Guo, Haiwei; Zhang, Bo; Qi, Zaojuan; Li, Changzhi; Ji, Jianwei; Dai, Tao; Wang, Aiqin; Zhang, Tao

    2017-02-08

    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. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Insights into lignin degradation and its potential industrial applications.

    Science.gov (United States)

    Abdel-Hamid, Ahmed M; Solbiati, Jose O; Cann, Isaac K O

    2013-01-01

    Lignocellulose is an abundant biomass that provides an alternative source for the production of renewable fuels and chemicals. The depolymerization of the carbohydrate polymers in lignocellulosic biomass is hindered by lignin, which is recalcitrant to chemical and biological degradation due to its complex chemical structure and linkage heterogeneity. The role of fungi in delignification due to the production of extracellular oxidative enzymes has been studied more extensively than that of bacteria. The two major groups of enzymes that are involved in lignin degradation are heme peroxidases and laccases. Lignin-degrading peroxidases include lignin peroxidase (LiP), manganese peroxidase (MnP), versatile peroxidase (VP), and dye-decolorizing peroxidase (DyP). LiP, MnP, and VP are class II extracellular fungal peroxidases that belong to the plant and microbial peroxidases superfamily. LiPs are strong oxidants with high-redox potential that oxidize the major non-phenolic structures of lignin. MnP is an Mn-dependent enzyme that catalyzes the oxidation of various phenolic substrates but is not capable of oxidizing the more recalcitrant non-phenolic lignin. VP enzymes combine the catalytic activities of both MnP and LiP and are able to oxidize Mn(2+) like MnP, and non-phenolic compounds like LiP. DyPs occur in both fungi and bacteria and are members of a new superfamily of heme peroxidases called DyPs. DyP enzymes oxidize high-redox potential anthraquinone dyes and were recently reported to oxidize lignin model compounds. The second major group of lignin-degrading enzymes, laccases, are found in plants, fungi, and bacteria and belong to the multicopper oxidase superfamily. They catalyze a one-electron oxidation with the concomitant four-electron reduction of molecular oxygen to water. Fungal laccases can oxidize phenolic lignin model compounds and have higher redox potential than bacterial laccases. In the presence of redox mediators, fungal laccases can oxidize non-phenolic

  9. Identification of the primary mechanism for fungal lignin degradation. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-06-01

    Many lignin-degrading fungi appear to lack lignin peroxidase (LiP), an enzyme generally thought important for fungal ligninolysis. The authors are working with one of these fungi, Ceriporiopsis subvermispora, an aggressive white-rotter that selectively removes lignin from wood. During this project period, they have obtained the following principal results: new polymeric lignin model compounds were developed to assist in the elucidation of fungal ligninolytic mechanisms; experiments with one of the polymeric lignin models showed that C. subvermispora cultures which express no detectable LiP activity are nevertheless able to degrade nonphenolic lignin structures, this result is significant because LiPs were previously considered essential for fungal attack on these recalcitrant structures, which constitute about 90% of lignin; manganese peroxidases (MnPs), which C. subvermispora does produce, catalyze the peroxidation of unsaturated fatty acids to give fatty acid hydroperoxides, fatty acid hydroperoxides are also used by MnP as oxidants (in place of H{sub 2}O{sub 2}) that support the MnP catalytic cycle, these results indicate that MnP turnover in the presence of unsaturated lipids generates reactive lipid oxyradicals that could act as oxidant of other molecules; MnP-mediated lipid peroxidation results in the co-oxidative cleavage of nonphenolic lignin structures, the MnP/lipid peroxidation system may therefore provide C. subvermispora and other LiP-negative fungi with a mechanism to degrade the principal structures of lignin.

  10. Genetics and chemistry of lignin degradation by Streptomyces

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, D.L.

    1992-01-01

    Our research goal was to define the involvement of lignin peroxidases and other extracellular enzymes in lignin degradation by Streptomyces. We examined the biochemistry and genetics of lignin degrading enzyme production by several strains of Streptomyces. The lignin peroxidase ALiP-P3 of S. viridosporus was characterized kinetically and its activity optimized for oxidation of 2,4-dichlorophenol and vanillyl-acetone. Sensitive spectrophotometric assays were developed for monitoring oxidation of these substrates. ALiP-P3 reaction chemistry was examined using both spectrophotometric assays and gas chromatography/mass spectroscopy. Results showed that the enzyme oxidizes phenolic lignin substructure models in strong preference to nonphenolic ones. The peroxidase was also shown to depolymerize native lignin. We also cloned the ALip-P3 gene S. lividans in plasmid vector pIJ702. The cloned gene was partially sequenced, We also immunologically characterized the lignin peroxidase of S. viridosporus T7A and showed it to be structurally related to peroxidases produced by other lignin-solubilizing Streptomyces, but not the the H8 lignin peroxidase of P. chrysosporium. Studies with peroxidase deficient mutants of strain T7A showed that lignin peroxidases of S. viridosporus are directly involved in the solubilization of lignin. Additional research showed that other enzymes are also probably involved in lignin solubilization, possibly including extracellular esterases.

  11. Method of producing prepolymers from hydroxyalkyl lignin derivatives

    OpenAIRE

    1990-01-01

    A method of producing prepolymeric materials from lignin is disclosed. The method uses lignin which has been hydroxyalkyl modified, such that the lignin is substantially non-phenolic and solvent soluble and/or liquid. The modified lignin is reacted with materials which yield prepolymers which may be polymerized according to known methods to produce useful polymers.

  12. Microbial degradation of lignin: how a bulky recalcitrant polymer is efficiently recycled in nature and how we can take advantage of this

    National Research Council Canada - National Science Library

    Ruiz-Dueñas, Francisco J; Martínez, Angel T

    2009-01-01

    .... The lignin polymer is highly recalcitrant towards chemical and biological degradation due to its molecular architecture, where different non-phenolic phenylpropanoid units form a complex three...

  13. New insights into the structure and composition of technical lignins: a comparative characterisation study

    NARCIS (Netherlands)

    Constant, Sandra; Wienk, Hans L.J.; Frissen, A.E.; Peinder, de Peter; Boelens, Rolf; Es, van D.S.; Grisel, Ruud J.H.; Weckhuysen, Bert M.; Huijgen, W.J.J.; Gosselink, R.J.A.; Bruijnincx, Pieter C.A.

    2016-01-01

    Detailed insight into the structure and composition of industrial (technical) lignins is needed to deviseefficient thermal, bio- or chemocatalytic valorisation strategies. Six such technical lignins covering threemain industrial pulping methods (Indulin AT Kraft, Protobind 1000 soda lignin and

  14. New insights into the structure and composition of technical lignins : A comparative characterisation study

    NARCIS (Netherlands)

    Constant, Sandra|info:eu-repo/dai/nl/374650519; Wienk, Hans L J|info:eu-repo/dai/nl/203884884; Frissen, Augustinus E.; Peinder, Peter De|info:eu-repo/dai/nl/325810818; Boelens, Rolf|info:eu-repo/dai/nl/070151407; Van Es, Daan S.; Grisel, Ruud J H; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397; Huijgen, Wouter J J; Gosselink, Richard J A; Bruijnincx, Pieter C A|info:eu-repo/dai/nl/33799529X

    2016-01-01

    Detailed insight into the structure and composition of industrial (technical) lignins is needed to devise efficient thermal, bio- or chemocatalytic valorisation strategies. Six such technical lignins covering three main industrial pulping methods (Indulin AT Kraft, Protobind 1000 soda lignin and

  15. New insights into the structure and composition of technical lignins: a comparative characterisation study

    NARCIS (Netherlands)

    Constant, Sandra; Wienk, Hans L.J.; Frissen, A.E.; Peinder, de Peter; Boelens, Rolf; Es, van D.S.; Grisel, Ruud J.H.; Weckhuysen, Bert M.; Huijgen, W.J.J.; Gosselink, R.J.A.; Bruijnincx, Pieter C.A.

    2016-01-01

    Detailed insight into the structure and composition of industrial (technical) lignins is needed to deviseefficient thermal, bio- or chemocatalytic valorisation strategies. Six such technical lignins covering threemain industrial pulping methods (Indulin AT Kraft, Protobind 1000 soda lignin and Alcel

  16. Genetics and chemistry of lignin degradation by Streptomyces. Final technical report

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, D.L.

    1992-12-31

    Our research goal was to define the involvement of lignin peroxidases and other extracellular enzymes in lignin degradation by Streptomyces. We examined the biochemistry and genetics of lignin degrading enzyme production by several strains of Streptomyces. The lignin peroxidase ALiP-P3 of S. viridosporus was characterized kinetically and its activity optimized for oxidation of 2,4-dichlorophenol and vanillyl-acetone. Sensitive spectrophotometric assays were developed for monitoring oxidation of these substrates. ALiP-P3 reaction chemistry was examined using both spectrophotometric assays and gas chromatography/mass spectroscopy. Results showed that the enzyme oxidizes phenolic lignin substructure models in strong preference to nonphenolic ones. The peroxidase was also shown to depolymerize native lignin. We also cloned the ALip-P3 gene S. lividans in plasmid vector pIJ702. The cloned gene was partially sequenced, We also immunologically characterized the lignin peroxidase of S. viridosporus T7A and showed it to be structurally related to peroxidases produced by other lignin-solubilizing Streptomyces, but not the the H8 lignin peroxidase of P. chrysosporium. Studies with peroxidase deficient mutants of strain T7A showed that lignin peroxidases of S. viridosporus are directly involved in the solubilization of lignin. Additional research showed that other enzymes are also probably involved in lignin solubilization, possibly including extracellular esterases.

  17. Industrial Utilization of Lignin Based on its Structure and Capability

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Chemical modification and industrial utilization of lignin based on its structure were reviewed in this paper. And its economic value and significance for the society and environmental protection were also evaluated.

  18. Calculation of IR-spectra of structural fragments of lignins

    Science.gov (United States)

    Derkacheva, O. Yu.; Ishankhodzhaeva, M. M.

    2016-12-01

    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.

  19. Structural characterization of the lignin from jute (Corchorus capsularis) fibers.

    Science.gov (United States)

    del Río, José C; Rencoret, Jorge; Marques, Gisela; Li, Jiebing; Gellerstedt, Göran; Jiménez-Barbero, Jesús; Martínez, Angel T; Gutiérrez, Ana

    2009-11-11

    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.

  20. Structural characterization of lignin from triploid of Populus tomentosa Carr.

    Science.gov (United States)

    Yuan, Tong-Qi; Sun, Shao-Ni; Xu, Feng; Sun, Run-Cang

    2011-06-22

    To improve yields while minimizing the extent of mechanical action (just 2 h of planetary ball-milling), the residual wood meal obtained from extraction of milled wood lignin (MWL) was sequentially treated with cellulolytic enzyme and alkali, and the yields of MWL, cellulolytic enzyme lignin (CEL), and alkaline lignin (AL) were 5.4, 23.2, and 16.3%, respectively. The chemical structures of the lignin fractions obtained were characterized by carbohydrate analysis, gel permeation chromatography (GPC), Fourier transform infrared (FT-IR) spectroscopy, and various advanced NMR spectroscopic techniques. The results showed that the lignin isolated as MWL during the early part of ball milling may originate mainly from the middle lamella. This lignin fraction was less degradable and contained more linear hemicelluloses and more C═O in unconjugated groups as well as more phenolic OH groups. Both 1D and 2D NMR spectra analyses confirmed that the lignin in triploid of Populus tomentosa Carr. is GSH-type and partially acylated at the γ-carbon of the side chain. Two-dimensional heteronuclear single-quantum coherence (¹³C-¹H) NMR of MWL, CEL, and AL showed a predominance of β-O-4' aryl ether linkages (81.1-84.5% of total side chains), followed by β-β' resinol-type linkages (12.2-16.4%), and lower amounts of β-5' phenylcoumaran (2.1-2.6%) and β-1' spirodienone-type (0.4-1.4%) linkages. The syringyl (S)/guaiacyl (G) ratios were estimated to be 1.43, 2.29, and 2.83 for MWL, CEL, and AL, respectively.

  1. The dual effects of lignin content on enzymatic hydrolysis using film composed of cellulose and lignin as a structure model.

    Science.gov (United States)

    Zhang, Lu; Zhang, Liming; Zhou, Tian; Wu, Yuying; Xu, Feng

    2016-01-01

    The degree of delignification during pretreatment is a critical question for economic conversion of biomass to sugar platform. Many models have been used to study the optimum lignin content in biomass, but few of them are able to study without disturbances, such as the complex component and structure of biomass. A novel film model composed of only cellulose and lignin was used to investigate the effect of lignin on enzymatic hydrolysis. High lignin-cellulose proportion (10.00-31.25%) hindered enzymatic hydrolysis, whereas low lignin-cellulose proportion (2.00-8.00%) showed a notable potential to promote enzymatic hydrolysis. The enzymatic hydrolysis rate of lignin-cellulose (6.00%) film was 11.5% higher than that of pure cellulose films. Further study indicated that the promotion was due to the enhancement of film porosity and roughness by residual lignin. Thus, based on the biomimetic model, excessive delignification is not recommended in view of efficient conversion and economy. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Utilization of lignin

    Energy Technology Data Exchange (ETDEWEB)

    Machihara, A.

    1981-01-01

    The chemical structure of lignin, the composition of pulping spent liquors, conversion of lignin into fine chemicals, utilization of lignin products, and physical and chemical properties of lignin and and derivatives are reviewed. (Refs 29).

  3. Engineering a fungal peroxidase that degrades lignin at very acidic pH

    NARCIS (Netherlands)

    Fernandez-Fueyo, E.; Ruiz-Duenas, F.J.; Martinez, A.T.

    2014-01-01

    Background Ligninolytic peroxidases are divided into three families: manganese peroxidases (MnPs), lignin peroxidases (LiPs), and versatile peroxidases (VPs). The latter two are able to degrade intact lignins, as shown using nonphenolic lignin model compounds, with VP oxidizing the widest range of r

  4. Engineering a fungal peroxidase that degrades lignin at very acidic pH

    NARCIS (Netherlands)

    Fernandez-Fueyo, E.; Ruiz-Duenas, F.J.; Martinez, A.T.

    2014-01-01

    Background Ligninolytic peroxidases are divided into three families: manganese peroxidases (MnPs), lignin peroxidases (LiPs), and versatile peroxidases (VPs). The latter two are able to degrade intact lignins, as shown using nonphenolic lignin model compounds, with VP oxidizing the widest range of

  5. Lignin Composition and Structure Differs between Xylem, Phloem and Phellem in Quercus suber L.

    Science.gov (United States)

    Lourenço, Ana; Rencoret, Jorge; Chemetova, Catarina; Gominho, Jorge; Gutiérrez, Ana; del Río, José C.; Pereira, Helena

    2016-01-01

    The composition and structure of lignin in different tissues—phellem (cork), phloem and xylem (wood)—of Quercus suber was studied. Whole cell walls and their respective isolated milled lignins were analyzed by pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS), two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR) and derivatization followed by reductive cleavage (DFRC). Different tissues presented varied p-hydroxyphenyl:guaiacyl:syringyl (H:G:S) lignin compositions. Whereas lignin from cork has a G-rich lignin (H:G:S molar ratio 2:85:13), lignin from phloem presents more S-units (H:G:S molar ratio of 1:58:41) and lignin from xylem is slightly enriched in S-lignin (H:G:S molar ratio 1:45:55). These differences were reflected in the relative abundances of the different interunit linkages. Alkyl-aryl ethers (β–O–4′) were predominant, increasing from 68% in cork, to 71% in phloem and 77% in xylem, as consequence of the enrichment in S-lignin units. Cork lignin was enriched in condensed structures such as phenylcoumarans (β-5′, 20%), dibenzodioxocins (5–5′, 5%), as corresponds to a lignin enriched in G-units. In comparison, lignin from phloem and xylem presented lower levels of condensed linkages. The lignin from cork was highly acetylated at the γ-OH of the side-chain (48% lignin acetylation), predominantly over G-units; while the lignins from phloem and xylem were barely acetylated and this occurred mainly over S-units. These results are a first time overview of the lignin structure in xylem, phloem (generated by cambium), and in cork (generated by phellogen), in agreement with literature that reports that lignin biosynthesis is flexible and cell specific. PMID:27833631

  6. Lignin Composition and Structure Differs between Xylem, Phloem and Phellem in Quercus suber L.

    Science.gov (United States)

    Lourenço, Ana; Rencoret, Jorge; Chemetova, Catarina; Gominho, Jorge; Gutiérrez, Ana; Del Río, José C; Pereira, Helena

    2016-01-01

    The composition and structure of lignin in different tissues-phellem (cork), phloem and xylem (wood)-of Quercus suber was studied. Whole cell walls and their respective isolated milled lignins were analyzed by pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS), two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR) and derivatization followed by reductive cleavage (DFRC). Different tissues presented varied p-hydroxyphenyl:guaiacyl:syringyl (H:G:S) lignin compositions. Whereas lignin from cork has a G-rich lignin (H:G:S molar ratio 2:85:13), lignin from phloem presents more S-units (H:G:S molar ratio of 1:58:41) and lignin from xylem is slightly enriched in S-lignin (H:G:S molar ratio 1:45:55). These differences were reflected in the relative abundances of the different interunit linkages. Alkyl-aryl ethers (β-O-4') were predominant, increasing from 68% in cork, to 71% in phloem and 77% in xylem, as consequence of the enrichment in S-lignin units. Cork lignin was enriched in condensed structures such as phenylcoumarans (β-5', 20%), dibenzodioxocins (5-5', 5%), as corresponds to a lignin enriched in G-units. In comparison, lignin from phloem and xylem presented lower levels of condensed linkages. The lignin from cork was highly acetylated at the γ-OH of the side-chain (48% lignin acetylation), predominantly over G-units; while the lignins from phloem and xylem were barely acetylated and this occurred mainly over S-units. These results are a first time overview of the lignin structure in xylem, phloem (generated by cambium), and in cork (generated by phellogen), in agreement with literature that reports that lignin biosynthesis is flexible and cell specific.

  7. Lignin composition and structure differs between xylem, phloem and phellem in Quercus suber L.

    Directory of Open Access Journals (Sweden)

    Ana Lourenço

    2016-10-01

    Full Text Available The composition and structure of lignin in different tissues - phellem (cork, phloem and xylem (wood - of Quercus suber was studied. Whole cell walls and their respective isolated milled lignins were analyzed by pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS, two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR and derivatization followed by reductive cleavage (DFRC. Different tissues presented varied p-hydroxyphenyl:guaiacyl:syringyl (H:G:S lignin compositions. Whereas lignin from cork has a G-rich lignin (H:G:S molar ratio 2:85:13, lignin from phloem presents more S-units (H:G:S molar ratio of 1:58:41 and lignin from xylem is slightly enriched in S-lignin (H:G:S molar ratio 1:45:55. These differences were reflected in the relative abundances of the different interunit linkages. Alkyl-aryl ethers (β–O–4´ were predominant, increasing from 68% in cork, to 71% in phloem and 77% in xylem, as consequence of the enrichment in S-lignin units. Cork lignin was enriched in condensed structures such as phenylcoumarans (β-5´, 20%, dibenzodioxocins (5-5´, 5%, as corresponds to a lignin enriched in G-units. In comparison, lignin from phloem and xylem presented lower levels of condensed linkages. The lignin from cork was highly acetylated at the γ-OH of the side-chain (48% lignin acetylation, predominantly over G-units; while the lignins from phloem and xylem were barely acetylated and this occurred mainly over S-units. These results are a first time overview of the lignin structure in xylem, phloem (generated by cambium, and in cork (generated by phellogen, in agreement with literature that lignin biosynthesis is flexible and cell specific.

  8. Mini-review: Current Understanding of the Correlation of Lignin Structure with Biomass Recalcitrance

    Science.gov (United States)

    Li, Mi; Pu, Yunqiao; Ragauskas, Arthur

    2016-11-01

    Lignin, a complex aromatic polymer in terrestrial plants, contributes significantly to biomass recalcitrance to microbial and/or enzymatic deconstruction. To reduce biomass recalcitrance, substantial endeavors have been exerted on pretreatment and lignin engineering in the past few decades. Lignin removal and/or alteration of lignin structure have been shown to result in reduced biomass recalcitrance with improved cell wall digestibility. While high lignin content is usually a barrier to a cost-efficient application of bioresource to biofuels, the direct correlation of lignin structure and its concomitant properties with biomass remains unclear due to the complexity of cell wall and lignin structure. Advancement in application of biorefinery to production of biofuels, chemicals, and biomaterials necessitates a fundamental understanding of the relationship of lignin structure and biomass recalcitrance. In this mini-review, we focus on recent investigations on the influence of lignin chemical properties on bioprocessability— pretreatment and enzymatic hydrolysis of biomass. Specifically, lignin-enzyme interaction and the effects of lignin compositional units, hydroxycinnamates, and lignin functional groups on biomass recalcitrance have been highlighted, which will be useful not only in addressing biomass recalcitrance but also in deploying renewable lignocelluloses efficiently.

  9. New insights into the structure and composition of technical lignins : A comparative characterisation study

    NARCIS (Netherlands)

    Constant, Sandra; Wienk, Hans L J; Frissen, Augustinus E.; Peinder, Peter De; Boelens, Rolf; Van Es, Daan S.; Grisel, Ruud J H; Weckhuysen, Bert M.; Huijgen, Wouter J J; Gosselink, Richard J A; Bruijnincx, Pieter C A

    2016-01-01

    Detailed insight into the structure and composition of industrial (technical) lignins is needed to devise efficient thermal, bio- or chemocatalytic valorisation strategies. Six such technical lignins covering three main industrial pulping methods (Indulin AT Kraft, Protobind 1000 soda lignin and Alc

  10. Multiphase materials with lignin. VI. Effect of cellulose derivative structure on blend morphology with lignin

    Science.gov (United States)

    Timothy G. Rials; Wolfgang G. Glasser

    1989-01-01

    Polymeric blends of lignin with ethyl cellulose (EC) and cellulose acetate/butyrate (CAB) prepared by solution casting from dioxane. Fracture surface analysis by scanning electron microscopy revealed phase separation when the lignin content exceeded 10% for blends with EC and 5% in the CAB system. While this phase behavior is as predicted for the EC blends, a greater...

  11. Investigation of structural modification and thermal characteristics of lignin after heat treatment.

    Science.gov (United States)

    Kim, Jae-Young; Hwang, Hyewon; Oh, Shinyoung; Kim, Yong-Sik; Kim, Ung-Jin; Choi, Joon Weon

    2014-05-01

    Milled wood lignin was subjected to heat treatment between 150 and 300°C to understand the pattern of its structural modification and thermal properties. When the temperature was elevated with interval of 50°C, the color of the lignin became dark brown and the lignin released various forms of phenols from terminal phenolic groups in the lignin, leading to two physical phenomena: (1) gradual weight loss of the lignin, up to 19% based on dry weight and (2) increase in the carbon content and decrease in the oxygen content. Nitrobenzene oxidation and (13)C NMR analyses confirmed a cleavage of β-O-4 linkage (depolymerization) and reduction of methoxyl as well as phenolic hydroxyl group were also characteristic in the lignin structure during heat treatment. Simultaneously with lignin depolymerization, GPC analysis provided a possibility that condensation between lignin fragments could also occur during heat treatment. TGA/DTG/DSC data revealed that thermal stability of lignin obviously increased after heat treatment, implicating the structural rearrangement of lignin to reduction of β-O-4 linkage as well as accumulation of CC bonds.

  12. Structural variation of bamboo lignin before and after ethanol organosolv pretreatment.

    Science.gov (United States)

    Bai, Yuan-Yuan; Xiao, Ling-Ping; Shi, Zheng-Jun; Sun, Run-Cang

    2013-10-28

    In order to make better use of lignocellulosic biomass for the production of renewable fuels and chemicals, it is necessary to disrupt its recalcitrant structure through pretreatment. Specifically, organosolv pretreatment is a feasible method. The main advantage of this method compared to other lignocellulosic pretreatment technologies is the extraction of high-quality lignin for the production of value-added products. In this study, bamboo was treated in a batch reactor with 70% ethanol at 180 °C for 2 h. Lignin fractions were isolated from the hydrolysate by centrifugation and then precipitated as ethanol organosolv lignin. Two types of milled wood lignins (MWLs) were isolated from the raw bamboo and the organosolv pretreated residue separately. After the pretreatment, a decrease of lignin (preferentially guaiacyl unit), hemicelluloses and less ordered cellulose was detected in the bamboo material. It was confirmed that the bamboo MWL is of HGS type (p-hydroxyphenyl (H), vanillin (G), syringaldehyde (S)) associated with a considerable amount of p-coumarate and ferulic esters of lignin. The ethanol organosolv treatment was shown to remove significant amounts of lignin and hemicelluloses without strongly affecting lignin primary structure and its lignin functional groups.

  13. Effect of mechanical activation on structure changes and reactivity in further chemical modification of lignin.

    Science.gov (United States)

    Zhao, Xiaohong; Zhang, Yanjuan; Hu, Huayu; Huang, Zuqiang; Yang, Mei; Chen, Dong; Huang, Kai; Huang, Aimin; Qin, Xingzhen; Feng, Zhenfei

    2016-10-01

    Lignin was treated by mechanical activation (MA) in a customized stirring ball mill, and the structure and reactivity in further esterification were studied. The chemical structure and morphology of MA-treated lignin and the esterified products were analyzed by chemical analysis combined with UV/vis spectrometer, FTIR,NMR, SEM and particle size analyzer. The results showed that MA contributed to the increase of aliphatic hydroxyl, phenolic hydroxyl, carbonyl and carboxyl groups but the decrease of methoxyl groups. Moreover, MA led to the decrease of particle size and the increase of specific surface area and roughness of surface in lignin. The reactivity of lignin was enhanced significantly for the increase of hydroxyl content and the improvement of mass transfer in chemical reaction caused by the changes of molecular structure and morphological structure. The process of MA is green and simple, and is an effective method for enhancing the reactivity of lignin. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Structural Analysis of Novel Lignin-derived Carbon Composite Anodes

    Energy Technology Data Exchange (ETDEWEB)

    McNutt, Nicholas W [ORNL; Rios, Orlando [ORNL; Feygenson, Mikhail [ORNL; Proffen, Thomas E [ORNL; Keffer, David J [ORNL

    2014-01-01

    The development of novel lignin-based carbon composite anodes consisting of nanocrystalline and amorphous domains motivates the understanding of a relationship of the structural properties characterizing these materials, such as crystallite size, intracrystallite dspacing, crystalline volume fraction and composite density, with their pair distribution functions (PDF), obtained from both molecular dynamics simulation and neutron scattering. A model for these composite materials is developed as a function of experimentally measurable parameters and realized in fifteen composite systems, three of which directly match all parameters of their experimental counterparts. The accurate reproduction of the experimental PDFs using the model systems validates the model. The decomposition of the simulated PDFs provides an understanding of each feature in the PDF and allows for the development of a mapping between the defining characteristics of the PDF and the material properties of interest.

  15. The effect of non-structural components and lignin on hemicellulose extraction.

    Science.gov (United States)

    Liu, Kai-Xuan; Li, Hong-Qiang; Zhang, Jie; Zhang, Zhi-Guo; Xu, Jian

    2016-08-01

    As the important structural component of corn stover, hemicellulose could be converted into a variety of high value-added products. However, high quality hemicellulose extraction is not an easy issue. The present study aims to investigate the effects of non-structural components (NSCs) and lignin removal on alkaline extraction of hemicellulose. Although NSCs were found to have a minimal effect on hemicellulose dissolution, they affected the color values of the hemicellulose extracts. The lignin limited the hemicellulose dissolution and increased the color value by binding to hemicellulose molecules and forming lignin-carbohydrate complexes. Sodium chlorite method can remove about 90% lignin from corn stover, especially the lignin connected to hemicellulose through p-coumaric and ferulic acids. Which increased the hemicellulose dissolution ratio to 93% and reduced the color value 14-28%, but the cost is about 20% carbohydrates lost. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Structural modification of hemicelluloses and lignin based on the biorefinery process with white-rot fungal.

    Science.gov (United States)

    Ma, Jian-Feng; Yang, Hai-Yan; Kun, Wang; Liu, Xing-E

    2016-11-20

    On the concept of biorefinery, hemicellulosic and lignin fractions were isolated from white-rot fungal Trametes velutina D10149 biodegraded poplar, and the structural modification was elucidated in detail according to the different incubation duration. Transversal-section Raman images showed that the fiber secondary walls were preferentially degraded, whereas the compound middle lamellae, including the cell corner regions, were mainly intact after 16 weeks incubation. More importantly, lignin and carbohydrates were simultaneously removed within the fiber secondary wall. From wet chemistry analysis, the yields and structural properties for both hemicellulosic and lignin fractions were not significantly altered. The synergistic effect of ligninolytic system finally obviously appeared after 16 weeks incubation, evidenced by the remarkable decrement of hemicellulose and lignin molecular weights. Additionally, the preferential degradation of S units in lignin biomacromolecule was further confirmed by composition analysis of cell wall phenolics and the integration of 2D NMR correlations in the aromatic region. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Effect of hydrothermal pretreatment on the structural changes of alkaline ethanol lignin from wheat straw

    Science.gov (United States)

    Chen, Xue; Li, Hanyin; Sun, Shaoni; Cao, Xuefei; Sun, Runcang

    2016-12-01

    Due to the enormous abundance of lignin and its unique aromatic nature, lignin has great potential for the production of industrially useful fuels, chemicals, and materials. However, the rigid and compact structure of the plant cell walls significantly blocks the separation of lignin. In this study, wheat straw was hydrothermally pretreated at different temperatures (120–200 °C) followed by post-treatment with 70% ethanol containing 1% NaOH to improve the isolation of lignin. Results demonstrated that the content of associated carbohydrates of the lignin fractions was gradually reduced with the increment of the hydrothermal severity. The structure of the lignins changed regularly with the increase of the pretreatment temperature from 120 to 200 °C. In particular, the contents of β-O-4‧, β-β‧, β-5‧ linkages and aliphatic OH in the lignins showed a tendency of decrease, while the content of phenolic OH and thermal stability of the lignin fractions increased steadily as the increment of the pretreatment temperature.

  18. Structural modification of lignin and characterization of pretreated wheat straw by ozonation.

    Science.gov (United States)

    Bule, Mahesh V; Gao, Allan H; Hiscox, Bill; Chen, Shulin

    2013-04-24

    Ozonolysis is potentially an effective method for pretreating lignocellulosic biomass to improve the production of fermentable sugars via enzymatic hydrolysis. Further understanding of the ozonolysis process and identifying specific lignin structural changes are crucial for improving the pretreatment process. Investigation into pretreatment of wheat straw using ozonolysisis is reported in this paper, with special emphasis on selective modification/degradation of lignin subunits. The ozonolysis was performed for 2 h with less than 60 mesh particles in order to achieve maximum lignin oxidation. The results showed that the lignin structure was significantly modified under these conditions, leading to higher sugar recovery of more than 50% which increased from 13.11% to 63.17% corresponding to the control and ozone treated samples, respectively. Moisture content was found to be an important parameter for improving sugar recovery. Ninety percent (w/w) moisture produced the highest sugar recovery. The concentration of acid soluble lignin in the ozone treated sample increased from 4% to 11% after 2 h treatment. NMR analysis revealed that the S2/6 and G2 lignin units in the wheat straw were most prone to oxidation by ozone as the concentration of aromatic units decreased while the carboxylic acids became more abundant. The experimental data suggest the degradation of β-O-4 moieties and aromatic ring opening in lignin subunits. The pyrolysis-gas chromatography/mass spectrometry results revealed that the rate of lignin unit degradation was in the following order: syringyl > guaiacyl > p-hydroxyphenyl. Long ozone exposure resulted in few condensed lignin structure formation. In addition, the formation of condensed units during this process increased the activation energy from ASTM-E, 259.74 kJ/mol; Friedman-E, 270.08 kJ/mol to ASTM-E, 509.29 kJ/mol; Friedman-E, 462.17 kJ/mol. The results provide new information in overcoming lignin barrier for lignocellulose utilization.

  19. CHEMICAL STRUCTURE AND PYROLYSIS RESPONSE OF BETA-O-4 LIGNIN MODEL POLYMER

    Directory of Open Access Journals (Sweden)

    Jiang-Yan Liu

    2011-04-01

    Full Text Available Hydroxyphenyl (H-type and guaiacyl (G-type lignin model polymers composed of the β–O–4 structure without gamma–hydroxymethyl groups were synthesized. The chemical structures of the H- and G-type lignin models were characterized by 1H- and 13C-NMR, as well as MALDI-TOF/MS. The pyrolysis response was analyzed by means of TG-DTG, Py-GC/MS, and a tube furnace technique. 1H-, 13C-NMR, and MALDI-TOF/MS showed that the lignin models were linear polymers. The polymers included the β–O–4 linkage, as in natural lignin. Pyrolytic products from H-type lignin model only possessed p-hydroxyphenyl structure without methoxyl groups, and the pyrolytic products from G-type lignin model only possessed guaiacyl structure with methoxyl groups. Pyrolysis products from H- and G- type lignin models were classified into char, gas, and liquid (bio-oil, and the gaseous products of two model compounds mainly consisted of H2, CO, CH4, CO2, and C2H4.

  20. Lignin nanoparticle synthesis

    Science.gov (United States)

    Dirk, Shawn M.; Cicotte, Kirsten Nicole; Wheeler, David R.; Benko, David A.

    2015-08-11

    A method including reducing a particle size of lignin particles to an average particle size less than 40 nanometers; after reducing the particle size, combining the lignin particles with a polymeric material; and forming a structure of the combination. A method including exposing lignin to a diazonium precursor including a functional group; modifying the lignin by introducing the functional group to the lignin; and combining the modified lignin with a polymeric material to form a composite. An apparatus including a composite of a polymer and lignin wherein the lignin has an average particle size less than 100 micrometers.

  1. The Structure of Lignin of Corn Stover and its Changes Induced by Mild Sodium Hydroxide Treatment

    Directory of Open Access Journals (Sweden)

    Dou-yong Min

    2014-03-01

    Full Text Available Corn stover is an abundant feedstock in the US that can be used for second generation bioethanol production. However, there is little useful data on structure of the lignin of corn stover. The following principal tasks will be addressed to profile the structure of corn stover: (1 separation of corn stover into stem, cob, and leaf; (2 isolation of cellulolytic enzyme lignins (CEL from extractive-free and the alkali-treated fractions; (3 quantification of p-coumarate and ferulate of fractions by HPLC. The results of alkaline nitrobenzene oxidation and 1H-13C HSQC NMR indicated: (1 the structure of lignin varied in the fractions; (2 a remarkable amount of p-coumarate and ferulate was identified and determined; (3 the remarkable structural changes of lignin induced by alkaline treatment were elucidated.

  2. [Chemical structure of bioethanol lignin by low-temperature alkaline catalytic hydrothermal treatment].

    Science.gov (United States)

    Liu, Xiao-Huan; Zhang, Ming-Ming; Wang, Ji-Fu; Xu, Yu-Zhi; Wang, Chun-Peng; Chu, Fu-Xiang

    2013-11-01

    In order to improve the reaction activity of bioethanol lignin, we investigated the activation of bioethanol lignin by a hydrothermal treatment method. Catalytic hydrothermal treatment of bioethanol lignin was performed at 180 degrees C for 3 h in the presence of alkaline solutions (NaOH, Na2 CO3, KOH and K2 CO3), the change in bioethanol lignin structures was studied comparatively by FTIR, 1H NMR,GPC and elemental analysis. FTIR spectra showed that after alkali hydrothermal treatment, the band at 1 375 cm(-1) attributed to the phenolic hydroxyl groups increased, and the band intensity at 1 116 cm(-1) attributed to the ether bond decreased. On the other hand, the band at 1 597 and 1 511 cm(-1) attributed to aromatic skeletal vibration remained almost unchanged. 1H NMR spectra showed that after alkali hydrothermal treatment, the number of aromatic methoxyl is increased, and based on the increment of the content of phenolic hydroxyl, the catalytic activity can be ranked as follows: KOH > NaOH > K2 CO3 > Na2 CO3. Especially for KOH, the increment of the content of phenolic hydroxyl was 170%, because the ion radius of potassium cation is bigger than sodium cation, so the potassium cations more easily formed cation adducts with lignin. GPC results showed that the molecular weight of alkali hydrothermal treatment lignin decreased and the molecular distribution got wider. Elemental analysis showed that hydrothermal treatment could break the interlinkage between lignin and protein, which can reduce the protein content and increase the purity of lignin, meanwhile, the content of O and H both decreased,while C fell, indicating that the bioethanol lignin had suffered a decarbonylation reaction. This is the most benefit of the lignin as a substitute for phenol.

  3. LIGNIN, STRUCTURE AND APPLICATIONS: DEPOLYMERIZATION METHODS FOR OBTAINING AROMATIC DERIVATIVES OF INDUSTRIAL INTEREST

    Directory of Open Access Journals (Sweden)

    Marvin Chávez-Sifontes

    2013-12-01

    Full Text Available In this article significant data related to the structural characteristics of lignin, the extraction and isolation processes from biomass, and also the characteristics of different types of commercial lignins are presented. The review focuses on the different depolymerization processes (hydrolysis, hydrogenolysis, hydrodeoxygenation, pyrolysis, among others up to now developed and investigated analyzing the different aromatic derivatives obtained in each case, as well as the interesting reactions some of them may undergo. Application possibilities for lignin and its derivatives in new industrial processes integrated into the bio-refinery of the future are finally assessed

  4. Structural changes of corn stover lignin during acid pretreatment.

    Science.gov (United States)

    Moxley, Geoffrey; Gaspar, Armindo Ribeiro; Higgins, Don; Xu, Hui

    2012-09-01

    In this study, raw corn stover was subjected to dilute acid pretreatments over a range of severities under conditions similar to those identified by the National Renewable Energy Laboratory (NREL) in their techno-economic analysis of biochemical conversion of corn stover to ethanol. The pretreated corn stover then underwent enzymatic hydrolysis with yields above 70 % at moderate enzyme loading conditions. The enzyme exhausted lignin residues were characterized by ³¹P NMR spectroscopy and functional moieties quantified and correlated to enzymatic hydrolysis yields. Results from this study indicated that both xylan solubilization and lignin degradation are important for improving the enzyme accessibility and digestibility of dilute acid pretreated corn stover. At lower pretreatment temperatures, there is a good correlation between xylan solubilization and cellulose accessibility. At higher pretreatment temperatures, lignin degradation correlated better with cellulose accessibility, represented by the increase in phenolic groups. During acid pretreatment, the ratio of syringyl/guaiacyl functional groups also gradually changed from less than 1 to greater than 1 with the increase in pretreatment temperature. This implies that more syringyl units are released from lignin depolymerization of aryl ether linkages than guaiacyl units. The condensed phenolic units are also correlated with the increase in pretreatment temperature up to 180 °C, beyond which point condensation reactions may overtake the hydrolysis of aryl ether linkages as the dominant reactions of lignin, thus leading to decreased cellulose accessibility.

  5. Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes

    Science.gov (United States)

    2012-01-01

    lignin structures and compositions could be linked to quantifiable changes in the composition of the cell wall and properties of the lignin including apparent content of the p-hydroxycinnamates while the limitations of S/G estimation in grasses is highlighted. PMID:22672858

  6. Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes

    Directory of Open Access Journals (Sweden)

    Li Muyang

    2012-06-01

    exhibiting a diversity of lignin structures and compositions could be linked to quantifiable changes in the composition of the cell wall and properties of the lignin including apparent content of the p-hydroxycinnamates while the limitations of S/G estimation in grasses is highlighted.

  7. Structural elucidation of sorghum lignins from an integrated biorefinery process based on hydrothermal and alkaline treatments.

    Science.gov (United States)

    Sun, Shao-Long; Wen, Jia-Long; Ma, Ming-Guo; Sun, Run-Cang

    2014-08-13

    An integrated process based on hydrothermal pretreatment (HTP) (i.e., 110-230 °C, 0.5-2.0 h) and alkaline post-treatment (2% NaOH at 90 °C for 2.0 h) has been performed for the production of xylooligosaccharide, lignin, and digestible substrate from sweet sorghum stems. The yield, purity, dissociation mechanisms, structural features, and structural transformations of alkali lignins obtained from the integrated process were investigated. It was found that the HTP process facilitated the subsequent alkaline delignification, releasing lignin with the highest yield (79.3%) and purity from the HTP residue obtained at 190 °C for 0.5 h. All of the results indicated that the cleavage of the β-O-4 linkages and degradation of β-β and β-5 linkages occurred under the harsh HTP conditions. Depolymerization and condensation reactions simultaneously occurred at higher temperatures (≥ 170 °C). Moreover, the thermostability of lignin was positively related to its molecular weight, but was also affected by the inherent structures, such as β-O-4 linkages and condensed units. These findings will enhance the understanding of structural transformations of the lignins during the integrated process and maximize the potential utilizations of the lignins in a current biorefinery process.

  8. Phenolic mediators enhance the manganese peroxidase catalyzed oxidation of recalcitrant lignin model compounds and synthetic lignin.

    Science.gov (United States)

    Nousiainen, Paula; Kontro, Jussi; Manner, Helmiina; Hatakka, Annele; Sipilä, Jussi

    2014-11-01

    Fungal oxidative enzymes, such as peroxidases and laccases, are the key catalysts in lignin biodegradation in vivo, and consequently provide an important source for industrial ligninolytic biocatalysts. Recently, it has been shown that some syringyl-type phenolics have potential as industrial co-oxidants or mediators, in laccase-catalyzed modification of lignocellulosic material. We have now studied the effect of such mediators with ligninolytic peroxidases on oxidation of the most recalcitrant lignin model compounds. We found that they are able to enhance the manganese peroxidase (MnP) catalyzed oxidation reactions of small non-phenolic compounds, veratryl alcohol and veratrylglycerol β-guaiacyl ether (adlerol), which are not usually oxidized by manganese peroxidases alone. In these experiments we compared two peroxidases from white-rot fungi, MnP from Phlebia sp. Nf b19 and versatile peroxidase (VP) from Bjerkandera adusta under two oxidation conditions: (i) the Mn(III) initiated mediated oxidation by syringyl compounds and (ii) the system involving MnP-dependent lipid peroxidation, both with production of (hydrogen) peroxides in situ to maintain the peroxidase catalytic cycle. It was found that both peroxidases produced α-carbonyl oxidation product of veratryl alcohol in clearly higher yields in reactions mediated by phenoxy radicals than in lipid-peroxyl radical system. The oxidation of adlerol, on the other hand, was more efficient in lipid-peroxidation-system. VP was more efficient than MnP in the oxidation of veratryl alcohol and showed its lignin peroxidase type activity in the reaction conditions indicated by some cleavage of Cα-Cβ-bond of adlerol. Finally, the mediator assisted oxidation conditions were applied in the oxidation of synthetic lignin (DHP) and the structural analysis of the oxidized polymers showed clear modifications in the polymer outcome, e.g. the oxidation resulted in reduced amount of aliphatic hydroxyls indicated by (31)P NMR

  9. Novel seed coat lignins in the Cactaceae: structure, distribution and implications for the evolution of lignin diversity.

    Science.gov (United States)

    Chen, Fang; Tobimatsu, Yuki; Jackson, Lisa; Nakashima, Jin; Ralph, John; Dixon, Richard A

    2013-01-01

    We have recently described a hitherto unsuspected catechyl lignin polymer (C-lignin) in the seed coats of Vanilla orchid and in cacti of one genus, Melocactus (Chen et al., Proc. Natl. Acad. Sci. USA. 2012, 109, 1772-1777.). We have now determined the lignin types in the seed coats of 130 different cactus species. Lignin in the vegetative tissues of cacti is of the normal guaiacyl/syringyl (G/S) type, but members of most genera within the subfamily Cactoidae possess seed coat lignin of the novel C-type only, which we show is a homopolymer formed by endwise β-O-4-coupling of caffeyl alcohol monomers onto the growing polymer resulting in benzodioxane units. However, the species examined within the genera Coryphantha, Cumarinia, Escobaria and Mammillaria (Cactoideae) mostly had normal G/S lignin in their seeds, as did all six species in the subfamily Opuntioidae that were examined. Seed coat lignin composition is still evolving in the Cactaceae, as seeds of one Mammillaria species (M. lasiacantha) possess only C-lignin, three Escobaria species (E. dasyacantha, E. lloydii and E. zilziana) contain an unusual lignin composed of 5-hydroxyguaiacyl units, the first report of such a polymer that occurs naturally in plants, and seeds of some species contain no lignin at all. We discuss the implications of these findings for the mechanisms that underlie the biosynthesis of these newly discovered lignin types.

  10. Organosolv ethanol lignin from hybrid poplar as a radical scavenger: relationship between lignin structure, extraction conditions, and antioxidant activity.

    Science.gov (United States)

    Pan, Xuejun; Kadla, John F; Ehara, Katsunobu; Gilkes, Neil; Saddler, Jack N

    2006-08-09

    Twenty-one organosolv ethanol lignin samples were prepared from hybrid poplar (Populus nigra xP. maximowiczii) under varied conditions with an experimental matrix designed using response surface methodology (RSM). The lignin preparations were evaluated as potential antioxidants. Results indicated that the lignins with more phenolic hydroxyl groups, less aliphatic hydroxyl groups, low molecular weight, and narrow polydispersity showed high antioxidant activity. Processing conditions affected the functional groups and molecular weight of the extracted organosolv ethanol lignins, and consequently influenced the antioxidant activity of the lignins. In general, the lignins prepared at elevated temperature, longer reaction time, increased catalyst, and diluted ethanol showed high antioxidant activity. Regression models were developed to enable the quantitative prediction of lignin characteristics and antioxidant activity based on the processing conditions.

  11. Structural characterization of lignin isolated from coconut (Cocos nucifera) coir fibers.

    Science.gov (United States)

    Rencoret, Jorge; Ralph, John; Marques, Gisela; Gutiérrez, Ana; Martínez, Ángel T; del Río, José C

    2013-03-13

    The structure of the isolated milled "wood" lignin from coconut coir has been characterized using different analytical methods, including Py-GC/MS, 2D NMR, DFRC, and thioacidolysis. The analyses demonstrated that it is a p-hydroxyphenyl-guaiacyl-syringyl (H-G-S) lignin, with a predominance of G units (S/G ratio 0.23) and considerable amounts of associated p-hydroxybenzoates. Two-dimensional NMR indicated that the main substructures present in this lignin include β-O-4' alkyl aryl ethers followed by phenylcoumarans and resinols. Two-dimensional NMR spectra also indicated that coir lignin is partially acylated at the γ-carbon of the side chain with p-hydroxybenzoates and acetates. DFRC analysis showed that acetates preferentially acylate the γ-OH in S rather than in G units. Despite coir lignin's being highly enriched in G-units, thioacidolysis indicated that β-β' resinol structures are mostly derived from sinapyl alcohol. Finally, we find evidence that the flavone tricin is incorporated into the coconut coir lignin, as has been recently noted for various grasses.

  12. Effect of lignin on water vapor barrier, mechanical, and structural properties of agar/lignin composite films.

    Science.gov (United States)

    Shankar, Shiv; Reddy, Jeevan Prasad; Rhim, Jong-Whan

    2015-11-01

    Biodegradable composite films were prepared using two renewable resources based biopolymers, agar and lignin alkali. The lignin was used as a reinforcing material and agar as a biopolymer matrix. The effect of lignin concentration (1, 3, 5, and 10wt%) on the performance of the composite films was studied. In addition, the mechanical, water vapor barrier, UV light barrier properties, FE-SEM, and TGA of the films were analyzed. The agar/lignin films exhibited higher mechanical and UV barrier properties along with lower water vapor permeability compared to the neat agar film. The FTIR and SEM results showed the compatibility of lignin with agar polymer. The swelling ratio and moisture content of agar/lignin composite films were decreased with increase in lignin content. The thermostability and char content of agar/lignin composite films increased with increased lignin content. The results suggested that agar/lignin films have a potential to be used as a UV barrier food packaging material for maintaining food safety and extending the shelf-life of the packaged food.

  13. Structural characterization of lignin: a potential source of antioxidants guaiacol and 4-vinylguaiacol.

    Science.gov (United States)

    Azadfar, Mohammadali; Gao, Allan Haiming; Bule, Mahesh V; Chen, Shulin

    2015-04-01

    The structure of lignin obtained from the ozone and soaking aqueous ammonia pretreatment of wheat straw has been characterized utilizing chemical analytical methods in order to reveal its antioxidant characteristics, including attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), pyrolysis/tetramethylammonium hydroxide-gas chromatography/mass spectrometry (Py/TMAH-GC/MS), gel permeation chromatography (GPC), ultra violet-visible spectroscopy (UV-vis), and 1,1-diphenyl-2-picrylhydrazyl (DPPH) antioxidant evaluation assay. The results demonstrated that the isolated lignin is a ρ-hydroxyphenyl- guaiacyl-syringyl (H-G-S) lignin, with S/G ratio of 0.35 and significant amounts of phenol 2-methoxy (guaiacol) and phenol 2-methoxy-4-vinyl (4-vinylguaiacol). The Py-GC/MS and Py/TMAH-GC/MS pyrograms indicated that the major units in this lignin are derived from hydroxycinnamic acids. The GPC results revealed the molecular weight of the lignin was considerably low and also the FTIR analysis showed that the lignin possessed hydroxyl and methoxy functional groups; the factors led to the extracted lignin having a comparable antioxidant activity to that of currently used commercial antioxidants. The UV-vis and DPPH antioxidant assay results suggested a percentage of inhibition of the DPPH radicals in the following order: guaiacol (103.6 ± 1.36)>butylated hydroxytoluene (103.3 ± 1)>ferulic acid (102.6 ± 0.79)>pretreated lignin (86.9 ± 0.34). Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Microwave-assisted organic acid extraction of lignin from bamboo: structure and antioxidant activity investigation.

    Science.gov (United States)

    Li, Ming-Fei; Sun, Shao-Ni; Xu, Feng; Sun, Run-Cang

    2012-10-01

    Microwave-assisted extraction in organic acid aqueous solution (formic acid/acetic acid/water, 3/5/2, v/v/v) was applied to isolate lignin from bamboo. Additionally, the structural features of the extracted lignins were thoroughly investigated in terms of C₉ formula, molecular weight distribution, FT-IR, (1)H NMR and HSQC spectroscopy. It was found that with an increase in the severity of microwave-assisted extraction, there was an increase of phenolic hydroxyl content in the lignin. In addition, an increase of the severity resulted in a decrease of the bound carbohydrate content as well as molecular weight of the lignin. Antioxidant activity investigation indicated that the radical scavenging index of the extracted lignins (0.35-1.15) was higher than that of BHT (0.29) but lower than that of BHA (3.85). The results suggested that microwave-assisted organic acid extraction provides a promising way to prepare lignin from bamboo with good antioxidant activity for potential application in the food industry. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. Purification, structural characterization, and modification of organosolv wheat straw lignin.

    Science.gov (United States)

    Mbotchak, Laurie; Le Morvan, Clara; Duong, Khanh Linh; Rousseau, Brigitte; Tessier, Martine; Fradet, Alain

    2015-06-03

    Biolignin, a wheat straw lignin produced by acetic acid/formic acid/water hydrolysis, was characterized by (31)P and (13)C-(1)H 2D NMR spectroscopy and by size-exclusion chromatography. Biolignin is a mixture of low molar mass compounds (Mn = 1660 g/mol) made up of S, G, and H units and of coumaric and ferulic acid units. β-5 and β-O-4 interunit linkages are partially acylated in the γ-position by acetate and p-coumarate groups. Deacylated samples with a low content of contaminants were obtained by combining alkaline hydrolysis and solvent extraction. The high phenolic OH content found by (31)P NMR reflects the presence of condensed aromatic units, such as 5-5 units. Reaction of purified lignin with ethanol and ethane-1,2-diol yielded esterified lignins much more soluble than Biolignin in common organic solvents. During this reaction, the secondary OH of β-O-4 linkages was simultaneously etherified. Phenol hydroxyethylation by 2-chloroethanol yielded samples containing only aliphatic hydroxyl groups.

  16. Structural Characterization of Lignins Isolated from Caragana sinica Using FT-IR and NMR Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    XIAOLing-ping; SHIZheng-jun; XUFeng; SUN Run-cang; Amar Kmohanty

    2011-01-01

    In order to efficiently explore and use woody biomass,six lignin fractions were isolated from dewaxed Caragana sinica via successive extraction with organic.solvents and alkaline solutions.The lignin structures were characterized by Fourier transform infrared spectroscopy (FT-IR) and 1D and 2D Nuclear Magnetic Resonance (NMR).FT-IR spectra revealed that the “core” of the lignin structure did not significantly change during the treatment under the conditions given.The results of 1 H and 13C NMR demonstrated that the lignin fraction L2,isolated with 70% ethanol containing 1% NaOH,was mainly composed of β-O-4 ether bonds together with G and S units and trace p-hydroxyphenyl unit.Based on the 2D HSQC NMR spectrum,the ethanol organosolv lignin fraction L1,extracted with 70% ethanol,presents a predominance of β-O-4' arylether linkages (61% of total side chains),and a low abundance of condensed carbon-carbon linked structures (such as β-β',β-1',and β-5') and a lower S/G ratio.Furthermore,a small percentage (ca.9%) of the linkage side chain was found to be acylated at the γ-carbon.

  17. Lignin-degrading peroxidases from genome of selective ligninolytic fungus Ceriporiopsis subvermispora.

    Science.gov (United States)

    Fernández-Fueyo, Elena; Ruiz-Dueñas, Francisco J; Miki, Yuta; Martínez, María Jesús; Hammel, Kenneth E; Martínez, Angel T

    2012-05-11

    The white-rot fungus Ceriporiopsis subvermispora delignifies lignocellulose with high selectivity, but until now it has appeared to lack the specialized peroxidases, termed lignin peroxidases (LiPs) and versatile peroxidases (VPs), that are generally thought important for ligninolysis. We screened the recently sequenced C. subvermispora genome for genes that encode peroxidases with a potential ligninolytic role. A total of 26 peroxidase genes was apparent after a structural-functional classification based on homology modeling and a search for diagnostic catalytic amino acid residues. In addition to revealing the presence of nine heme-thiolate peroxidase superfamily members and the unexpected absence of the dye-decolorizing peroxidase superfamily, the search showed that the C. subvermispora genome encodes 16 class II enzymes in the plant-fungal-bacterial peroxidase superfamily, where LiPs and VPs are classified. The 16 encoded enzymes include 13 putative manganese peroxidases and one generic peroxidase but most notably two peroxidases containing the catalytic tryptophan characteristic of LiPs and VPs. We expressed these two enzymes in Escherichia coli and determined their substrate specificities on typical LiP/VP substrates, including nonphenolic lignin model monomers and dimers, as well as synthetic lignin. The results show that the two newly discovered C. subvermispora peroxidases are functionally competent LiPs and also suggest that they are phylogenetically and catalytically intermediate between classical LiPs and VPs. These results offer new insight into selective lignin degradation by C. subvermispora.

  18. Mild acetosolv process to fractionate bamboo for the biorefinery: structural and antioxidant properties of the dissolved lignin.

    Science.gov (United States)

    Li, Ming-Fei; Sun, Shao-Ni; Xu, Feng; Sun, Run-Cang

    2012-02-22

    Fractionation of lignocellulosic material into its constitutive components is of vital importance for the production of biofuels as well as other value-added chemicals. The conventional acetosolv processes are mainly focused on the production of pulp from woody lignocelluloses. In this study, a mild acetosolv process was developed to fractionate bamboo under atmospheric pressure to obtain cellulosic pulp, water-soluble fraction, and acetic acid lignin. The structural features of the lignins obtained under various conditions were characterized with elemental analysis, sugar analysis, alkaline nitrobenzene oxidation, gel permeation chromatography (GPC), (1)H nuclear magnetic resonance ((1)H NMR), and heteronuclear single-quantum coherence (HSQC) spectroscopy. As compared to milled wood lignin (MWL) of bamboo, acetic acid lignins had low impurities (carbohydrates 2.48-4.56%) mainly due to the cleavage of linkages between lignin and carbohydrates. In addition, acetic acid lignins showed a low proportion of syringyl (S) units. Due to the cleavage of linkages between lignin units, acetic acid lignins had weight-average molecular weights ranging from 4870 to 5210 g/mol, less than half that of MWL (13000 g/mol). In addition, acetic acid lignins showed stronger antioxidant activity mainly due to the significant increase of free phenolic hydroxyls. The lignins obtained with such low impurities, high free phenolic hydroxyls, and medium molecular weights are promising feedstocks to replace petroleum chemicals.

  19. Unravelling lignin formation and structure. Final report, April 1, 1988--March 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, N.G. [Washington State Univ., Pullman, WA (United States). Inst. of Biological Chemistry

    1991-12-31

    During this study, we established that the Fagaceae exclusively accumulate Z-monolignois/glucosides, and not the E-isomers. Evidence for the presence of a novel E{yields}Z isomerse has been obtained. Our pioneering work in lignin biosynthesis and structure in situ has also progressed smoothly. We established the bonding environments of a woody angiosperm, Leucanea leucocephala, as well as wheat (T. aestivum) and tobacco (N. tabacum). A cell culture system from Pinus taeda was developed which seems ideal for investigating the early stages of lignification. These cultures excrete peroxidase isozymes, considered to be specifically involved in lignin deposition. We also studied the effect of the putative lignin-degrading enzyme, lignin peroxidase, on monolignols and dehydropolymerisates therefrom. In all cases, polymerization was observed, and not degradation; these polymers are identical to that obtained with horseradish peroxidases/H{sub 2}O{sub 2}. It seems inconceivable that these enzymes can be considered as being primarily responsible for lignin biodegradation.

  20. Structural features of lignin macromolecules extracted with ionic liquid from poplar wood.

    Science.gov (United States)

    Kim, Jae-Young; Shin, Eun-Jin; Eom, In-Yong; Won, Keehoon; Kim, Yong Hwan; Choi, Donha; Choi, In-Gyu; Choi, Joon Weon

    2011-10-01

    1-Ethyl-3-methylimidazolium acetate ([Emim][CH₃COO]) was used for the extraction of lignin from poplar wood (Populus albaglandulosa), which was called to ionic liquid lignin (ILL) and structural features of ILL were compared with the corresponding milled wood lignin (MWL). Yields of ILL and MWL were 5.8±0.3% and 4.4±0.4%, respectively. The maximum decomposition rate (V(M)) and temperature (T(M)) corresponding to V(M) were 0.25%/ °C and 308.2 °C for ILL and 0.30%/ °C and 381.3 °C for MWL. The amounts of functional groups (OMe and phenolic OH) appeared to be similar for both lignins; approximately 15.5% and 6.7% for ILL and 14.4% and 6.3% for MWL. However, the weight average molecular weight (M(w)) of ILL (6347 Da) was determined to be 2/3-fold of that of MWL (10,002 Da) and polydispersity index (PDI: M(w)/M(n)) suggested that the lignin fragments were more uniform in the ILL (PDI 1.62) than in the MWL (PDI 2.64). Copyright © 2011 Elsevier Ltd. All rights reserved.

  1. Leucaena leucocephala (Lam.) de Wit., "subabul" stem lignin: Isolation, structural characterization and thermal properties.

    Science.gov (United States)

    Yearla, Srinivasa Rao; Padmasree, Kollipara

    2016-06-01

    Lignin is the second most abundant renewable biopolymer on earth after cellulose. It is being used in many industrial applications due to its abundance. In the present study, lignin was isolated from the stems of Leucaena leucocephala (Lam.) de Wit., a high biomass yielding plant using acidic dioxane under N2 atmosphere. Structural characterization of isolated dioxane lignin (DL) was performed by analytical techniques: UV, FT-IR, ¹H NMR and ¹³C NMR. Their monolignol content was determined by nitrobenzene oxidation followed by HPLC-MS/MS analysis. The data was compared with commercial alkali lignin (AL). The results showed that DL is of hardwood guaiacyl-syringyl (GS) type, whereas AL is softwood type with more guaiacyl units and trace amounts of p-hydroxyphenyl units (H). Thermogravimetric analysis (TGA) of DL showed two stage thermal degradation profile similar to AL. The DTGmax for DL and AL were found in the second major loss event of second stage of TGA at 424°C and 404°C, respectively. Differential scanning calorimetry (DSC) study exhibited the glass transition temperatures (Tg) at 132°C and 122°C for DL and AL, respectively. The results from thermal stability studies suggest that dioxane lignin isolated from the "miracle tree" (subabul) can be exploited in various thermoplastic industrial applications.

  2. Comparison on structural modification of industrial lignin by wet ball milling and ionic liquid pretreatment

    Directory of Open Access Journals (Sweden)

    Yongshui Qu

    2015-06-01

    Full Text Available As the most abundant aromatic compounds, lignin is still underutilized due to its relatively low quality. In order to improve its quality, two pretreatment technologies, wet ball milling (WBM and ionic liquid pretreatment (ILP were tested on the industrial lignin and evaluated on the average molecular weight and polydispersity, surface morphology, and functional groups changes. The results showed that the lignin pretreated by the WBM with phosphoric acid presented dramatic decrease of polydipersity (23% and increase of phenolic hydroxyl content (9%. While, the ILP treated samples exhibited the significant reduction of the average molecular weight and polydispersity. The decrease on the particle size and the emergence of the porous structure were found when treated with [Emim][OAc]. In addition, the remarkable reduction of the methoxy groups were observed to be 50% and 45% after treated with [Bmim]Cl and [Emim][OAc], respectively.

  3. Effect of lignin structure and surfactant on cellulase adsorption by lignin%木质素结构以及表面活性剂对木质素吸附纤维素酶的影响

    Institute of Scientific and Technical Information of China (English)

    姚兰; 赵建; 谢益民; 杨海涛; 曲音波

    2012-01-01

    As substitute of petrol, bioethanol production from lignocelluloses is one of hot point of research in recent years. A main obstacle of bioethanol production in commercial scale is its cost.'One of the most important methods to solve the key problem is raising yield of cellulose hydrolysis by enzyme. However, content and type of lignin in lignocellulosic substrates has a significant effect on the hydrolysis process, as lignin has double actions: as a physical barrier that decreases accessibility of cellulase to cellulose, and as an attractant that adsorbs cellulases i. e. forming non-productive binding. In this paper, structure and adsorption for cellulase of three kinds of ligin, milled wood lignin, Klasson lignin and alkaline lignin were studied, and various surfactants were screened and used for improving enzymatic hydrolysis of lignocelluloses because they have a great impact on cellulase adsorption on lignin. The results showed that there are different structure characteristics for the three kinds of lignin: the highest ability of adsorption for cellulase is Klasson lignin, and then milled wood lignin, the lowest alkaline lignin. The surfactant that can significantly increase enzymatic hydrolysis yield of lignocelluloses is PEG-8000, because it can make cellulase desorption from lignin and reactivation for hydrolysis of cellulose.

  4. Lignin Structure and Aggregation Behavior in a Two-Component Ionic Liquid Solvent System

    Directory of Open Access Journals (Sweden)

    Susanne Bylin

    2014-08-01

    Full Text Available Ionic liquids are of potential interest in the processing of lignocellulosic biomass. In this study, the ionic liquid co-solvent system of 1-methylimidazole (MIM and 1-ethyl-3-methyl-imidazolium acetate (EMIMAc was used to solvate LignoBoost lignin fractionated from black liquor obtained from a kraft paper mill. Lignin ethanol-precipitated (LEP and ethanol-soluble (LES fractions were characterized via gel permeation chromatography (GPC and 13C- and 31P-nuclear magnetic resonance spectroscopy (NMR to determine structural characteristics and their relationship to polymer solubility in the system. Polymer integrity and solubility were optimal at ~20% lignin loading (w/w. Results showed that LEPs were generally of higher apparent molecular weight (Mw and enriched with condensed/aliphatic ether linkages and aliphatic hydroxyls. The LESs had a lower apparent Mw and were enriched with carboxylic and phenolic groups. This newly gained knowledge on lignin fractionation and aggregation in the present solvent system provides future opportunities for tuning fractionation/extraction to suit a specific biomass-derived product, e.g., carbon fibers.

  5. Lignin peroxidase functionalities and prospective applications.

    Science.gov (United States)

    Falade, Ayodeji O; Nwodo, Uchechukwu U; Iweriebor, Benson C; Green, Ezekiel; Mabinya, Leonard V; Okoh, Anthony I

    2017-02-01

    Ligninolytic extracellular enzymes, including lignin peroxidase, are topical owing to their high redox potential and prospective industrial applications. The prospective applications of lignin peroxidase span through sectors such as biorefinery, textile, energy, bioremediation, cosmetology, and dermatology industries. The litany of potentials attributed to lignin peroxidase is occasioned by its versatility in the degradation of xenobiotics and compounds with both phenolic and non-phenolic constituents. Over the years, ligninolytic enzymes have been studied however; research on lignin peroxidase seems to have been lagging when compared to other ligninolytic enzymes which are extracellular in nature including laccase and manganese peroxidase. This assertion becomes more pronounced when the application of lignin peroxidase is put into perspective. Consequently, a succinct documentation of the contemporary functionalities of lignin peroxidase and, some prospective applications of futuristic relevance has been advanced in this review. Some articulated applications include delignification of feedstock for ethanol production, textile effluent treatment and dye decolourization, coal depolymerization, treatment of hyperpigmentation, and skin-lightening through melanin oxidation. Prospective application of lignin peroxidase in skin-lightening functions through novel mechanisms, hence, it holds high value for the cosmetics sector where it may serve as suitable alternative to hydroquinone; a potent skin-lightening agent whose safety has generated lots of controversy and concern. © 2016 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

  6. 3D structure prediction of lignolytic enzymes lignin peroxidase and manganese peroxidase based on homology modelling

    Directory of Open Access Journals (Sweden)

    SWAPNIL K. KALE

    2016-04-01

    Full Text Available Lignolytic enzymes have great biotechnological value in biopulping, biobleaching, and bioremediation. Manganese peroxidase (EC 1:11:1:13 and lignin peroxidase (EC 1:11:1:14 are extracellular and hem-containing peroxidases that catalyze H2O2-dependent oxidation of lignin. Because of their ability to catalyse oxidation of a wide range of organic compounds and even some inorganic compounds, they got tremendous industrial importance. In this study, 3D structure of lignin and manganese peroxidase has been predicted on the basis of homology modeling using Swiss PDB workspace. The physicochemical properties like molecular weight, isoelectric point, Grand average of hydropathy, instability and aliphatic index of the target enzymes were performed using Protparam. The predicted secondary structure of MnP has 18 helices and 6 strands, while LiP has 20 helices and 4 strands. Generated 3D structure was visualized in Pymol. The generated model for MnP and LiP has Z-score Qmean of 0.01 and -0.71, respectively. The predicted models were validated through Ramachandran Plot, which indicated that 96.1 and 95.5% of the residues are in most favored regions for MnP and LiP respectively. The quality of predicted models were assessed and confirmed by VERIFY 3D, PROCHECK and ERRAT. The modeled structure of MnP and LiP were submitted to the Protein Model Database.

  7. Structural Basis of Stereospecificity in the Bacterial Enzymatic Cleavage of β-Aryl Ether Bonds in Lignin*

    Science.gov (United States)

    Helmich, Kate E.; Pereira, Jose Henrique; Gall, Daniel L.; Heins, Richard A.; McAndrew, Ryan P.; Bingman, Craig; Deng, Kai; Holland, Keefe C.; Noguera, Daniel R.; Simmons, Blake A.; Sale, Kenneth L.; Ralph, John; Donohue, Timothy J.; Adams, Paul D.; Phillips, George N.

    2016-01-01

    Lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, we present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50–70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin. PMID:26637355

  8. Structural Basis of Stereospecificity in the Bacterial Enzymatic Cleavage of β-Aryl Ether Bonds in Lignin.

    Science.gov (United States)

    Helmich, Kate E; Pereira, Jose Henrique; Gall, Daniel L; Heins, Richard A; McAndrew, Ryan P; Bingman, Craig; Deng, Kai; Holland, Keefe C; Noguera, Daniel R; Simmons, Blake A; Sale, Kenneth L; Ralph, John; Donohue, Timothy J; Adams, Paul D; Phillips, George N

    2016-03-04

    Lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, we present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50-70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin.

  9. Effect of replacing polyol by organosolv and kraft lignin on the property and structure of rigid polyurethane foam

    Directory of Open Access Journals (Sweden)

    Pan Xuejun

    2013-01-01

    Full Text Available Abstract Background Lignin is one of the three major components in plant cell walls, and it can be isolated (dissolved from the cell wall in pretreatment or chemical pulping. However, there is a lack of high-value applications for lignin, and the commonest proposal for lignin is power and steam generation through combustion. Organosolv ethanol process is one of the effective pretreatment methods for woody biomass for cellulosic ethanol production, and kraft process is a dominant chemical pulping method in paper industry. In the present research, the lignins from organosolv pretreatment and kraft pulping were evaluated to replace polyol for producing rigid polyurethane foams (RPFs. Results Petroleum-based polyol was replaced with hardwood ethanol organosolv lignin (HEL or hardwood kraft lignin (HKL from 25% to 70% (molar percentage in preparing rigid polyurethane foam. The prepared foams contained 12-36% (w/w HEL or 9-28% (w/w HKL. The density, compressive strength, and cellular structure of the prepared foams were investigated and compared. Chain extenders were used to improve the properties of the RPFs. Conclusions It was found that lignin was chemically crosslinked not just physically trapped in the rigid polyurethane foams. The lignin-containing foams had comparable structure and strength up to 25-30% (w/w HEL or 19-23% (w/w HKL addition. The results indicated that HEL performed much better in RPFs and could replace more polyol at the same strength than HKL because the former had a better miscibility with the polyol than the latter. Chain extender such as butanediol could improve the strength of lignin-containing RPFs.

  10. Physicochemical and structural characterization of alkali soluble lignins from oil palm trunk and empty fruit-bunch fibers.

    Science.gov (United States)

    Sun, R; Fang, J M; Tomkinson, J; Bolton, J

    1999-07-01

    Six alkali soluble lignin fractions were extracted from the cell wall materials of oil palm trunk and empty fruit-bunch (EFB) fibers with 5% NaOH, 10% NaOH, and 24% KOH/2% H(3)BO(3). All of the lignin fractions contained rather low amounts of associated neutral sugars (0.8-1.2%) and uronic acids (1.1-2.0%). The lignin fractions isolated with 5% NaOH from the lignified palm trunk and EFB fibers gave a relatively higher degree of polymerization as shown by weight-average molecular weights ranging between 2620 and 2840, whereas the lignin fractions isolated with 10% NaOH and 24% KOH/2% H(3)BO(3) from the partially delignified palm trunk and EFB fibers showed a relatively lower degree of polymerization, as shown by weight-average molecular weights ranging between 1750 and 1980. The results obtained by alkaline nitrobenzene oxidation showed that all of the lignin preparations contained a high proportion of noncondensed syringyl units with small amounts of noncondensed guaiacyl and fewer p-hydroxyphenyl units. The lignin fraction extracted with 5% NaOH from the lignified EFB fiber was mainly composed of beta-O-4 ether-linked units. Small amounts of 5-5', beta-5, and beta-beta' carbon-carbon linkages were also found to be present between the lignin structural units. Further studies showed that uronic, p-hydroxybenzoic, and ferulic acids in the cell walls of palm fibers were esterified to lignin.

  11. Structural transformation of hemicelluloses and lignin from triploid poplar during acid-pretreatment based biorefinery process.

    Science.gov (United States)

    Wang, Kun; Yang, Haiyan; Yao, Xi; Xu, Feng; Sun, Run-Cang

    2012-07-01

    In order to understand the behaviors of hemicelluloses and lignin under the given acidic conditions with increasing severity, the structural characteristics were elucidated in detail by both wet chemistry methods and spectroscopic analyses in this study. Although acidic pretreatment significantly hydrolyzed the glycosidic linkages in xylan backbone and then reduced the molecular weight of xylan from 89,600 to 19,630 g/mol, a slightly increased amount of glucuronic acid was observed, probably attributing to the maintenance of ester bonds. The serious structural variation occurred in lignin macromolecule was evidenced by the extensive degradation of β-O-4 ether linkages and resinol substructure, together with the changes in the ratios of the three monolignols in ester-bond, ether-bond and non-condensed phenolic compounds. At the most severity, obvious condensation reactions introduced the clear shift of C(2) and C(5) correlations and the absence of C(6) correlation in guaiacyl units by 2D HSQC analysis. Copyright © 2012 Elsevier Ltd. All rights reserved.

  12. Manipulation of Guaiacyl and Syringyl Monomer Biosynthesis in an Arabidopsis Cinnamyl Alcohol Dehydrogenase Mutant Results in Atypical Lignin Biosynthesis and Modified Cell Wall Structure

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Nickolas A.; Tobimatsu, Yuki; Ciesielski, Peter N.; Ximenes, Eduardo; Ralph, John; Donohoe, Bryon S.; Ladisch, Michael; Chapple, Clint

    2015-08-01

    Modifying lignin composition and structure is a key strategy to increase plant cell wall digestibility for biofuel production. Disruption of the genes encoding both cinnamyl alcohol dehydrogenases (CADs), including CADC and CADD, in Arabidopsis thaliana results in the atypical incorporation of hydroxycinnamaldehydes into lignin. Another strategy to change lignin composition is downregulation or overexpression of ferulate 5-hydroxylase (F5H), which results in lignins enriched in guaiacyl or syringyl units, respectively. Here, we combined these approaches to generate plants enriched in coniferaldehyde-derived lignin units or lignins derived primarily from sinapaldehyde. The cadc cadd and ferulic acid hydroxylase1 (fah1) cadc cadd plants are similar in growth to wild-type plants even though their lignin compositions are drastically altered. In contrast, disruption of CAD in the F5H-overexpressing background results in dwarfism. The dwarfed phenotype observed in these plants does not appear to be related to collapsed xylem, a hallmark of many other lignin-deficient dwarf mutants. cadc cadd, fah1 cadc cadd, and cadd F5H-overexpressing plants have increased enzyme-catalyzed cell wall digestibility. Given that these CAD-deficient plants have similar total lignin contents and only differ in the amounts of hydroxycinnamaldehyde monomer incorporation, these results suggest that hydroxycinnamaldehyde content is a more important determinant of digestibility than lignin content.

  13. Isolation and structural characterization of sugarcane bagasse lignin after dilute phosphoric acid plus steam explosion pretreatment and its effect on cellulose hydrolysis.

    Science.gov (United States)

    Zeng, Jijiao; Tong, Zhaohui; Wang, Letian; Zhu, J Y; Ingram, Lonnie

    2014-02-01

    The structure of lignin after dilute phosphoric acid plus steam explosion pretreatment process of sugarcane bagasse in a pilot scale and the effect of the lignin extracted by ethanol on subsequent cellulose hydrolysis were investigated. The lignin structural changes caused by pretreatment were identified using advanced nondestructive techniques such as gel permeation chromatography (GPC), quantitative (13)C, and 2-D nuclear magnetic resonance (NMR). The structural analysis revealed that ethanol extractable lignin preserved basic lignin structure, but had relatively lower amount of β-O-4 linkages, syringyl/guaiacyl units ratio (S/G), p-coumarate/ferulate ratio, and other ending structures. The results also indicated that approximately 8% of mass weight was extracted by pure ethanol. The bagasse after ethanol extraction had an approximate 22% higher glucose yield after enzyme hydrolysis compared to pretreated bagasse without extraction. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Polymerization of different lignins by laccase

    NARCIS (Netherlands)

    Mattinen, M.L.; Suortti, T.; Gosselink, R.J.A.; Argyropoulos, D.S.; Evtuguin, D.; Suurnäkki, A.; Jong, de E.; Tamminen, T.

    2008-01-01

    In this study the oxidative polymerization of different lignins, i.e. Flax Soda lignin, Spruce EMAL, and Eucalyptus Dioxane lignin by Trametes hirsuta laccase was compared. Initially the structures of the different lignins were compared by Fourier transform infrared spectroscopy. The reactivity of l

  15. Lignin-based monomers: Utilization in high-performance polymers and the effects of their structures on polymer properties

    Science.gov (United States)

    Stanzione, Joseph F., III

    With the uncertainty of petroleum reserves and future crude oil prices, lignocellulosic biomass is becoming an increasingly valuable resource for the sustainable development of fuels, chemicals, and materials, including vinyl ester resins (VERs). Petroleum-based VERs are used to produce polymer composites for a wide variety of commercial applications. Although possessing relatively high moduli, strengths, and glass transition temperatures, commercial VERs typically contain high concentrations of a reactive diluent, such as styrene. However, these reactive diluents are often considered hazardous air pollutants (HAPs), volatile organic compounds (VOCs), and anticipated carcinogens. Moreover, bisphenol-A, which has gained considerable attention due to potential associated health-related issues, is utilized as a precursor in the synthesis of VERs. A green chemistry and engineering approach in the development of new VERs and renewable reactive diluents that are based on lignin is presented in this dissertation. Lignin, which is currently an abundant, renewable waste product of the paper and pulping industry, is primarily burned as a low value fuel. However, lignin has the potential to be a low cost feedstock in future lignocellulosic biorefineries that could yield highly valuable aromatic chemicals (lignin model compounds, LMCs) when strategically depolymerized. The incorporation of aromaticity in a resin's chemical structure is known to improve overall polymer composite performance and the high aromatic content found in lignin is ideal for novel resin development. Highlighted in this dissertation are three projects: (1) the synthesis and characterization of a lignin-based bio-oil resin/reactive diluent, (2) the use of functionalized LMCs as styrene replacements in VERs, and (3) the synthesis and characterization of a vanillin-based resin. Through the use of traditional and new polymer theory coupled with spectroscopic, thermal, and mechanical techniques, structure

  16. Characterisation of structure-dependent functional properties of lignin with infrared spectroscopy

    NARCIS (Netherlands)

    Boeriu, C.G.; Bravo, D.; Gosselink, R.J.A.; Dam, van J.E.G.

    2004-01-01

    Fourier-transformed infrared spectroscopy (FT-IR) was evaluated as an analytical technique for the estimation of the chemical composition and functional properties of lignin. A sample set containing various non-wood, hardwood and softwood lignins isolated by different processing technologies was use

  17. Influence of lignin on morphology, structure and thermal behavior of polylactic acid-based biocomposites

    Science.gov (United States)

    Canetti, Maurizio; Cacciamani, Adriana; Bertini, Fabio

    2016-05-01

    Polylactic acid (PLA) is a thermoplastic biodegradable polymer that can be made from annually renewable resources. Lignin is a natural amorphous polyphenolic macromolecule inexpensive and easily available. In the present study PLA and acetylated lignin biocomposites were prepared by casting from chloroform solution. PLA can crystallize from the melt in the α and α' forms, depending on the adopted crystallization conditions. The presence of the lignin in the biocomposites can interfere with the crystal formation process. Isothermal crystallizations were performed at different temperatures, the presence of lignin causes an increase of the time of crystallization, while the overall crystallization rate and the spherulite radial growth rate decrease with enhancing the lignin content in the biocomposites.

  18. COMMERCIAL VIABILITY ANALYSIS OF LIGNIN BASED CARBON FIBRE

    OpenAIRE

    2014-01-01

    Lignin is a rich renewable source of aromatic compounds. As a potentialpetroleum feedstock replacement, lignin can reduce environmental impacts such ascarbon emission. Due to its complex chemical structure, lignin is currently underutilized.Exploiting lignin as a precursor for carbon fibre adds high economic value to lignin andencourages further development in lignin extraction technology. This report includes apreliminary cost analysis and identifies the key aspects of lignin-based carbon fi...

  19. Mechanochemical modification of lignin and application of the modified lignin for thermoplastics and thermosets

    Science.gov (United States)

    Guo, Xiaojie; Zhang, Jinwen; Xin, Junna

    In this work, mechanochemical modification of lignin and use of the modified lignin in thermoplastics and thermosets were studied. Oleated lignin was successfully prepared by transesterification between lignin and methyl, and the oleation reaction was performed in a solvent-free and room temperature ball milling process with a relatively short time. PLA/lignin blends were prepared through melt extrusion. Compared with the PLA/lignin blends, the PLA/oleated lignin blends exhibited finer dispersion of lignin in the blends, increased glass transition temperature and higher tensile properties, suggesting improved compatibility between lignin and PLA. Carboxylic and anhydride groups were also introduced into the structure of lignin via mechanochemical modification, and the resulting lignin derivatives were used as curing agents for epoxies. The dynamic mechanical properties and thermal stability of the cured epoxy resins were studied using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA).

  20. Effect of Chemical Structure on Pyrolysis Behavior of Alcell Mild Acidolysis Lignin

    Directory of Open Access Journals (Sweden)

    Chao Liu

    2014-12-01

    Full Text Available In this study, two purified mild acidolysis lignins (MAL extracted from triploid poplar, i.e., Alcell MAL and Alkali MAL, were compared. Some properties, including elemental contents, higher heating value (HHV, functional hydroxyl group compositions, and molecular weights, were tested to characterize the structure of these two MALs. The releasing laws of gases and the distribution of products were also investigated through the use of thermogravimetric Fourier transform infrared (TG-FTIR and pyrolysis-gas chromatography combined with mass spectrometry (Py-GC/MS. The results showed that both MALs had pyrolytic advantages, largely because of their unique chemical structures. However, although the species of volatiles from Alkali MAL were similar to those from Alcell MAL, the releasing temperature range for Alcell MAL was relatively narrow and the volatiles from it were concentrated. Among the fast pyrolytic products, phenols were the most abundant. The yield of 2,6-dimethoxy-4-(2-propenylphenol, which was the dominant product, was 25.66% for Alcell MAL and 20.77% for Alkali MAL, respectively. Overall, pyrolytic products from Alcell MAL were more enriched.

  1. Isolation and Structural Characterization of Lignin from Cotton Stalk Treated in an Ammonia Hydrothermal System

    Science.gov (United States)

    Kang, Sumin; Xiao, Lingping; Meng, Lingyan; Zhang, Xueming; Sun, Runcang

    2012-01-01

    To investigate the potential for the utilization of cotton stalk, ammonia hydrothermal treatment was applied to fractionate the samples into aqueous ammonia-soluble and ammonia-insoluble portions. The ammonia-soluble portion was purified to yield lignin fractions. The lignin fractions obtained were characterized by wet chemistry (carbohydrate analysis) and spectroscopy methods (FT-IR, 13C and 1H-13C HSQC NMR spectroscopy) as well as gel permeation chromatography (GPC). The results showed that the cotton stalk lignin fractions were almost absent of neutral sugars (0.43%–1.29%) and had relatively low average molecular weights (1255–1746 g/mol). The lignin fractions belonged to typical G-S lignin, which was composed predominately of G-type units (59%) and noticeable amounts of S-type units (40%) together with a small amount of H-type units (~1%). Furthermore, the ammonia-extractable lignin fractions were mainly composed of β-O-4′ inter-unit linkages (75.6%), and small quantities of β-β′ (12.2%), together with lower amounts of β-5′ carbon-carbon linkages (7.4%) and p-hydroxycinnamyl alcohol end groups. PMID:23203120

  2. Both phenolic and non-phenolic green tea fractionsinhibit migration of cancer cells

    Directory of Open Access Journals (Sweden)

    Ean-Jeong Seo

    2016-11-01

    Full Text Available Green tea consumption is associated with chemoprevention of many cancer types. Fresh tea leaves are rich in polyphenolic catechins, which can constitute up to 30% of the dry leaf weight. While the polyphenols of green tea have been well investigated, it is still largely unknown, whether or not non-phenolic constituents also reveal chemopreventive and anti-metastatic effects.In this study, we investigated the effects of a fraction of green tea rich in phenolic compounds (PF, a non-phenolic fraction (NPF, which contains glyceroglycolipids (GGL, and a pure glyceroglycolipid compound isolated from the non-phenolic fraction in human cancer.Dried green tea leaves were extracted and applied to a Sephadex LH-20 column. The resazurin reduction assay was used to investigate the cytotoxicity of green tea samples towards human HepG2 hepatocellular carcinoma and normal AML12 hepatocytes cells. Gene expression profiling was performed by mRNA microarray hybridization and the microarray results were validated by RT-PCR. The scratch migration assay was used to investigate the effects of green tea samples on cell migration in vitro. The changes of microtubule dynamics were observed using fluorescence microscopy.PF and NPF were prepared from methanol extract of green tea. A GGL was isolated from NPF. All three green tea samples did not show significant cytotoxic activity up to 10 µg/mL in both HepG2 and AML12 cells, whereas cytotoxicity of the control drug doxorubicin was observed with both cell lines (IC50 on AML12: 0.024 µg/mL, IC50 on HepG2: 2.103 µg/mL. We identified three sets of genes differentially expressed upon treatment with the green tea samples. The genes were associated with cytoskeleton formation, cellular movement and morphology. The correlation coefficients between mRNA expression values determined by microarray and RT-PCR were R = 0.94. HepG2 and U2OS cells treated with green tea extracts showed the delayed closures. Besides, the number of

  3. Pyrolysis - gas chromatography - mass spectrometry of lignins

    Energy Technology Data Exchange (ETDEWEB)

    Martin, F.; Saiz-Jimenez, C.; Gonzalez-Vila, F.J.

    1979-01-01

    Milled wood lignins from spruce, beech and bamboo were pyrolysed. The high-boiling products of pyrolysis were studied by GLC and mass spectrometry. The forty-three products identified provide information on the structural units of lignin.

  4. Design of Potent and Druglike Nonphenolic Inhibitors for Catechol O-Methyltransferase Derived from a Fragment Screening Approach Targeting the S-Adenosyl-l-methionine Pocket.

    Science.gov (United States)

    Lerner, Christian; Jakob-Roetne, Roland; Buettelmann, Bernd; Ehler, Andreas; Rudolph, Markus; Rodríguez Sarmiento, Rosa María

    2016-11-23

    A fragment screening approach designed to target specifically the S-adenosyl-l-methionine pocket of catechol O-methyl transferase allowed the identification of structurally related fragments of high ligand efficiency and with activity on the described orthogonal assays. By use of a reliable enzymatic assay together with X-ray crystallography as guidance, a series of fragment modifications revealed an SAR and, after several expansions, potent lead compounds could be obtained. For the first time nonphenolic and small low nanomolar potent, SAM competitive COMT inhibitors are reported. These compounds represent a novel series of potent COMT inhibitors that might be further optimized to new drugs useful for the treatment of Parkinson's disease, as adjuncts in levodopa based therapy, or for the treatment of schizophrenia.

  5. Studies on the photochemistry of 1,7-diphenyl-1,6-heptadiene-3,5-dione, a non-phenolic curcuminoid model.

    Science.gov (United States)

    Sundaryono, Agus; Nourmamode, Aziz; Gardrat, Christian; Grelier, Stéphane; Bravic, Georges; Chasseau, Daniel; Castellan, Alain

    2003-09-01

    The comparative photostability of curcumin 1, and two non-phenolic curcuminoids: 1,7-diphenyl-1,6-heptadiene-3,5-dione 2 (unsubstituted curcumin) and dimethylcurcumin 3 in non-degassed dilute solutions (approximately 3-5 x 10(-5) mol l(-1)) has been established by UV-visible absorption spectroscopy; disappearance quantum yields were measured. The similar behavior of the three studied curcuminoids is indicative of only a moderate role of phenol groups in the photodegradation process. Structural analysis of the photodegradation products of compound 2 in more concentrated solution (approximately 3.6 x 10(-3) mol l(-1)) shows formation of benzaldehyde, cinnamaldehyde, 2'-hydroxy-5',6'-benzochalcone 4, flavanone 5 and some other unidentified photoproducts. Flavanone 5 is formed by irradiation of chalcone 4. It represents a unique example of photochemical conversion of a diarylheptanoid molecule into a flavonoid, another very important class of natural products.

  6. Impact of the homogenization process on the structure and antioxidant properties of chitosan-lignin composite films.

    Science.gov (United States)

    Crouvisier-Urion, Kevin; Lagorce-Tachon, Aurélie; Lauquin, Camille; Winckler, Pascale; Tongdeesoontorn, Wirongrong; Domenek, Sandra; Debeaufort, Frédéric; Karbowiak, Thomas

    2017-12-01

    This work investigated the impact of two homogenization treatments, High Shear (HS) and High Pressure (HP), on the structure and antioxidant activity of chitosan-lignin bio-composite films. Laser light scattering analysis revealed that smaller lignin particles were obtained after HP processing, around 0.6μm, compared to HS treatment, between 2.5 and 5μm. Moreover, these particles were more homogeneously distributed in the chitosan film matrix after HP process, while some aggregates remained after HS treatment, as highlighted by two-photon microscopy. The surface hydrophobicity of the composite films, as measured by water contact angle, increased after the two homogenization treatments. Finally, the antioxidant activity of the composite films was determined using the DPPH· assay. No significant difference in the radical scavenging activity was noticeable, neither after HS nor HP processing. However, a migration of lignin residues from the film to the extraction medium was noticed, particularly for HP process. Copyright © 2017. Published by Elsevier Ltd.

  7. Rapid Py-GC/MS assessment of the structural alterations of lignins in genetically modified plants

    NARCIS (Netherlands)

    Rencoret, Jorge; Del Río, José Carlos; Nierop, Klaas G J|info:eu-repo/dai/nl/182329895; Gutiérrez, Ana; Ralph, John

    Genetic modifications for perturbing the lignin pathway in three different species of angiosperm plants, including non-woody (Arabidopsis and alfalfa) and woody (poplar) plants, were readily evaluated by analytical pyrolysis coupled to gas chromatography-mass spectrometry (Py-GC/MS). Pyrolysis

  8. Photodegradation of Acidolysis Lignin from BCMP

    Directory of Open Access Journals (Sweden)

    Ahmad Jahan Latibari

    2008-12-01

    Full Text Available A mild acidic dioxane extraction method was employed to isolate lignin from hardwood bleached chemimechanical pulp (BCMP. The isolated lignin was then purified and undergone elemental analysis. To study the photodegradation behavior, the lignin samples were impregnated onto the Whatman filter papers and irradiated with UV light for various periods. The photolyzed lignin was then recovered and analyzed by 1H-NMR spectroscopy. Phenylpropane-based formula (C9 of CMP pulp lignin and the photolyzed samples were then established with elemental analysis and 1H-NMR spectroscopy data. The results indicated that the benzaldehyde and benzoic acid type compounds were the main photodegradation products of BCMP lignin. The lignin photodegradation probably involved the degradation of phenylcoumaran units. Irradiation also increased the phenolic hydroxyl group content and decreased that of methoxyl groups, due to demethoxylation. The degrees of aromatic ring condensation were increased upon continuing the irradiation time, which imples the formation of condensed structures in photolyzed lignin.

  9. Photodegradation of acidolysis lignin from BCMP.

    Science.gov (United States)

    Azadfallah, Mohammad; Mirshokraei, Seyed Ahmad; Latibari, Ahmad Jahan

    2008-12-15

    A mild acidic dioxane extraction method was employed to isolate lignin from hardwood bleached chemimechanical pulp (BCMP). The isolated lignin was then purified and undergone elemental analysis. To study the photodegradation behavior, the lignin samples were impregnated onto the Whatman filter papers and irradiated with UV light for various periods. The photolyzed lignin was then recovered and analyzed by (1)H-NMR spectroscopy. Phenylpropane-based formula (C(9)) of CMP pulp lignin and the photolyzed samples were then established with elemental analysis and (1)H-NMR spectroscopy data. The results indicated that the benzaldehyde and benzoic acid type compounds were the main photodegradation products of BCMP lignin. The lignin photodegradation probably involved the degradation of phenylcoumaran units. Irradiation also increased the phenolic hydroxyl group content and decreased that of methoxyl groups, due to demethoxylation. The degrees of aromatic ring condensation were increased upon continuing the irradiation time, which imples the formation of condensed structures in photolyzed lignin.

  10. Structural elucidation of lignin polymers of Eucalyptus chips during organosolv pretreatment and extended delignification.

    Science.gov (United States)

    Wen, Jia-Long; Sun, Shao-Long; Yuan, Tong-Qi; Xu, Feng; Sun, Run-Cang

    2013-11-20

    Effective delignification of lignocelluloses is a very important to guarantee the economic feasibility of organosolv-based biorefinery. Eucalyptus chips were successively subjected to organosolv pretreatment (AEOP) and extended delignification (ED) process in the present study. The effects of delignification processes were scientifically evaluated by component analysis, SEM, and CP-MAS NMR techniques. It was found that the integrated process of organosolv pretreatment and subsequent delignification resulted in an effective delignification. The fundamental chemistry of the lignin obtained after these processes was thoroughly investigated by FT-IR, multidimensional NMR ((31)P-, (13)C-, and 2D-HSQC NMR), and GPC techniques. It was observed that an extensive cleavage of aryl ether linkages, ethoxylation, and some condensation reactions occurred in AEOP process, while α-oxidation mainly took place in alkaline hydrogen peroxide (AHP) process. It is believed that better understanding the fundamental chemistry of lignin facilitates the optimization of the delignification process. More importantly, well-defined of lignin polymers will facilitate their value-added applications in current and future biorefineries.

  11. Lignin Valorization: Improving Lignin Processing in the Biorefinery

    Energy Technology Data Exchange (ETDEWEB)

    Ragauskas, Arthur [Georgia Institute of Technology, Atlanta; Beckham, Gregg [National Renewable Energy Laboratory (NREL); Biddy, Mary J [National Renewable Energy Laboratory (NREL); Chandra, Richard [University of British Columbia, Vancouver; Chen, Fang [University of North Texas; Davis, Dr. Mark F. [National Renewable Energy Laboratory (NREL); Davison, Brian H [ORNL; Dixon, Richard [University of North Texas; Gilna, Paul [ORNL; Keller, Martin [ORNL; Langan, Paul [ORNL; Naskar, Amit K [ORNL; Saddler, Jack N [University of British Columbia, Vancouver; Tschaplinski, Timothy J [ORNL; Tuskan, Gerald A [ORNL; Wyman, Charles E, [University of California, Riverside; Harber, Karen S [ORNL

    2014-01-01

    Research and development activities directed toward commercial production of cellulosic ethanol have created the opportunity to dramatically increase the transformation of lignin to value-added products. Here we highlight recent advances in this lignin valorization effort. Discovery of genetic variants in native populations of bioenergy crops and direct manipulation of biosynthesis pathways have produced lignin feedstocks with favorable properties for recovery and downstream conversion. Advances in analytical chemistry and computational modeling detail the structure of the modified lignin and direct bioengineering strategies for future targeted properties. Refinement of biomass pretreatment technologies has further facilitated lignin recovery, and this coupled with genetic engineering will enable new uses for this biopolymer, including low-cost carbon fibers, engineered plastics and thermoplastic elastomers, polymeric foams, fungible fuels, and commodity chemicals.

  12. Lignin degradation during plant litter photodegradation

    Science.gov (United States)

    Lin, Y.; King, J. Y.

    2014-12-01

    Lignin is the second most abundant compound, after cellulose, synthesized by plants. Numerous studies have demonstrated that initial lignin concentration is negatively correlated with litter decomposition rate under both laboratory and field conditions. Thus lignin is commonly considered to be a "recalcitrant" compound during litter decomposition. However, lignin can also serve as a radiation-absorbing compound during photodegradation, the process through which solar radiation breaks down organic matter. Here, we synthesize recent studies concerning lignin degradation during litter photodegradation and report results from our study on how photodegradation changes lignin chemistry at a molecular scale. Recent field studies have found that litter with high initial lignin concentration does not necessarily exhibit high mass loss during photodegradation. A meta-analysis (King et al. 2012) even found a weak negative correlation between initial lignin concentration and photodegradation rate. Contradicting results have been reported with regard to the change in lignin concentration during photodegradation. Some studies have found significant loss of lignin during photodegradation, while others have not. In most studies, loss of lignin only accounts for a small proportion of the overall mass loss. Using NMR spectroscopy, we found significant loss of lignin structural units containing beta-aryl ether linkages during photodegradation of a common grass litter, Bromus diandrus, even though conventional forage fiber analysis did not reveal changes in lignin concentration. Both our NMR and fiber analyses supported the idea that photodegradation induced loss of hemicellulose, which was mainly responsible for the litter mass loss during photodegradation. Our results suggest that photodegradation induces degradation, but not necessarily complete breakdown, of lignin structures and consequently exposes hemicellulose and cellulose to microbial decomposition. We conclude that lignin

  13. Identification of the structure and origin of a thioacidolysis marker compound for ferulic acid incorporation into angiosperm lignins (and an indicator for cinnamoyl CoA reductase deficiency).

    Science.gov (United States)

    Ralph, John; Kim, Hoon; Lu, Fachuang; Grabber, John H; Leplé, Jean-Charles; Berrio-Sierra, Jimmy; Derikvand, Mohammad Mir; Jouanin, Lise; Boerjan, Wout; Lapierre, Catherine

    2008-01-01

    A molecular marker compound, derived from lignin by the thioacidolysis degradative method, for structures produced when ferulic acid is incorporated into lignin in angiosperms (poplar, Arabidopsis, tobacco), has been structurally identified as 1,2,2-trithioethyl ethylguaiacol [1-(4-hydroxy-3-methoxyphenyl)-1,2,2-tris(ethylthio)ethane]. Its truncated side chain and distinctive oxidation state suggest that it derives from ferulic acid that has undergone bis-8-O-4 (cross) coupling during lignification, as validated by model studies. A diagnostic contour for such structures is found in two-dimensional (13)C-(1)H correlated (HSQC) NMR spectra of lignins isolated from cinnamoyl CoA reductase (CCR)-deficient poplar. As low levels of the marker are also released from normal (i.e. non-transgenic) plants in which ferulic acid may be present during lignification, notably in grasses, the marker is only an indicator for CCR deficiency in general, but is a reliable marker in woody angiosperms such as poplar. Its derivation, together with evidence for 4-O-etherified ferulic acid, strongly implies that ferulic acid is incorporated into angiosperm lignins. Its endwise radical coupling reactions suggest that ferulic acid should be considered an authentic lignin precursor. Moreover, ferulic acid incorporation provides a new mechanism for producing branch points in the polymer. The findings sharply contradict those reported in a recent study on CCR-deficient Arabidopsis.

  14. Structural and functional characterization of solute binding proteins for aromatic compounds derived from lignin: p-coumaric acid and related aromatic acids.

    Science.gov (United States)

    Tan, Kemin; Chang, Changsoo; Cuff, Marianne; Osipiuk, Jerzy; Landorf, Elizabeth; Mack, Jamey C; Zerbs, Sarah; Joachimiak, Andrzej; Collart, Frank R

    2013-10-01

    Lignin comprises 15-25% of plant biomass and represents a major environmental carbon source for utilization by soil microorganisms. Access to this energy resource requires the action of fungal and bacterial enzymes to break down the lignin polymer into a complex assortment of aromatic compounds that can be transported into the cells. To improve our understanding of the utilization of lignin by microorganisms, we characterized the molecular properties of solute binding proteins of ATP-binding cassette transporter proteins that interact with these compounds. A combination of functional screens and structural studies characterized the binding specificity of the solute binding proteins for aromatic compounds derived from lignin such as p-coumarate, 3-phenylpropionic acid and compounds with more complex ring substitutions. A ligand screen based on thermal stabilization identified several binding protein clusters that exhibit preferences based on the size or number of aromatic ring substituents. Multiple X-ray crystal structures of protein-ligand complexes for these clusters identified the molecular basis of the binding specificity for the lignin-derived aromatic compounds. The screens and structural data provide new functional assignments for these solute-binding proteins which can be used to infer their transport specificity. This knowledge of the functional roles and molecular binding specificity of these proteins will support the identification of the specific enzymes and regulatory proteins of peripheral pathways that funnel these compounds to central metabolic pathways and will improve the predictive power of sequence-based functional annotation methods for this family of proteins.

  15. Lignin chemistry: biosynthetic study and structural characterisation of coniferyl alcohol oligomers formed in vitro in a micellar environment.

    Science.gov (United States)

    Reale, Samantha; Attanasio, Francesca; Spreti, Nicoletta; De Angelis, Francesco

    2010-05-25

    Model coniferyl alcohol lignin (the so-called dehydrogenative polymerisate, DHP) was produced in water under homogeneous conditions guaranteed by the presence of a micellised cationic surfactant. A complete study of the activity of the enzymatic system peroxidase/H(2)O(2) under our reaction conditions was reported and all the reaction products up to the pentamer were characterised by (1)H NMR spectroscopy and ESI mass spectrometry. Our system, and the molecules that have been generated in it, represent a closer mimicry of the natural microenvironment since an enzyme, under micellar conditions, reproduces the cell system better than in buffer alone. On the basis of the oligomers structures a new biosynthetic perspective was proposed that focused attention on a coniferyl alcohol dimeric quinone methide as the key intermediate of the reaction. A formal, strictly alternate sequence of a radical and an ionic step underlines the reaction, thus generating ordered oligolignols structures. Alternatively to other model lignins, our olignols present a lower degree of radical coupling between oligomeric units. This offers a closer biosynthetic situation to the observation of a low rate of radical generation in the cell wall.

  16. FT-Raman investigation of milled-wood lignins : softwood, hardwood, and chemically modified black spruce lignins

    Science.gov (United States)

    Umesh P. Agarwal; James D. McSweeny; Sally A. Ralph

    2011-01-01

    Raman spectroscopy is being increasingly applied to study wood and other lignin-containing biomass/biomaterials. Lignin’s contribution to the Raman spectra of such materials needs to be understood in the context of various lignin structures, substructures, and functional groups so that lignin-specific features could be identified and the spectral information could be...

  17. IDENTIFICATION OF THE STRUCTURE AND ORIGIN OF A THIOACIDOLYSIS MARKER COMPOUND FOR FERULIC ACID INCORPORATION INTO ANGIOSPERM LIGNINS (AND AN INDICATOR FOR CINNAMOYL-CoA REDUCTASE DEFICIENCY)

    Science.gov (United States)

    A molecular marker compound, derived from lignin by the thioacidolysis degradative method, for structures produced when ferulic acid is incorporated into lignification in angiosperms (poplar, Arabidopsis, tobacco), has been structurally identified as 1,2,2-trithioethyl ethylguaiacol [1-(4-hydroxy-3-...

  18. Impact of lignin and carbohydrate chemical structures on degradation reactions during hardwood kraft pulping processes

    Directory of Open Access Journals (Sweden)

    Ricardo B. Santos

    2013-02-01

    Full Text Available Most studies aimed at determining rates of hardwood delignification and carbohydrate degradation have focused on understanding the behavior of a single wood species. Such studies tend to determine either the delignification rate or the rate of carbohydrate degradation without examining the potential interactions resulting from related variables. The current study provides a comprehensive evaluation on both lignin and carbohydrate degradation during kraft pulping of multiple hardwood species. The kraft delignification rates of E. urograndis, E. nitens, E. globulus, sweet gum, maple, red oak, red alder, cottonwood, and acacia were obtained. Furthermore, the kinetics of glucan, xylan, and total carbohydrate dissolution during the bulk phase of the kraft pulping process for the above species were also investigated. The wide ranges of delignification and carbohydrate degradation rates were correlated to wood chemical characteristics. It appears that the S/G ratio and lignin-carbohydrate-complexes (LCCs are the main characteristics responsible for the differences in kraft pulping performance among the hardwoods studied.

  19. Impact of steam explosion on the wheat straw lignin structure studied by solution-state nuclear magnetic resonance and density functional methods.

    Science.gov (United States)

    Heikkinen, Harri; Elder, Thomas; Maaheimo, Hannu; Rovio, Stella; Rahikainen, Jenni; Kruus, Kristiina; Tamminen, Tarja

    2014-10-29

    Chemical changes of lignin induced by the steam explosion (SE) process were elucidated. Wheat straw was studied as the raw material, and lignins were isolated by the enzymatic mild acidolysis lignin (EMAL) procedure before and after the SE treatment for analyses mainly by two-dimensional (2D) [heteronuclear single-quantum coherence (HSQC) and heteronuclear multiple-bond correlation (HMBC)] and (31)P nuclear magnetic resonance (NMR). The β-O-4 structures were found to be homolytically cleaved, followed by recoupling to β-5 linkages. The homolytic cleavage/recoupling reactions were also studied by computational methods, which verified their thermodynamic feasibility. The presence of the tricin bound to wheat straw lignin was confirmed, and it was shown to participate in lignin reactions during the SE treatment. The preferred homolytic β-O-4 cleavage reaction was calculated to follow bond dissociation energies: G-O-G (guaiacyl) (69.7 kcal/mol) > G-O-S (syringyl) (68.4 kcal/mol) > G-O-T (tricin) (67.0 kcal/mol).

  20. Ligninolytic peroxidase genes in the oyster mushroom genome: heterologous expression, molecular structure, catalytic and stability properties, and lignin-degrading ability

    Science.gov (United States)

    2014-01-01

    Background The genome of Pleurotus ostreatus, an important edible mushroom and a model ligninolytic organism of interest in lignocellulose biorefineries due to its ability to delignify agricultural wastes, was sequenced with the purpose of identifying and characterizing the enzymes responsible for lignin degradation. Results Heterologous expression of the class II peroxidase genes, followed by kinetic studies, enabled their functional classification. The resulting inventory revealed the absence of lignin peroxidases (LiPs) and the presence of three versatile peroxidases (VPs) and six manganese peroxidases (MnPs), the crystal structures of two of them (VP1 and MnP4) were solved at 1.0 to 1.1 Å showing significant structural differences. Gene expansion supports the importance of both peroxidase types in the white-rot lifestyle of this fungus. Using a lignin model dimer and synthetic lignin, we showed that VP is able to degrade lignin. Moreover, the dual Mn-mediated and Mn-independent activity of P. ostreatus MnPs justifies their inclusion in a new peroxidase subfamily. The availability of the whole POD repertoire enabled investigation, at a biochemical level, of the existence of duplicated genes. Differences between isoenzymes are not limited to their kinetic constants. Surprising differences in their activity T50 and residual activity at both acidic and alkaline pH were observed. Directed mutagenesis and spectroscopic/structural information were combined to explain the catalytic and stability properties of the most interesting isoenzymes, and their evolutionary history was analyzed in the context of over 200 basidiomycete peroxidase sequences. Conclusions The analysis of the P. ostreatus genome shows a lignin-degrading system where the role generally played by LiP has been assumed by VP. Moreover, it enabled the first characterization of the complete set of peroxidase isoenzymes in a basidiomycete, revealing strong differences in stability properties and providing

  1. POLYMERIZATION OF DIFFERENT LIGNINS BY LACCASE

    Directory of Open Access Journals (Sweden)

    Maija-Liisa Mattinen

    2008-02-01

    Full Text Available In this study the oxidative polymerization of different lignins, i.e. Flax Soda lignin, Spruce EMAL, and Eucalyptus Dioxane lignin by Trametes hirsuta laccase was compared. Initially the structures of the different lignins were compared by Fourier transform infrared spectroscopy. The reactivity of laccase with the different types of lignins in the absence of mediators was examined and verified by oxygen consumption measurements. The molecular weight distributions of treated and untreated lignins were determined by two different size exclusion chromatography methods. Furthermore, the potential of matrix-assisted laser desorption/ionisation-time of flight-mass spectroscopy for determination of the absolute molecular weights of the different lignins was evaluated. The data showed that all the technical lignins could be activated and polymerized by laccase to different degrees. The efficiency as indicated by measurements of the degree of polymerization was found to increase in the order of Spruce EMAL < Eucalyptus Dioxane lignin < Flax Soda lignin. Overall, this data supplies foundations for using enzymes more efficiently in the enzymatic upgrading of lignin.

  2. Systematic Parameterization of Lignin for the CHARMM Force Field

    Energy Technology Data Exchange (ETDEWEB)

    Vermaas, Joshua; Petridis, Loukas; Beckham, Gregg; Crowley, Michael

    2017-07-06

    Plant cell walls have three primary components, cellulose, hemicellulose, and lignin, the latter of which is a recalcitrant, aromatic heteropolymer that provides structure to plants, water and nutrient transport through plant tissues, and a highly effective defense against pathogens. Overcoming the recalcitrance of lignin is key to effective biomass deconstruction, which would in turn enable the use of biomass as a feedstock for industrial processes. Our understanding of lignin structure in the plant cell wall is hampered by the limitations of the available lignin forcefields, which currently only account for a single linkage between lignins and lack explicit parameterization for emerging lignin structures both from natural variants and engineered lignin structures. Since polymerization of lignin occurs via radical intermediates, multiple C-O and C-C linkages have been isolated , and the current force field only represents a small subset of lignin the diverse lignin structures found in plants. In order to take into account the wide range of lignin polymerization chemistries, monomers and dimer combinations of C-, H-, G-, and S-lignins as well as with hydroxycinnamic acid linkages were subjected to extensive quantum mechanical calculations to establish target data from which to build a complete molecular mechanics force field tuned specifically for diverse lignins. This was carried out in a GPU-accelerated global optimization process, whereby all molecules were parameterized simultaneously using the same internal parameter set. By parameterizing lignin specifically, we are able to more accurately represent the interactions and conformations of lignin monomers and dimers relative to a general force field. This new force field will enables computational researchers to study the effects of different linkages on the structure of lignin, as well as construct more accurate plant cell wall models based on observed statistical distributions of lignin that differ between

  3. THE EFFECT OF GROWTH REGULATOR ON STRUCTURAL AND NON-STRUCTURAL CARBOHYDRATES AND LIGNIN CONTENT IN SELECTED GRASS SPECIES AND CULTIVARS

    Directory of Open Access Journals (Sweden)

    Grażyna Anna Ciepiela

    2015-06-01

    Full Text Available The research was undertaken to determine the effect of the biostimulant Kelpak SL, derived from brown seaweed species Ecklonia maxima (kelp, on structural and non-structural carbohydrates, as well as lignin content in orchard grass and Braun’s festulolium. The experiment was a split-plot arrangement with three replicates. It was set up at the experimental facility of the University of Natural Sciences and Humanities, Siedlce, in late April 2009. The following factors were examined: an application of the plant growth regulator Kelpak SL applied at the rate of 2 dm3· ha-1 vs an untreated control (0 dm3· ha-1, pure sown grass species and cultivars grown in monoculture: Dactylis glomerata, cv. Amila and Tukan, as well as Festulolium braunii cv. Felopa and Agula. This study revealed that an application of Kelpak significantly reduced cellulose, hemicellulose and lignin contents of the grasses but significantly increased non-structural carbohydrates, regardless of the remaining factors. Non-structural carbohydrates were the highest in Kelpak-treated Festulolium braunii (on average, 232.7 g · kg-1.

  4. Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, M. R.; Kim, S.; Chmely, S. C.; Foust, T. D.; Beckham, G. T.

    2013-01-01

    Carbon-oxygen bonds are the primary inter-monomer linkages lignin polymers in plant cell walls, and as such, catalyst development to cleave these linkages is of paramount importance to deconstruct biomass to its constituent monomers for the production of renewable fuels and chemicals. For many decades, acid catalysis has been used to depolymerize lignin. Lignin is a primary component of plant cell walls, which is connected primarily by aryl-ether linkages, and the mechanism of its deconstruction by acid is not well understood, likely due to its heterogeneous and complex nature compared to cellulose. For effective biomass conversion strategies, utilization of lignin is of significant relevance and as such understanding the mechanisms of catalytic lignin deconstruction to constituent monomers and oligomers is of keen interest. Here, we present a comprehensive experimental and theoretical study of the acid catalysis of a range of dimeric species exhibiting the b-O-4 linkage, the most common inter-monomer linkage in lignin. We demonstrate that the presence of a phenolic species dramatically increases the rate of cleavage in acid at 150 degrees C. Quantum mechanical calculations on dimers with the para-hydroxyl group demonstrate that this acid-catalyzed pathway differs from the nonphenolic dimmers. Importantly, this result implies that depolymerization of native lignin in the plant cell wall will proceed via an unzipping mechanism wherein b-O-4 linkages will be cleaved from the ends of the branched, polymer chains inwards toward the center of the polymer. To test this hypothesis further, we synthesized a homopolymer of b-O-4 with a phenolic hydroxyl group, and demonstrate that it is cleaved in acid from the end containing the phenolic hydroxyl group. This result suggests that genetic modifications to lignin biosynthesis pathways in plants that will enable lower severity processes to fractionate lignin for upgrading and for easier access to the carbohydrate fraction of

  5. Lignin-Derived Advanced Carbon Materials.

    Science.gov (United States)

    Chatterjee, Sabornie; Saito, Tomonori

    2015-12-07

    Lignin is a highly abundant source of renewable carbon that can be considered as a valuable sustainable source of biobased materials. By applying specific pretreatments and manufacturing methods, lignin can be converted into a variety of value-added carbon materials. However, the physical and chemical heterogeneities of lignin complicate its use as a feedstock. Herein lignin manufacturing process, the effects of pretreatments and manufacturing methods on the properties of product lignin, and structure-property relationships in various applications of lignin-derived carbon materials, such as carbon fibers, carbon mats, activated carbons, carbon films, and templated carbon, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. SYNTHESIS AND CHARACTERIZATION OF KRAFT LIGNIN-BASED EPOXY RESINS

    Directory of Open Access Journals (Sweden)

    Nour Eddine El Mansouri

    2011-05-01

    Full Text Available Epoxidization is an interesting way to develop a new application of lignin and therefore to improve its application potential. In this work, kraft lignin-based epoxy resins were obtained by the epoxidization reaction, using the kraft lignin recovered directly from pulping liquor and modified by a methylolation reaction. The methylolated lignins were obtained by the reaction of original kraft lignin with formaldehyde and glyoxal, which is a less volatile and less toxic aldehyde. 1H-NMR spectroscopy showed that methylolated kraft lignin has more hydroxymethyl groups than glyoxalated kraft lignin. For the epoxidization reaction we studied the influence of the lignin:NaOH (w/w ratio, temperature, and time of the reaction on the properties of the prepared epoxidized lignins. The structures of lignin-based epoxy resins were followed by epoxy index test and FTIR spectroscopy. Optimal conditions were obtained for lignin-based epoxy resin produced at lignin/NaOH = 1/3 at 70 ºC for 3h. Thermogravimetry analysis (TGA revealed that the epoxidization enhances the thermal stability of lignins and may allow a wider temperature range for applications with lignin epoxy-PF blends.

  7. Effect of Lignin Structure on Antioxidation in Polypropylene%木质素结构在聚丙烯中抗氧化作用的影响

    Institute of Scientific and Technical Information of China (English)

    郑秋闿; 范晶晶; 许凯; 陈鸣才

    2013-01-01

    Effects of lignins extracted from cornstalk,birch and pine on antioxidantive properties of PP at the contents of 0.2% to 1.0% were investigated by testing oxidation induced temperature on DSC.The results showed that the three lignins with different structure had some effect on antioxidation,of which the lignin of coniferous wood had the best effect.The IR and 1H-NMR analysis showed that abundant guaiacylpropane units and no syringylpropane unit were found in the lignin structure of pine.Besides both guaiacylpropane and syringylpropane units were found in the lignin structure of cornstalk and birch,which could explain the difference in antioxidantive effects.The results of the IR and 1H-NMR analysis indicated that hydroxyls contributed a lot to lignin antioxidant activity.%采用氧化诱导温度测试方法,研究了添加0.2% ~1.0%桦木木质素、松木木质素和玉米秆木质素的聚丙烯的抗氧化性能.结果表明,3种结构不同的木质素都有一定的抗氧化效果,其中针叶材木质素的抗氧化效果最好.通过红外光谱和核磁共振氢谱分析了各种木质素的结构,发现针叶材木质素中含有大量的愈创木基丙烷结构,而没有紫丁香基丙烷结构的存在;阔叶材木质素和草本木质素中既有愈创木基丙烷结构也有紫丁香基丙烷结构,从结构上解释了来源不同的木质素抗氧化效果不同的原因.结合不同木质素样品的红外光谱和核磁共振氢谱分析得知,羟基对木质素的抗氧化性有较大贡献.

  8. Effect of the molecular structure of lignin-based polyoxyethylene ether on enzymatic hydrolysis efficiency and kinetics of lignocelluloses.

    Science.gov (United States)

    Lin, Xuliang; Qiu, Xueqing; Zhu, Duming; Li, Zihao; Zhan, Ningxin; Zheng, Jieyi; Lou, Hongming; Zhou, Mingsong; Yang, Dongjie

    2015-10-01

    Effect of the molecular structure of lignin-based polyoxyethylene ether (EHL-PEG) on enzymatic hydrolysis of Avicel and corn stover was investigated. With the increase of PEG contents and molecular weight of EHL-PEG, glucose yield of corn stover increased. EHL-PEG enhanced enzymatic hydrolysis of corn stover significantly at buffer pH 4.8-5.5. Glucose yield of corn stover at 20% solid content increased from 32.8% to 63.8% by adding EHL-PEG, while that with PEG4600 was 54.2%. Effect of EHL-PEG on enzymatic hydrolysis kinetics of cellulose film was studied by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). An enhancing mechanism of EHL-PEG on enzymatic hydrolysis kinetics of cellulose was proposed. Cellulase aggregates dispersed by EHL-PEG excavated extensive cavities into the surface of cellulose film, making the film become more loose and exposed. After the maximum enzymatic hydrolysis rate, the film was mainly peeled off layer by layer until equilibrium. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Improving the pH-stability of Versatile Peroxidase by Comparative Structural Analysis with a Naturally-Stable Manganese Peroxidase (+ correction)

    NARCIS (Netherlands)

    Saez-Jimenez, V.; Fernandez Fueyo, E.; Madrano, F.J.; Romero, A.; Martinez, A.T.; Ruiz-Duenas, F.J.

    2015-01-01

    Versatile peroxidase (VP) from the white-rot fungus Pleurotus eryngii is a high redox potential peroxidase of biotechnological interest able to oxidize a wide range of recalcitrant substrates including lignin, phenolic and non-phenolic aromatic compounds and dyes. However, the relatively low stabili

  10. Genetic Augmentation of Syringyl Lignin in Low-lignin Aspen Trees, Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Chung-Jui Tsai; Mark F. Davis; Vincent L. Chiang

    2004-11-10

    As a polysaccharide-encrusting component, lignin is critical to cell wall integrity and plant growth but also hinders recovery of cellulose fibers during the wood pulping process. To improve pulping efficiency, it is highly desirable to genetically modify lignin content and/or structure in pulpwood species to maximize pulp yields with minimal energy consumption and environmental impact. This project aimed to genetically augment the syringyl-to-guaiacyl lignin ratio in low-lignin transgenic aspen in order to produce trees with reduced lignin content, more reactive lignin structures and increased cellulose content. Transgenic aspen trees with reduced lignin content have already been achieved, prior to the start of this project, by antisense downregulation of a 4-coumarate:coenzyme A ligase gene (Hu et al., 1999 Nature Biotechnol 17: 808- 812). The primary objective of this study was to genetically augment syringyl lignin biosynthesis in these low-lignin trees in order to enhance lignin reactivity during chemical pulping. To accomplish this, both aspen and sweetgum genes encoding coniferaldehyde 5-hydroxylase (Osakabe et al., 1999 PNAS 96: 8955-8960) were targeted for over-expression in wildtype or low-lignin aspen under control of either a constitutive or a xylem-specific promoter. A second objective for this project was to develop reliable and cost-effective methods, such as pyrolysis Molecular Beam Mass Spectrometry and NMR, for rapid evaluation of cell wall chemical components of transgenic wood samples. With these high-throughput techniques, we observed increased syringyl-to-guaiacyl lignin ratios in the transgenic wood samples, regardless of the promoter used or gene origin. Our results confirmed that the coniferaldehyde 5-hydroxylase gene is key to syringyl lignin biosynthesis. The outcomes of this research should be readily applicable to other pulpwood species, and promise to bring direct economic and environmental benefits to the pulp and paper industry.

  11. Structure and Biochemestry of Laccases from the Lignin-Degrading Basidiomycete, Ganoderma lucidum

    Energy Technology Data Exchange (ETDEWEB)

    C.A.Reddy, PI

    2005-06-30

    G. lucidum is one of the most important and widely distributed ligninolytic white rot fungi from habitats such as forest soils, agricultural soils, and tropical mangrove ecosystems and produce laccases as an important family of lignin modifying enzymes. Biochemically, laccases are blue multi copper oxidases that couple four electron reduction of molecular oxygen to water. There is a growing interest in the use of laccases for a variety of industrial applications such as bio-pulping and biobleaching as well as in their ability to detoxify a wide variety of toxic environmental pollutants. These key oxidative enzymes are found in all the three domains of life: Eukaryota. Prokarya, and Archaea. Ganoderma lucidum (strain no.103561) produces laccase with some of the highest activity (17,000 micro katals per mg of protein) reported for any laccases to date. Our results showed that this organism produces at least 11 different isoforms of laccase based on variation in mol. weight and/or PI. Our Studies showed that the presence of copper in the medium yields 15- to 20-fold greater levels of enzyme by G. lucidum. Dialysation of extra cellular fluid of G. lucidum against 10mM sodium tartrate (pH5.5) gave an additional 15 to 17 fold stimulation of activity with an observed specific activity of 17,000 {micro}katals/mg protein. Dialysis against acetate buffer gave five fold increase in activity while dialysis against glycine showed inhibition of activity. Purification by FPLC and preparative gel electrophoresis gave purified fractions that resolved into eleven isoforms as separated by isoelectric focusing, and the PI,s were 4.7, 4.6, 4.5, 4.3, 4.2, 4.1, 3.8, 3.7, 3.5, 3.4 and 3.3. Genomic clones of laccase were isolated using G. lucidum DNA as a template and using inverse PCR and forward/reverse primers corresponding to the sequences of the conserved copper binding region in the N-terminal domain of one of the laccases of this organism. Inverse PCR amplication of HindIII digested

  12. Structure and Biochemestry of Laccases from the Lignin-Degrading Basidiomycete, Ganoderma lucidum

    Energy Technology Data Exchange (ETDEWEB)

    C.A.Reddy, PI

    2005-06-30

    G. lucidum is one of the most important and widely distributed ligninolytic white rot fungi from habitats such as forest soils, agricultural soils, and tropical mangrove ecosystems and produce laccases as an important family of lignin modifying enzymes. Biochemically, laccases are blue multi copper oxidases that couple four electron reduction of molecular oxygen to water. There is a growing interest in the use of laccases for a variety of industrial applications such as bio-pulping and biobleaching as well as in their ability to detoxify a wide variety of toxic environmental pollutants. These key oxidative enzymes are found in all the three domains of life: Eukaryota. Prokarya, and Archaea. Ganoderma lucidum (strain no.103561) produces laccase with some of the highest activity (17,000 micro katals per mg of protein) reported for any laccases to date. Our results showed that this organism produces at least 11 different isoforms of laccase based on variation in mol. weight and/or PI. Our Studies showed that the presence of copper in the medium yields 15- to 20-fold greater levels of enzyme by G. lucidum. Dialysation of extra cellular fluid of G. lucidum against 10mM sodium tartrate (pH5.5) gave an additional 15 to 17 fold stimulation of activity with an observed specific activity of 17,000 {micro}katals/mg protein. Dialysis against acetate buffer gave five fold increase in activity while dialysis against glycine showed inhibition of activity. Purification by FPLC and preparative gel electrophoresis gave purified fractions that resolved into eleven isoforms as separated by isoelectric focusing, and the PI,s were 4.7, 4.6, 4.5, 4.3, 4.2, 4.1, 3.8, 3.7, 3.5, 3.4 and 3.3. Genomic clones of laccase were isolated using G. lucidum DNA as a template and using inverse PCR and forward/reverse primers corresponding to the sequences of the conserved copper binding region in the N-terminal domain of one of the laccases of this organism. Inverse PCR amplication of HindIII digested

  13. Modulating lignin in plants

    Science.gov (United States)

    Apuya, Nestor; Bobzin, Steven Craig; Okamuro, Jack; Zhang, Ke

    2013-01-29

    Materials and methods for modulating (e.g., increasing or decreasing) lignin content in plants are disclosed. For example, nucleic acids encoding lignin-modulating polypeptides are disclosed as well as methods for using such nucleic acids to generate transgenic plants having a modulated lignin content.

  14. Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization.

    Science.gov (United States)

    Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M; Héroguel, Florent; Li, Yanding; Kim, Hoon; Meilan, Richard; Chapple, Clint; Ralph, John; Luterbacher, Jeremy S

    2016-10-21

    Practical, high-yield lignin depolymerization methods could greatly increase biorefinery productivity and profitability. However, development of these methods is limited by the presence of interunit carbon-carbon bonds within native lignin, and further by formation of such linkages during lignin extraction. We report that adding formaldehyde during biomass pretreatment produces a soluble lignin fraction that can be converted to guaiacyl and syringyl monomers at near theoretical yields during subsequent hydrogenolysis (47 mole % of Klason lignin for beech and 78 mole % for a high-syringyl transgenic poplar). These yields were three to seven times those obtained without formaldehyde, which prevented lignin condensation by forming 1,3-dioxane structures with lignin side-chain hydroxyl groups. By depolymerizing cellulose, hemicelluloses, and lignin separately, monomer yields were between 76 and 90 mole % for these three major biomass fractions. Copyright © 2016, American Association for the Advancement of Science.

  15. Organosolv Lignin-Based Wood Adhesive. Influence of the Lignin Extraction Conditions on the Adhesive Performance

    Directory of Open Access Journals (Sweden)

    Issam Dababi

    2016-09-01

    Full Text Available Ethanol organosolv alfa grass lignins were extracted in the presence of sulfuric acid or Lewis acids (Sc(OTf3, FeCl3 as catalysts and subjected to a comprehensive structural characterization by solid state 13C NMR, GPC, MALDI-TOF, and ASAP-MS/MS. The impact of the severity of the treatment and of the nature of the acid catalyst on the recovered lignin structure was investigated. The lignins isolated at high severity were highly recondensed and partly composed of regular structures composed of furan-like rings. The alfa (Stipa tenacissima L. organosolv lignins were used for the preparation of formaldehyde-free adhesives which were characterized by TMA and used for the preparation of particleboard without any addition of synthetic resin. It has been demonstrated for the first time that: (1 the addition of 10% to 30% of organosolv alfa lignin in a tannin-based adhesive improved the adhesive performance; and (2 the conditions of the lignin extraction strongly impact the lignin-based adhesive performances. The highly recondensed lignin extracted with sulfuric acid as a catalyst allowed the production of resins with improved performances. Formulations composed of 50% glyoxalated alfa lignin and 50% of Aleppo Pine tannins yielded good internal bond strength results for the panels (IB = 0.45 MPa and satisfied relevant international standard specifications for interior-grade panels.

  16. STUDY ON THE STRUCTURAL CHANGE OF LIGNIN DURING AUTO-CATALYZED ETHANOL-WATER PULPING OF ASPEN BY 1H-NMR

    Directory of Open Access Journals (Sweden)

    Jinghui Zhou

    2009-08-01

    Full Text Available This study concerns the structural change of lignin during auto-catalyzed ethanol-water pulping of aspen by 1H-NMR. The results showed that the linkages of alkyl-aryl ether of lignin, such as the α-ether linkages (α-O-4 and the β-ether linkages (β-O-4, were broken and the alkyl part formed carbenium at the Cα and Cβ of the aliphatic branch. Meanwhile, the aryl part of ether accepted one H+ and formed phenol. Because of the electronegative effect originating from the electron cloud of phenyl, partial carbenium of Cβ was rearranged. Due to its ether or hydroxyl linkage, rearranging to Cβ, the Cα was changed into carbenium and formed a new β-O-4 alkyl-aryl ether. The β-O-4 alkyl-aryl ether was not stable and broken further. So the large molecule of lignin was disintegrated into a smaller one and dissolved into ethanol. Finally, the α+ carbenium reformed α-O-4 linkages of ether with phenol.

  17. Characterization of the effects of lignin and lignin complex particles as filler on a polystyrene film

    Energy Technology Data Exchange (ETDEWEB)

    El-Zawawy, Waleed K., E-mail: wkzawawy@yahoo.com [Cellulose and Paper Department, National Research Center, El-Tahrir St., Giza (Egypt); Ibrahim, Maha M. [Cellulose and Paper Department, National Research Center, El-Tahrir St., Giza (Egypt); Belgacem, Mohamed Naceur; Dufresne, Alain [Grenoble Institute of Technology (INP) - The International School of Paper, Print Media and Biomaterials (PAGORA), BP 65, 38402 Saint Martin d' Heres cedex, Grenoble (France)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer We have studied the use of Co(II) to form a complex with the lignin. We use first vanillin as the lignin model and we observed a change in color for the produced complex depending on the light wavelength. The use of other transition metals does not give the same observation. Black-Right-Pointing-Pointer The use of the transition metal with the lignin precipitated from the black liquor after pulping of agricultural residues, gave a fluorescent color under fluorescent microscope. Black-Right-Pointing-Pointer We applied the resulted lignin complex to prepare polymer film that can be used as special polymer packaging which can be color changed under different wavelengths. - Abstract: The work in this research outlines the use of lignin precipitated from lignocellulosic substrate as fillers after modified with transition metal cations, Fe(III), Ni(II) and Co(II), in the production of a polystyrene based composite for polymer packaging applications. Virgin polystyrene was compared with lignin and lignin complex filled composites with loading of 5% by weight prepared using twin screw extrusion. The lignin complexes were first characterized by the UV spectra to identify the new absorption bands occurred due to the complex formation. Moreover, lignin model, namely vanillin, was used to notify the geometric structure of the resulting complexes applying the GC mass spectra. Scanning electron microscopy was used to indicate the change in the morphological structure of the filler particles. On the other hand, the mechanical and thermal analysis for the resulting polymer composites was studied and it was noticed that the type of lignin or lignin complex plays a roll in the results. The inclusion of the Co(II)-lignin complex was observed to increase the tensile strength of the resulting polymer composite and a decrease of the glass transition temperature. Furthermore, light wave lengths and UV fluorescent microscope were used to identify

  18. Lignin biomass conversion into chemicals and fuels

    DEFF Research Database (Denmark)

    Melián Rodríguez, Mayra

    % of the weight and 40% of the energy content of lignocellulosic biomass. While designated applications for cellulose already exist in form of the current pulp and paper production as well as its prospective hydrolysis and fermentation into biofuels (mainly bioethanol), sustainable ways to valorize the lignin...... fraction of wood are yet to be established, due to its poor solubility and complex heterogeneous structure. This constitutes a major drawback in the economic viability of a biorefinery, where complete valorization of lignocellulosic biomass is necessary. For this reason, and due to its potential...... as a valuable feedstock for the production of organic chemicals, lignin valorization has become an important issue to solve. For a better understanding and analysis of the catalytic performance of lignin, it is common to use lignin model compounds, which contain the most significant linkages present in lignin...

  19. Multidimensional NMR analysis reveals truncated lignin structures in wood decayed by the brown rot basidiomycete Postia placenta

    Science.gov (United States)

    Daniel J. Yelle; Dongsheng Wei; John Ralph; Kenneth E. Hammel

    2011-01-01

    Lignocellulose biodegradation, an essential step in terrestrial carbon cycling, generally involves removal of the recalcitrant lignin barrier that otherwise prevents infiltration by microbial polysaccharide hydrolases. However, fungi that cause brown rot of wood, a major route for biomass recycling in coniferous forests, utilize wood polysaccharides efficiently while...

  20. Analytical methodology for sulfonated lignins

    NARCIS (Netherlands)

    Brudin, S.; Schoenmakers, P.

    2010-01-01

    There is a significant need to characterize and classify lignins and sulfonated lignins. Lignins have so far received a good deal of attention, whereas this is not true for sulfonated lignins. There is a clear demand for a better understanding of sulfonated lignins on a chemical as well as physical

  1. Analytical methodology for sulfonated lignins

    NARCIS (Netherlands)

    Brudin, S.; Schoenmakers, P.

    2010-01-01

    There is a significant need to characterize and classify lignins and sulfonated lignins. Lignins have so far received a good deal of attention, whereas this is not true for sulfonated lignins. There is a clear demand for a better understanding of sulfonated lignins on a chemical as well as physical

  2. 硫酸盐浆残余木素在漆酶/介体体系中的降解%Degradation of Residual Lignin in Kraft Pulp by Laccase and Mediator System

    Institute of Scientific and Technical Information of China (English)

    付时雨; 詹怀宇; 何为

    2002-01-01

    桉木硫酸盐浆(EMCC浆)用漆酶/介体(N-羟基-N-乙酰苯胺)体系(LMS)进行处理.采用GPC、FTIR和2D13C-1H-NMR技术分析了原浆木素、LMS处理过的浆中残余木素以及E段废液中分离出来的木素,并在碱性条件下用硝基苯氧化上述木素.实验结果表明,LMS处理后桉木EMCC浆中残余木素发生很大的变化,大多数非缩合的木素结构单元被降解.NMR研究结果表明,LMS处理的浆中木素和E段废液木素的β-O-4和β-5结构消失,紫丁香基结构的信号大大减弱,而木素中二苯乙烯结构、二苯甲烷结构和非酚型的5-5'结构在LMS生物处理时比较稳定,难于降解.LMS处理时木素发生α-位羟基的氧化产生α-羰基,并在其后的碱处理段被降解成小分子量的碎片.纸浆残余木素经漆酶/介体体系处理发生一定的苯环开环作用,使木素的羧基增加.%Eucalyptus EMCC pulp was treated with laccase and N-acetyl-N-hydroxyl-aniline system. The residual lignin from the original pulp and the LMS treated pulp, as well as lignin isolated from the E-stage effluent, were prepared, then analyzed using GPC, FTIR and 2D13C-1H-NMR techniques, and oxidized by nitrobenzene in the alkaline condition. The results indicated that the structure of residual lignin undertook a lot of changes in the eucalyptus EMCC pulp after LMS treatment, most of noncondensed substructures of lignin were degraded. The NMR studies showed the disappearance of β-O-4 and β-5 bonds in the structure of residual lignin from LMS treated pulp and the lignin from E-stage effluent, and the signal strength of syringyl structure decreased greatly. Stilbene, dibenzene methane and non-phenolic 5-5' type substructures in lignin were stable to LMS treatment, and difficult to be degraded. During the LMS treatment, α-carbon with hydroxyl group in lignin was subjected to oxidize to α-carbonyl, which can be degraded by alkaline extraction to fragment with small molecular weight; open

  3. Towards a detailed understanding of the structural variability in lignins: A new approach. Progress report, April 1991--June 1993

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, N.G.; Towers, G.H.N.

    1993-12-31

    This reporting period witnessed a number of exciting and important breakthroughs in the study of lignin synthesis in plants and resulted in a significant deviation from the work plan originally proposed. Taken together, the authors` results reveal an emerging picture of a highly ordered assembly of the lignin polymer at the plasma membrane/cell-wall interface, in contrast to original considerations projecting a random series of coupling reactions. The Progress Report is divided into two sections: the first section reflects the interlocking research completed to date in the laboratories of N.G. Lewis and G.H.N. Towers. In the broadest sense, the Lewis group has focused mainly on woody plants, whereas the Towers laboratory examined similar processes in cereals/grasses. The second section compiles published work, a summary of manuscripts in preparation, and work currently underway for year three of the existing grant.

  4. Bacteria and lignin degradation

    Institute of Scientific and Technical Information of China (English)

    Jing LI; Hongli YUAN; Jinshui YANG

    2009-01-01

    Lignin is both the most abundant aromatic (phenolic) polymer and the second most abundant raw material.It is degraded and modified by bacteria in the natural world,and bacteria seem to play a leading role in decomposing lignin in aquatic ecosystems.Lignin-degrading bacteria approach the polymer by mechanisms such as tunneling,erosion,and cavitation.With the advantages of immense environmental adaptability and biochemical versatility,bacteria deserve to be studied for their ligninolytic potential.

  5. Immunolocalization of 8-5' and 8-8' linked structures of lignin in cell walls of Chamaecyparis obtusa using monoclonal antibodies.

    Science.gov (United States)

    Kiyoto, Shingo; Yoshinaga, Arata; Tanaka, Naoyuki; Wada, Munehisa; Kamitakahara, Hiroshi; Takabe, Keiji

    2013-03-01

    Mouse monoclonal antibodies were generated against dehydrodiconiferyl alcohol- or pinoresinol-p-aminohippuric acid (pAHA)-bovine serum albumin (BSA) conjugate as probes that specifically react with 8-5' or 8-8' linked structure of lignin in plant cell walls. Hybridoma clones were selected that produced antibodies that positively reacted with dehydrodiconiferyl alcohol- or pinoresinol-pAHA-BSA and negatively reacted with pAHA-BSA and guaiacylglycerol-beta-guaiacyl ether-pAHA-BSA conjugates containing 8-O-4' linkage. Eight clones were established for each antigen and one of each clone that positively reacted with wood sections was selected. The specificity of these antibodies was examined by competitive ELISA tests using various lignin dimers with different linkages. The anti-dehydrodiconiferyl alcohol antibody reacted specifically with dehydrodiconiferyl alcohol and did not react with other model compounds containing 8-O-4', 8-8', or 5-5' linkages. The anti-pinoresinol antibody reacted specifically with pinoresinol and syringaresinol and did not react with the other model compounds containing 8-O-4', 8-5', or 5-5' linkages. The antibodies also did not react with dehydrodiconiferyl alcohol acetate or pinoresinol acetate, indicating that the presence of free phenolic or aliphatic hydroxyl group was an important factor in their reactivity. In sections of Japanese cypress (Chamaecyparis obtusa), labeling by the anti-dehydrodiconiferyl alcohol antibody was found in the secondary walls of phloem fibers and in the compound middle lamellae, and secondary walls of tracheids. Weak labeling by the anti-pinoresinol antibody was found in secondary walls of phloem fibers and secondary walls and compound middle lamellae of developed tracheids. These labelings show the localization of 8-5' and 8-8' linked structure of lignin in the cell walls.

  6. Lignin from Micro- to Nanosize: Production Methods

    Science.gov (United States)

    Beisl, Stefan; Miltner, Angela; Friedl, Anton

    2017-01-01

    Lignin is the second most abundant biopolymer after cellulose. It has long been obtained as a by-product of cellulose production in pulp and paper production, but had rather low added-value applications. A changing paper market and the emergence of biorefinery projects should generate vast amounts of lignin with the potential of value addition. Nanomaterials offer unique properties and the preparation of lignin nanoparticles and other nanostructures has therefore gained interest as a promising technique to obtain value-added lignin products. Due to lignin’s high structural and chemical heterogeneity, methods must be adapted to these different types. This review focuses on the ability of different formation methods to cope with the huge variety of lignin types and points out which particle characteristics can be achieved by which method. The current research’s main focus is on pH and solvent-shifting methods where the latter can yield solid and hollow particles. Solvent shifting also showed the capability to cope with different lignin types and solvents and antisolvents, respectively. However, process conditions have to be adapted to every type of lignin and reduction of solvent demand or the integration in a biorefinery process chain must be focused. PMID:28604584

  7. Lignin from Micro- to Nanosize: Production Methods

    Directory of Open Access Journals (Sweden)

    Stefan Beisl

    2017-06-01

    Full Text Available Lignin is the second most abundant biopolymer after cellulose. It has long been obtained as a by-product of cellulose production in pulp and paper production, but had rather low added-value applications. A changing paper market and the emergence of biorefinery projects should generate vast amounts of lignin with the potential of value addition. Nanomaterials offer unique properties and the preparation of lignin nanoparticles and other nanostructures has therefore gained interest as a promising technique to obtain value-added lignin products. Due to lignin’s high structural and chemical heterogeneity, methods must be adapted to these different types. This review focuses on the ability of different formation methods to cope with the huge variety of lignin types and points out which particle characteristics can be achieved by which method. The current research’s main focus is on pH and solvent-shifting methods where the latter can yield solid and hollow particles. Solvent shifting also showed the capability to cope with different lignin types and solvents and antisolvents, respectively. However, process conditions have to be adapted to every type of lignin and reduction of solvent demand or the integration in a biorefinery process chain must be focused.

  8. Added value of lignin as lignin-based hybrid polyurethane for a compatibilizing agent

    Science.gov (United States)

    Ilmiati, S.; Haris Mustafa, J.; Yaumal, A.; Hanum, F.; Chalid, M.

    2017-07-01

    As biomass-based material, lignin contains abundant hydroxyl groups promising to be used as chain extender in building hybrid polyurethanes. Consisting of polyehtylene glycol (PEG) content as hydrophobic part and lignin as hydrophilic part, the hybrid PU is expected to be as a novel compatibilizing agent in new materials production such as polyblends and composites. The hybrid PU was synthesized via two reaction stages, viz. pre-polyurethanization through reacting 4,4'-Methylenebis (Cyclohexyl Isocyanate) (HMDI) and PEG as polyol, and chain extention through adding lignin in the pre-polyurethanization system. The composition effect of lignin in hybrid PU syntehsis, to chemical structure corelated to hydrophobic to hydrophilic ratio, thermal and morphological properties, was evaluated by measuring NMR, FTIR, DSC, TGA and FE-SEM. The experiments showed that addition of lignin was able to extend the pre-polyurethane into hybrid polyurethane and to increase the lignin/polyol ratio in the hybrid polyurethanes, which were indicated by NMR and FTIR Analysis. And change of the ratio lead to increase the glass transition from 60.9 until 62.1°C and degradation temperature from 413.9 until 416.0°C. Observation of the morphology implied that addition of lignin gave more agglomerations. A Further investigation for this characterization study should be focused on a feasibility for this modified lignin as a novel compatibilizing agent.

  9. Biotechnological modification of lignin

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    A literature search of organisms capable of degrading lignin was conducted. Four fungi were selected for study and these were Phanerochaete chrysosporium, Chrysosporium pruinosum, Phlebia tremellosus and Trametes versicolor. Other organisms, Pleurotus ostreatus, Pleurotus florida and Lentinus edodes were also tested in preliminary experiments. All cultures were screened for their ability to degrade the lignin component of aspen sawdust and also lignin extracted from steam-exploded wood. This type of screen was followed by analysis of culture filtrates for the presence of ligninase, the marker enzyme for lignin degradation. Phanerochaete chrysosporium and consequently chosen for further studies in fermentors. Considerable efforts were directed to production of ligninase in fermentors. Only when Chrysosporium pruinosum was pre-cultured in a shake flask for 4 days and then transferred to a fermentor could ligninase activity be detected. The enzyme from shake flasks has been concentrated ready for use in bench-scale studies on cell-free depolymerization of lignin. 13 refs., 8 tabs.

  10. Characteristics of lignin from flax shives as affected by extraction conditions.

    Science.gov (United States)

    Ross, Kelly; Mazza, Giuseppe

    2010-10-20

    Lignin, a polyphenolic molecule, is a major constituent of flax shives. This polyphenolic molecular structure renders lignin a potential source of a variety of commercially viable products such as fine chemicals. This work compares the performance of different lignin isolation methods. Lignin from flax shive was isolated using both conventional alkaline extraction method and a novel experimental pressurized low polarity water (PLPW) extraction process. The lignin yields and chemical composition of the lignin fractions were determined. The conventional alkali treatment with 1.25 M NaOH, heated at 80 °C for 5 h, extracted 92 g lignin per kg flax shives, while lignin yields from the PLPW extracts ranged from 27 to 241 g lignin per kg flax shives. The purity and monomeric composition of the lignins obtained from the different extraction conditions was assessed via UV spectroscopy and alkaline nitrobenzene oxidation. Lignin obtained from conventional alkali treatment with 1.25 M NaOH, heated at 80 °C for 5 h was of low purity and exhibited the lowest yields of nitrobenzene oxidation products. With respect to alkali assisted PLPW extractions, temperature created an opposing effect on lignin yield and nitrobenzene oxidation products. More lignin was extracted as temperature increased, yet the yield of nitrobenzene oxidation products decreased. The low yield of nitrobenzene oxidation products may be attributed to either the formation of condensed structures or the selective dissolution of condensed structures of lignin during the pressurized alkaline high temperature treatment. Analytical pyrolysis, using pyroprobe GC-MS, was used to investigate the molecular composition of the lignin samples. The total yield of pyrolysis lignin products was 13.3, 64.7, and 30.5% for the 1.25 M NaOH extracted lignin, alkaline assisted PLPW extracted lignin, and the unprocessed flax shives, respectively. Key lignin derived compounds such as guaiacol, 4-vinyl guaiacol, 4-methyl guaiacol

  11. Lignin-Retaining Transparent Wood.

    Science.gov (United States)

    Li, Yuanyuan; Fu, Qiliang; Rojas, Ramiro; Yan, Min; Lawoko, Martin; Berglund, Lars

    2017-09-11

    Optically transparent wood, combining optical and mechanical performance, is an emerging new material for light-transmitting structures in buildings with the aim of reducing energy consumption. One of the main obstacles for transparent wood fabrication is delignification, where around 30 wt % of wood tissue is removed to reduce light absorption and refractive index mismatch. This step is time consuming and not environmentally benign. Moreover, lignin removal weakens the wood structure, limiting the fabrication of large structures. A green and industrially feasible method has now been developed to prepare transparent wood. Up to 80 wt % of lignin is preserved, leading to a stronger wood template compared to the delignified alternative. After polymer infiltration, a high-lignin-content transparent wood with transmittance of 83 %, haze of 75 %, thermal conductivity of 0.23 W mK(-1) , and work-tofracture of 1.2 MJ m(-3) (a magnitude higher than glass) was obtained. This transparent wood preparation method is efficient and applicable to various wood species. The transparent wood obtained shows potential for application in energy-saving buildings. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  12. Advanced Model Compounds for Understanding Acid-Catalyzed Lignin Depolymerization: Identification of Renewable Aromatics and a Lignin-Derived Solvent.

    Science.gov (United States)

    Lahive, Ciaran W; Deuss, Peter J; Lancefield, Christopher S; Sun, Zhuohua; Cordes, David B; Young, Claire M; Tran, Fanny; Slawin, Alexandra M Z; de Vries, Johannes G; Kamer, Paul C J; Westwood, Nicholas J; Barta, Katalin

    2016-07-20

    The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges to methodology development. Ideally, new methods should be tested on model compounds that are complex enough to mirror the structural diversity in lignin but still of sufficiently low molecular weight to enable facile analysis. In this contribution, we present a new class of advanced (β-O-4)-(β-5) dilinkage models that are highly realistic representations of a lignin fragment. Together with selected β-O-4, β-5, and β-β structures, these compounds provide a detailed understanding of the reactivity of various types of lignin linkages in acid catalysis in conjunction with stabilization of reactive intermediates using ethylene glycol. The use of these new models has allowed for identification of novel reaction pathways and intermediates and led to the characterization of new dimeric products in subsequent lignin depolymerization studies. The excellent correlation between model and lignin experiments highlights the relevance of this new class of model compounds for broader use in catalysis studies. Only by understanding the reactivity of the linkages in lignin at this level of detail can fully optimized lignin depolymerization strategies be developed.

  13. Analysis of Lignin-Polysaccharide Complexes Formed during Grass Lignin Degradation by Cultures of Pleurotus Species.

    Science.gov (United States)

    Gutierrez, A; Bocchini, P; Galletti, G C; Martinez, A T

    1996-06-01

    A brown material, precipitable with ethanol, was formed during wheat straw and lignin degradation by liquid cultures of different species of Pleurotus. Fourier transform infrared spectroscopy and cross-polarization and magic-angle-spinning (sup13)C nuclear magnetic resonance spectroscopy showed that most of the precipitable material was formed from exopolysaccharide secreted by the fungus but it also contained an aromatic fraction. The results of acid hydrolysis, methylation analysis, and Smith degradation indicated that the major exopolysaccharide produced by these fungi is a (1(symbl)3)-(beta)-glucan branched at C-6 every two or three residues along the main chain. The presence of lignin or straw in the culture medium had little effect on the composition and structure of the extracellular polysaccharide. Cross-polarization and magic-angle-spinning (sup13)C nuclear magnetic resonance spectroscopy provided an estimation of the aromatic content of the lignin-polysaccharide complexes, assigning 20% of the total (sup13)C signal in the material recovered from cultures of Pleurotus eryngii in lignin medium to aromatic carbon. Analytical pyrolysis indicated that the aromatic fractions of the lignin-polysaccharide complexes were derived from lignin, since products characteristic of pyrolytic breakdown of H (p-hydroxyphenylpropane), G (guaiacylpropane), and S (syringylpropane) lignin units were identified. These complexes cannot be fractionated by treatment with polyvinylpyrrolidone or extraction with lignin solvents, suggesting that the two polymers were chemically linked. Moreover, differences in composition with respect to the original lignin indicated that this macromolecule was modified by the fungi during the process of formation of the lignin-polysaccharide complexes.

  14. Lignin Sulfonation - A different Approach

    DEFF Research Database (Denmark)

    Bjørkmann, Anders

    2001-01-01

    . It was found that lignin is very reactive, that is why the sulfonation chemistry alone does not necessarily determine its dissolution rate. It became evident that the ultrastructure dispersion of lignin in wood is beneficial for its dissolution. For W, the rate was much higher at pH 1.5 than at 6. MW lignin...... and MWL dissolved (after extraction of the "immediate" lignin) at higher rates than W lignin. For MWL, the rate difference between pH 1.5 and 6 was moderate, compared to W lignin. Borohydride reduction did not affect the lignin dissolution from W, but gave a large decrease of sulfonation rate for MWL...

  15. Catalytic efficiency of natural and synthetic compounds used as laccase-mediators in oxidising veratryl alcohol and a kraft lignin, estimated by electrochemical analysis

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez Arzola, K. [Department of Microbiology and Cell Biology, Faculty of Pharmacy, University of La Laguna, 38206 La Laguna, Tenerife (Spain); Arevalo, M.C. [Department of Physical Chemistry, Faculty of Chemistry, University of La Laguna, 38206 La Laguna, Tenerife (Spain)], E-mail: carevalo@ull.es; Falcon, M.A. [Department of Microbiology and Cell Biology, Faculty of Pharmacy, University of La Laguna, 38206 La Laguna, Tenerife (Spain)], E-mail: mafalcon@ull.es

    2009-03-30

    The electrochemical properties of eighteen natural and synthetic compounds commonly used to expand the oxidative capacity of laccases were evaluated in an aqueous buffered medium using cyclic voltammetry. This clarifies which compounds fulfil the requisites to be considered as redox mediators or enhancers. Cyclic voltammetry was also applied as a rapid way to assess the catalytic efficiency (CE) of those compounds which oxidise a non-phenolic lignin model (veratryl alcohol, VA) and a kraft lignin (KL). With the exception of gallic acid and catechol, all assayed compounds were capable of oxidising VA with varying CE. However, only some of them were able to oxidise KL. Although the oxidised forms of HBT and acetovanillone were not electrochemically stable, their reduced forms were quickly regenerated in the presence of VA. They thus act as chemical catalysts. Importantly, HBT and HPI did not attack the KL via the same mechanism as in VA oxidation. Electrochemical evidence suggests that violuric acid oxidises both substrates by an electron transfer mechanism, unlike the other N-OH compounds HBT and HPI. Acetovanillone was found to be efficient in oxidising VA and KL, even better than the synthetic mediators TEMPO, violuric acid or ABTS. Most of the compounds produced a generalised increase in the oxidative charge of KL, probably attributed to chain reactions arising between the phenolic and non-phenolic components of this complex molecule.

  16. Lignin phenols derivatives in lichens.

    Science.gov (United States)

    Zavarzina, A G; Romankevich, E A; Peresypkin, V I; Ulyantzev, A S; Belyaev, N A; Zavarzin, A A

    2015-01-01

    Lignin monophenols have been measured in the cupric oxide oxidation products from lichens of different systematic groups. It is shown for the first time that syringyl structures in most lichens strongly dominate over vanillyl and p-hydroxyl ones (S/V 7-583, S/P 3-30). This distinguishes lichens from algae and mosses (p-hydroxyl phenols are dominant) and from higher plants (S/V ratios are from 0 in gymnosperms to 1.1-5.2 in angiosperms). Molecular ratios of phenols as well as the ratios of acids to aldehydes in lichens were different from lignin of higher plants, suggesting contribution of non-lignin phenols in CuO oxidation products. The contents of syringyl and vanillyl phenols in some lichen species were comparable to non-woody tissues of higher plants. Results of the study suggest that lichens can be important source of aromatic structures in soils and hydrosphere, particularly in the regions were lichens are abundant.

  17. De novo assembly, transcriptome characterization, lignin accumulation, and anatomic characteristics: novel insights into lignin biosynthesis during celery leaf development.

    Science.gov (United States)

    Jia, Xiao-Ling; Wang, Guang-Long; Xiong, Fei; Yu, Xu-Run; Xu, Zhi-Sheng; Wang, Feng; Xiong, Ai-Sheng

    2015-02-05

    Celery of the family Apiaceae is a biennial herb that is cultivated and consumed worldwide. Lignin is essential for cell wall structural integrity, stem strength, water transport, mechanical support, and plant pathogen defense. This study discussed the mechanism of lignin formation at different stages of celery development. The transcriptome profile, lignin distribution, anatomical characteristics, and expression profile of leaves at three stages were analyzed. Regulating lignin synthesis in celery growth development has a significant economic value. Celery leaves at three stages were collected, and Illumina paired-end sequencing technology was used to analyze large-scale transcriptome sequences. From Stage 1 to 3, the collenchyma and vascular bundles in the petioles and leaf blades thickened and expanded, whereas the phloem and the xylem extensively developed. Spongy and palisade mesophyll tissues further developed and were tightly arranged. Lignin accumulation increased in the petioles and the mesophyll (palisade and spongy), and the xylem showed strong lignification. Lignin accumulation in different tissues and at different stages of celery development coincides with the anatomic characteristics and transcript levels of genes involved in lignin biosynthesis. Identifying the genes that encode lignin biosynthesis-related enzymes accompanied by lignin distribution may help elucidate the regulatory mechanisms of lignin biosynthesis in celery.

  18. Isolation and Characterization of Gramineae and Fabaceae Soda Lignins

    Science.gov (United States)

    Domínguez-Robles, Juan; Sánchez, Rafael; Espinosa, Eduardo; Savy, Davide; Mazzei, Pierluigi; Piccolo, Alessandro; Rodríguez, Alejandro

    2017-01-01

    Some agricultural residues such as wheat or barley straw, as well as certain fast-growing plants like Leucaena leucocephala and Chamaecytisus proliferus, could be used as raw materials for the paper industry as an alternative to traditional plants (eucalyptus, pine, etc.). In the present study, four types of lignin obtained from the spent liquors produced by the pulping processes using the abovementioned feedstocks were isolated and characterized. Lignin samples were acquired through an acid precipitation from these spent liquors. The characterization of the precipitated lignin samples were performed using a Fourier transform infrared spectroscopy (FT-IR) and both liquid- and solid-state nuclear magnetic resonance spectroscopy (NMR) to analyse the chemical structure, and thermogravimetric analysis (TGA) for determining the thermal properties. Additionally, chemical composition of lignin fractions was also measured. Even though they were of different botanical origin, all the studied samples except for wheat straw lignin had a similar chemical composition and thermal behaviour, and identical chemical structure. Wheat straw lignin showed a greater amount of Klason lignin and lower carbohydrate content. Furthermore, this lignin sample showed a higher thermal stability and significantly different cross-peak patterns in the 2D-NMR experiments. The molecular structures corresponding to p-coumarate (PCA), ferulate (FA) and cinnamyl aldehyde end-groups (J) were only detected in wheat isolated lignin. PMID:28165411

  19. Isolation and Characterization of Gramineae and Fabaceae Soda Lignins

    Directory of Open Access Journals (Sweden)

    Juan Domínguez-Robles

    2017-02-01

    Full Text Available Some agricultural residues such as wheat or barley straw, as well as certain fast-growing plants like Leucaena leucocephala and Chamaecytisus proliferus, could be used as raw materials for the paper industry as an alternative to traditional plants (eucalyptus, pine, etc.. In the present study, four types of lignin obtained from the spent liquors produced by the pulping processes using the abovementioned feedstocks were isolated and characterized. Lignin samples were acquired through an acid precipitation from these spent liquors. The characterization of the precipitated lignin samples were performed using a Fourier transform infrared spectroscopy (FT-IR and both liquid- and solid-state nuclear magnetic resonance spectroscopy (NMR to analyse the chemical structure, and thermogravimetric analysis (TGA for determining the thermal properties. Additionally, chemical composition of lignin fractions was also measured. Even though they were of different botanical origin, all the studied samples except for wheat straw lignin had a similar chemical composition and thermal behaviour, and identical chemical structure. Wheat straw lignin showed a greater amount of Klason lignin and lower carbohydrate content. Furthermore, this lignin sample showed a higher thermal stability and significantly different cross-peak patterns in the 2D-NMR experiments. The molecular structures corresponding to p-coumarate (PCA, ferulate (FA and cinnamyl aldehyde end-groups (J were only detected in wheat isolated lignin.

  20. Treatment of Lignin Precursors to Improve their Suitability for Carbon Fibers: A Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Ryan [GrafTech International Holdings Inc.; Naskar, Amit [Oak Ridge National Laboratory; Gallego, Nidia [Oak Ridge National Laboratory; Dai, Xuliang [GrafTech International Holdings Inc.; Hausner, Andrew [GrafTech International Holdings Inc.

    2015-04-17

    Lignin has been investigated as a carbon fiber precursor since the 1960s. Although there have been a number of reports of successful lignin-based carbon fiber production at the lab scale, lignin-based carbon fibers are not currently commercially available. This review will highlight some of the known challenges, and also the reported methods for purifying and modifying lignin to improve it as a precursor. Lignin can come from different sources (e.g. hardwood, softwood, grasses) and extraction methods (e.g. organosolv, kraft), meaning that lignin can be found with a diversity of purity and structure. The implication of these conditions on lignin as carbon fiber precursor is not comprehensively known, especially as the lignin landscape is evolving. The work presented in this review will help guide the direction of a project between GrafTech and ORNL to develop lignin carbon fiber technology, as part of a cooperative agreement with the DOE Advanced Manufacturing Office.

  1. Sphingobium sp. SYK-6 LigG involved in lignin degradation is structurally and biochemically related to the glutathione transferase ω class.

    Science.gov (United States)

    Meux, Edgar; Prosper, Pascalita; Masai, Eiji; Mulliert, Guillermo; Dumarçay, Stéphane; Morel, Mélanie; Didierjean, Claude; Gelhaye, Eric; Favier, Frédérique

    2012-11-16

    SpLigG is one of the three glutathione transferases (GSTs) involved in the process of lignin breakdown in the soil bacterium Sphingobium sp. SYK-6. Sequence comparisons showed that SpLigG and several proteobacteria homologues form an independent cluster within cysteine-containing GSTs. The relationship between SpLigG and other GSTs was investigated. The X-ray structure and biochemical properties of SpLigG indicate that this enzyme belongs to the omega class of glutathione transferases. However, the hydrophilic substrate binding site of SpLigG, together with its known ability to stereoselectively deglutathionylate the physiological substrate α-glutathionyl-β-hydroxypropiovanillone, argues for broadening the definition of the omega class.

  2. CHARACTERISTICS OF LIGNIN REACTIONS IN SODA COOKING OF WHEAT STRAW——PART 1 REACTION OF UNCONDENSED LIGNIN

    Institute of Scientific and Technical Information of China (English)

    HuaminZhai; YuanzongLai

    2004-01-01

    Characteristics of uncondensed lignin reactions in soda cooking of wheat straw were studied. Mild and intense cooking conditions were used to get the pulp sample in which lignin was dissolved physically and the pulp sample in which lignin was dissolved chemically respectively. The pulp samples were analyzed by phenolic group determination, alkaline nitrobenzene oxidation and ozonation method. The results indicated that around 90% of lignin in wheat straw is alkali-soluble at the mild conditions, is basically dissolved physically without chemical change. The phenolic group content was not changed greatly, the nitrobenzene oxidation yield only changed slightly during the mild cooking. The phenolic group content was increased obviously and uncondensed lignin content was decreased very much when the intense cooking conditions were applied and the delignification was over 90%. The lignin structure was changed greatly during this period.

  3. Dynamics and turnover of lignins in soils: a review

    Science.gov (United States)

    Thevenot, M.; Rumpel, C.; Dignac, M.-F.

    2009-04-01

    other hand, other studies suggest contradictory results, suggesting the retention of a large part of the initial lignin input and its preservation in the organo-mineral fraction (Hofmann et al., 2009; Dümig et al., 2009). This contradiction could be due to the existence of two pools of lignins in soils: one pool of fresh lignin residues with a fast turnover and one of protected lignins with a slow turnover (Lobe et al., 2002; Rasse et al., 2006). However, the mechanisms of protection are not yet clear, and could be related to chemical variation in the structure of the lignins leading a decrease of their degradability (chemical protection) and/or to interactions between a fraction of the lignins with the mineral phase of the soil (physical protection). In conclusion, this review suggests that lignins greatly influence the bulk SOC dynamics, but their fate in soils needs to be elucidated. To this end, the future researches could focus on the relations between the lignin distribution and the environmental parameters, and on the kinetic pools of lignins in soils. Burke I.C., Yonker C.M., Parton W. J., Cole C. V., Schimel D. S., Flach K., 1989. Soil Science Society of America Journal 53, 800-805. Dümig A., Rumpel C., Dignac M.-F., Schad P., Ingrid Kögel-Knabner I., 2008. Organic Geochemistry, Submitted. Lobe I., Du Preez C.C, Amelung A., 2002. European Journal of Soil Science 53, 553-562. Hofmann A., Heim A., Christensen B.T., Miltner A., Gehre M., Schmidt M.W.I., 2009. European Journal of Soil Science, Accepted. Rasse D.P., Dignac M.-F., Bahri H., Rumpel C., Mariotti A., Chenu C., 2006. European Journal of Soil Science 57, 530-538.

  4. Silencing CHALCONE SYNTHASE in Maize Impedes the Incorporation of Tricin into Lignin and Increases Lignin Content1[OPEN

    Science.gov (United States)

    2017-01-01

    Lignin is a phenolic heteropolymer that is deposited in secondary-thickened cell walls, where it provides mechanical strength. A recent structural characterization of cell walls from monocot species showed that the flavone tricin is part of the native lignin polymer, where it is hypothesized to initiate lignin chains. In this study, we investigated the consequences of altered tricin levels on lignin structure and cell wall recalcitrance by phenolic profiling, nuclear magnetic resonance, and saccharification assays of the naturally silenced maize (Zea mays) C2-Idf (inhibitor diffuse) mutant, defective in the CHALCONE SYNTHASE Colorless2 (C2) gene. We show that the C2-Idf mutant produces highly reduced levels of apigenin- and tricin-related flavonoids, resulting in a strongly reduced incorporation of tricin into the lignin polymer. Moreover, the lignin was enriched in β-β and β-5 units, lending support to the contention that tricin acts to initiate lignin chains and that, in the absence of tricin, more monolignol dimerization reactions occur. In addition, the C2-Idf mutation resulted in strikingly higher Klason lignin levels in the leaves. As a consequence, the leaves of C2-Idf mutants had significantly reduced saccharification efficiencies compared with those of control plants. These findings are instructive for lignin engineering strategies to improve biomass processing and biochemical production. PMID:27940492

  5. Cellulose structure and lignin distribution in normal and compression wood of the Maidenhair tree (Ginkgo biloba L.)

    Institute of Scientific and Technical Information of China (English)

    Seppo Andersson; Yurong Wang; Raili Ponni; Tuomas Hanninen; Marko Mononen; Haiqing Ren; Ritva Serimaa; Pekka Saranpaa

    2015-01-01

    We studied in detail the mean microfibril angle and the width of cellulose crystals from the pith to the bark of a 15-year-old Maidenhair tree (Ginkgo biloba L.). The orientation of cellulose microfibrils with respect to the cell axis and the width and length of cellulose crystallites were determined using X-ray diffraction. Raman microscopy was used to compare the lignin distribution in the cell wall of normal/opposite and compression wood, which was found near the pith. Ginkgo biloba showed a relatively large mean microfibril angle, varying between 19° and 39° in the S2 layer, and the average width of cellulose crystallites was 3.1–3.2 nm. Mild compres-sion wood without any intercellular spaces or helical cavities was observed near the pith. Slit-like bordered pit openings and a heavily lignified S2L layer confirmed the presence of compression wood. Ginkgo biloba showed typical features present in the juvenile wood of conifers. The microfibril angle remained large over the 14 annual rings. The entire stem disc, with a diameter of 18 cm, was considered to consist of juvenile wood. The properties of juvenile and compression wood as well as the cellulose orientation and crystalline width indicate that the wood formation of G. biloba is similar to that of modern conifers.

  6. Cellulose structure and lignin distribution in normal and compression wood of the Maidenhair tree (Ginkgo biloba L.).

    Science.gov (United States)

    Andersson, Seppo; Wang, Yurong; Pönni, Raili; Hänninen, Tuomas; Mononen, Marko; Ren, Haiqing; Serimaa, Ritva; Saranpää, Pekka

    2015-04-01

    We studied in detail the mean microfibril angle and the width of cellulose crystals from the pith to the bark of a 15-year-old Maidenhair tree (Ginkgo biloba L.). The orientation of cellulose microfibrils with respect to the cell axis and the width and length of cellulose crystallites were determined using X-ray diffraction. Raman microscopy was used to compare the lignin distribution in the cell wall of normal/opposite and compression wood, which was found near the pith. Ginkgo biloba showed a relatively large mean microfibril angle, varying between 19° and 39° in the S2 layer, and the average width of cellulose crystallites was 3.1-3.2 nm. Mild compression wood without any intercellular spaces or helical cavities was observed near the pith. Slit-like bordered pit openings and a heavily lignified S2L layer confirmed the presence of compression wood. Ginkgo biloba showed typical features present in the juvenile wood of conifers. The microfibril angle remained large over the 14 annual rings. The entire stem disc, with a diameter of 18 cm, was considered to consist of juvenile wood. The properties of juvenile and compression wood as well as the cellulose orientation and crystalline width indicate that the wood formation of G. biloba is similar to that of modern conifers.

  7. Lignins : natural polymers from oxidative coupling of 4-hydroxyphenyl-propanoids

    Science.gov (United States)

    John Ralph; Knut Lundquist; Gosta Brunow; Fachuang Lu; Hoon Kim; Paul F. Schatz; Jane M. Marita; Ronald D. Hatfield; Sally A. Ralph; Jorgen Holst Christensen; Wout Boerjan

    2004-01-01

    Lignins are complex natural polymers resulting from oxidative coupling of, primarily, 4-hydroxyphenylpropanoids. An understanding of their nature is evolving as a result of detailed structural studies, recently aided by the availability of lignin-biosynthetic-pathway mutants and transgenics. The currently accepted theory is that the lignin polymer is formed by...

  8. Lewis acid-catalyzed depolymerization of soda lignin in supercritical ethanol/water mixtures

    NARCIS (Netherlands)

    Güvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Emiel J M

    2016-01-01

    The depolymerization of lignin model compounds and soda lignin by super Lewis acidic metal triflates has been investigated in a mixture of ethanol and water at 400 °C. The strong Lewis acids convert representative model compounds for the structure-forming linkages in lignin, namely α-O-4, 5-O-4

  9. Through Lignin Biodegradation to Lignin-based Plastics

    Science.gov (United States)

    Wang, Yun-Yan

    The consequences of strong noncovalent intermolecular interactions between oligomeric and/or polymeric lignin components are encountered during enzyme-catalyzed lignin degradation and in the properties of lignin-based plastics. A new chapter in the 30-year quest for functional lignin-depolymerizing enzymes has been opened. The lignin-degrading capacity of the flavin-dependent monooxygenase, salicylate hydroxylase acting as a putative lignin depolymerase, has been characterized using a water-soluble native softwood lignin substrate under mildly acidic aqueous conditions. When macromolecular lignins undergo lignin-depolymerase catalyzed degradation, the cleaved components tend to associate with one another, or with nearby associated lignin complexes, through processes mediated by the enzyme acting in a non-catalytic capacity. As a result, the radius of gyration (Rg) falls rapidly to approximately constant values, while the weight-average molecular weight (Mw) of the substrate rises more slowly to an extent dependent on enzyme concentration. Xylanase, when employed in an auxiliary capacity, is able to facilitate dissociation of the foregoing complexes through its interactions with the lignin depolymerase. The flavin-dependent lignin depolymerase must be reduced before reaction with oxygen can occur to form the hydroperoxy intermediate that hydroxylates the lignin substrate prior to cleavage. In the absence of the cofactor, NADH, the necessary reducing power can be provided (albeit more slowly) by the lignin substrate itself. Under such conditions, a simultaneous decrease in R g and Mw is initially observed during the enzymatic process through which the lignin is cleaved. The partially degraded product-lignins arising from lignin depolymerase activity can be readily converted into polymeric materials with mechanical properties that supersede those of polystyrene. Methylation and blending of ball-milled softwood lignins with miscible low-Tg polymers, or simple low

  10. Lignin-rich Enzyme Lignin (LREL), a Cellulase-treated Lignin-Carbohydrate Derived from Plants, Activates Myeloid Dendritic Cells via Toll-like Receptor 4 (TLR4)

    Science.gov (United States)

    Tsuji, Ryohei; Koizumi, Hideki; Aoki, Dan; Watanabe, Yuta; Sugihara, Yoshihiko; Matsushita, Yasuyuki; Fukushima, Kazuhiko; Fujiwara, Daisuke

    2015-01-01

    Lignin-carbohydrates, one of the major cell wall components, are believed to be the structures that form chemical linkage between lignin and cell wall polysaccharides. Due to the molecular complexity of lignin-containing substances, their isolation and the assignment of their biological activities have so far remained a difficult task. Here, we extracted two lignin-containing carbohydrates, lignin-rich enzyme lignin (LREL) and pure enzyme lignin (PEL), from barley husk and demonstrated that they act as immune stimulators of dendritic cells (DCs), which are particularly important in linking innate and adaptive immunity. Thioacidolysis, acid hydrolysis, and mild alkali hydrolysis of both LREL and PEL revealed that their immunostimulatory activities depended on the lignin structure and/or content, neutral sugar content (especially the characteristic distribution of galactose and mannose), and presence of an ester bond. Furthermore, we showed that the immunostimulatory potency of the lignin-carbohydrate depended on its molecular weight and degree of polymerization. We also demonstrated that the LREL-induced activation of DCs was mediated via TLR4. Thus, LREL-induced increases in the expression levels of several cell surface marker proteins, production of inflammatory cytokines IL-12p40 and TNF-α, and activation and nuclear translocation of transcription factors, as was observed in the WT DCs, were completely abrogated in DCs derived from the TLR4−/− mice but not in DCs derived from the TLR2−/−, TLR7−/−, and TLR9−/− mice. We further demonstrated that LRELs isolated from other plant tissues also activated DCs. These immunostimulatory activities of lignin-carbohydrates, extracted from edible plant tissues, could have potential relevance in anti-infectious immunity and vaccine adjuvants. PMID:25548274

  11. Engineering Plant Biomass Lignin Content and Composition for Biofuels and Bioproducts

    Directory of Open Access Journals (Sweden)

    Cassie Marie Welker

    2015-07-01

    Full Text Available Lignin is an aromatic biopolymer involved in providing structural support to plant cell walls. Compared to the other cell wall polymers, i.e., cellulose and hemicelluloses, lignin has been considered a hindrance in cellulosic bioethanol production due to the complexity involved in its separation from other polymers of various biomass feedstocks. Nevertheless, lignin is a potential source of valuable aromatic chemical compounds and upgradable building blocks. Though the biosynthetic pathway of lignin has been elucidated in great detail, the random nature of the polymerization (free radical coupling process poses challenges for its depolymerization into valuable bioproducts. The absence of specific methodologies for lignin degradation represents an important opportunity for research and development. This review highlights research development in lignin biosynthesis, lignin genetic engineering and different biological and chemical means of depolymerization used to convert lignin into biofuels and bioproducts.

  12. Formic-acid-induced depolymerization of oxidized lignin to aromatics.

    Science.gov (United States)

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J; Stahl, Shannon S

    2014-11-13

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  13. Formic-acid-induced depolymerization of oxidized lignin to aromatics

    Science.gov (United States)

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.; Stahl, Shannon S.

    2014-11-01

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  14. Chemical characterization of lignin from kraft pulping black liquor of Acacia mangium

    Science.gov (United States)

    Hermiati, Euis; Risanto, Lucky; Lubis, M. Adly Rahandi; Laksana, Raden Permana Budi; Dewi, Aniva Rizkia

    2017-01-01

    In order to know the proper use of lignin derived from pulping process of A. mangium, it is important to study the characteristics of lignin obtained from this species. The objective of this research was to study the characteristics of lignin isolated from kraft pulping black liquor of A. mangium. Lignin was isolated from the black liquor by single step and two step acid precipitation. The lignins were characterized for their moisture, ash, acid soluble lignin (ASL), and acid insoluble lignin (AIL) contents. Elemental composition, FTIR spectra, UV spectra, and microscopic structure using SEM were also analyzed. The yield of lignin obtained through one step precipitation of black liquor (45.76%) was much higher than that through two step precipitation (7.38%), while ash contents of lignin from one step and two step precipitations were almost the same. Ultimate analysis shows that carbon content in lignin from one step precipitation was lower than that from two step precipitation, while hydrogen, oxygen, nitrogen and sulfur content were relatively the same. Two step precipitation could increase the AIL and decrease the ASL content of the lignin isolate. Results of UV analysis show that in neutral medium (dioxane-water) the two lignin isolates had strong absorbance at 240 nm, while in alkaline medium (NaOH pH 12) there were strong absorption at 210 nm, and weak absorption at 280 nm. The FT-IR spectra reveal that the two lignin isolates had similar functional groups. This means that the removal of sugar from lignin did not change the lignin structure. The SEM analysis shows that both lignin isolates still contain some dirts.

  15. NMR of lignins

    Science.gov (United States)

    John Ralph; Larry L. Landucci

    2010-01-01

    This chapter will consider the basic aspects and findings of several forms of NMR spectroscopy, including separate discussions of proton, carbon, heteronuclear, and multidimensional NMR. Enhanced focus will be on 13C NMR, because of its qualitative and quantitative importance, followed by NMR’s contributions to our understanding of lignin...

  16. EFFECT OF LIGNIN CONTENT ON ENZYMATIC HYDROLYSIS OF FURFURAL RESIDUES

    Directory of Open Access Journals (Sweden)

    Jianxin Jiang

    2011-02-01

    Full Text Available The enzymatic saccharification of pretreated furfural residues with different lignin content was studied to verify the effect of lignin removal in the hydrolysis process. The results showed that the glucose yield was improved by increasing the lignin removal. A maximum glucose yield of 96.8% was obtained when the residue with a lignin removal of 51.4% was hydrolyzed for 108 h at an enzyme loading of 25 FPU/g cellulose. However, further lignin removal did not increase the hydrolysis. The effect of enzyme loading on the enzymatic hydrolysis was also explored in this work. It was concluded that a high glucose yield of 90% was achieved when the enzyme dosage was reduced from 25 to 15 FPU/g cellulose, which was cost-effective for the sugar and ethanol production. The structures of raw material and delignified samples were further characterized by XRD and scanning electron microscopy (SEM.

  17. Lignin-Based Thermoplastic Materials.

    Science.gov (United States)

    Wang, Chao; Kelley, Stephen S; Venditti, Richard A

    2016-04-21

    Lignin-based thermoplastic materials have attracted increasing interest as sustainable, cost-effective, and biodegradable alternatives for petroleum-based thermoplastics. As an amorphous thermoplastic material, lignin has a relatively high glass-transition temperature and also undergoes radical-induced self-condensation at high temperatures, which limits its thermal processability. Additionally, lignin-based materials are usually brittle and exhibit poor mechanical properties. To improve the thermoplasticity and mechanical properties of technical lignin, polymers or plasticizers are usually integrated with lignin by blending or chemical modification. This Review attempts to cover the reported approaches towards the development of lignin-based thermoplastic materials on the basis of published information. Approaches reviewed include plasticization, blending with miscible polymers, and chemical modifications by esterification, etherification, polymer grafting, and copolymerization. Those lignin-based thermoplastic materials are expected to show applications as engineering plastics, polymeric foams, thermoplastic elastomers, and carbon-fiber precursors.

  18. CHARACTERIZATION OF FRACTIONATED LIGNINS POLYMERIZED BY FUNGAL LACCASES

    Directory of Open Access Journals (Sweden)

    Daniel van de Pas

    2011-04-01

    Full Text Available Lignins are important biopolymers that can be converted into value-added materials by enzymatic treatments. However, the heterogeneity of the lignin polymer makes it a challenging material to modify. Thus, chemical fractionation was used to obtain lignins with high homogeneity in order to assess their biotechnological utilization. Commercial Alcell, birch organosolv lignins, and steam-exploded pine and eucalypt lignins were sequentially fractionated by ether, ether/acetone 4:1 (v:v, and acetone. All fractions were structurally characterized prior to treatments with Thielavia arenaria, Trametes hirsuta, and Melanocarpus albomyces laccases. The reactivities of the enzymes towards the lignins were determined by oxygen consumption measurements, and the degree of polymerization was confirmed by size exclusion chromatography. Field emission scanning electron microscopy revealed that the surfaces of the lignin nanoparticles were dispersed in the enzyme treatment, suggesting an increase in hydrophilicity of the surfaces detected as loosened morphology. Hence, it was concluded that enzyme-aided valorization is an attractive means for lignin modification, provided that optimum reaction conditions are employed.

  19. Renewable bio ionic liquids-water mixtures-mediated selective removal of lignin from rice straw: visualization of changes in composition and cell wall structure.

    Science.gov (United States)

    Hou, Xue-Dan; Li, Ning; Zong, Min-Hua

    2013-07-01

    Pretreatment of rice straw by using renewable cholinium amino acids ionic liquids ([Ch][AA] ILs)-water mixtures and the subsequent enzymatic hydrolysis of the residues were conducted in the present work. Of the eight mixtures composed of ILs and water, most were found to be effective for rice straw pretreatment. After pretreatment with 50% ILs-water mixtures, the enzymatic digestion of the lignocellulosic biomass was enhanced significantly, thus leading to satisfactory sugar yields of >80% for glucose and approximately 50% for xylose. To better understand the ILs pretreatment mechanism, confocal laser scanning microscopy combined with immunolabeling and transmission electron microscopy were used to visualize changes in the contents and distribution of two major components--lignin and xylan. The results coupled with changes in chemical structures (infrared spectra) of the substrates indicated occurrence of extensive delignification, especially in cell corner and compound middle lumen of cell walls, which made polysaccharides more accessible to enzymes. This pretreatment process is promising for large-scale application because of the high sugar yields, easy handling, being environmentally benign and highly tolerant to moisture, and significantly reduced cost and energy consumption.

  20. High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

    Energy Technology Data Exchange (ETDEWEB)

    Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

    2016-12-01

    High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

  1. Radical Nature of C-Lignin

    Energy Technology Data Exchange (ETDEWEB)

    Berstis, Laura; Elder, Thomas; Crowley, Michael; Beckham, Gregg T.

    2016-10-03

    The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxane ..alpha..- and ..beta..-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the ..alpha..-bond within the benzodioxane linkage is consistently greater than that of the ..beta..-bond in all dimers of each stereochemical arrangement, explained by the ability the ..alpha..-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest

  2. Toward a better understanding of the lignin isolation process from wood.

    Science.gov (United States)

    Guerra, Anderson; Filpponen, Ilari; Lucia, Lucian A; Saquing, Carl; Baumberger, Stephanie; Argyropoulos, Dimitris S

    2006-08-09

    The recently developed protocol for isolating enzymatic mild acidolysis lignins (EMAL) coupled with the novel combination of derivatization followed by reductive cleavage (DFRC) and quantitative (31)P NMR spectroscopy were used to better understand the lignin isolation process from wood. The EMAL protocol is shown to offer access at lignin samples that are more representative of the overall lignin present in milled wood. The combination of DFRC/(31)P NMR provided a detailed picture on the effects of the isolation conditions on the lignin structure. More specifically, we have used vibratory and ball milling as the two methods of wood pulverization and have compared their effects on the lignin structures and molecular weights. Vibratory-milling conditions cause substantial lignin depolymerization. Lignin depolymerization occurs via the cleavage of uncondensed beta-aryl ether linkages, while condensed beta-aryl ethers and dibenzodioxocins were found to be resistant to such mechanical action. Condensation and side chain oxidations were induced mechanochemically under vibratory-milling conditions as evidenced by the increased amounts of condensed phenolic hydroxyl and carboxylic acid groups. Alternatively, the mild mechanical treatment offered by ball milling was found not to affect the isolated lignin macromolecular structure. However, the overall lignin yields were found to be compromised when the mechanical action was less intense, necessitating longer milling times under ball-milling conditions. As compared to other lignin preparations isolated from the same batch of milled wood, the yield of EMAL was about four times greater than the corresponding milled wood lignin (MWL) and about two times greater as compared to cellulolytic enzyme lignin (CEL). Molecular weight distribution analyses also pointed out that the EMAL protocol allows the isolation of lignin fractions that are not accessed by any other lignin isolation procedures.

  3. Isolation and characterization of lignin from the oak wood bioethanol production residue for adhesives.

    Science.gov (United States)

    Lee, Soo Jung; Kim, Hyun Joo; Cho, Eun Jin; Song, Younho; Bae, Hyeun-Jong

    2015-01-01

    Lignin was isolated from the residue of bioethanol production with oak wood via alkaline and catalyzed organosolv treatments at ambient temperature to improve the purity of lignin for the materials application. The isolated lignins were analyzed for their chemical composition by nitrobenzene oxidation method and their functionality was characterized via wet chemistry method, element analysis, (1)H NMR, GPC and FTIR-ATR. The isolated lignin by acid catalyzed organosolv treatment (Acid-OSL) contained a higher lignin content, aromatic proton, phenolic hydroxyl group and a lower nitrogen content that is more reactive towards chemical modification. The lignin-based adhesives were prepared and the bond strength was measured to evaluate the enhanced reactivity of lignin by the isolation. Two steps of phenolation and methylolation were applied for the modification of the isolated lignins and their tensile strengths were evaluated for the use as an adhesive. The acid catalyzed organosolv lignin-based adhesives had comparable bond strength to phenol-formaldehyde adhesives. The analysis of lignin-based adhesives by FTIR-ATR and TGA showed structural similarity to phenol adhesive. The results demonstrate that the reactivity of lignin was enhanced by isolation from hardwood bioethanol production residues at ambient temperature and it could be used in a value-added application to produce lignin-based adhesives.

  4. Enzymatic Degradation of Lignin in Soil: A Review

    Directory of Open Access Journals (Sweden)

    Rahul Datta

    2017-07-01

    Full Text Available Lignin is a major component of soil organic matter and also a rich source of carbon dioxide in soils. However, because of its complex structure and recalcitrant nature, lignin degradation is a major challenge. Efforts have been made from time to time to understand the lignin polymeric structure better and develop simpler, economical, and bio-friendly methods of degradation. Certain enzymes from specialized bacteria and fungi have been identified by researchers that can metabolize lignin and enable utilization of lignin-derived carbon sources. In this review, we attempt to provide an overview of the complexity of lignin’s polymeric structure, its distribution in forest soils, and its chemical nature. Herein, we focus on lignin biodegradation by various microorganism, fungi and bacteria present in plant biomass and soils that are capable of producing ligninolytic enzymes such as lignin peroxidase (LiP, manganese peroxidase (MnP, versatile peroxidase (VP, and dye-decolorizing peroxidase (DyP. The relevant and recent reports have been included in this review.

  5. Effects of lignin on the anaerobic degradation of (ligno) cellulosic wastes by rumen microorganisms

    Energy Technology Data Exchange (ETDEWEB)

    Camp, H.J.M. op den; Verhagen, F.J.M.; Kivaisi, A.K.; Windt, F.E. de; Lubberding, H.J.; Gijzen, H.J.; Vogels, G.D.

    1988-10-01

    There appeared to be a clear correlation between the lignin content (% of TS) of several waste and natural materials and their degradability by rumen microorgansims. Materials with lignin contents higher than 25% were not degraded within 72 h. The effects of Kraft pine lignin and some lignin momomers on filter paper degradation, methane production and CMCase activity were tested. Testing these compounds in concentrations comparable to natural conditions showed minor effects. At higher concentrations p-coumaric acid strongly inhibited cellulose degradation and methane production in batch cultures. Influence of lignin compounds on degradation is discussed in relation to structural effects and enzyme or growth inhibition.

  6. Lignin-derived thermoplastic co-polymers and methods of preparation

    Science.gov (United States)

    Naskar, Amit K.; Saito, Tomonori; Pickel, Joseph M.; Baker, Frederick S.; Eberle, Claude Clifford; Norris, Robert E.; Mielenz, Jonathan Richard

    2014-06-10

    The present invention relates to a crosslinked lignin comprising a lignin structure having methylene or ethylene linking groups therein crosslinking between phenyl ring carbon atoms, wherein said crosslinked lignin is crosslinked to an extent that it has a number-average molecular weight of at least 10,000 g/mol, is melt-processible, and has either a glass transition temperature of at least 100.degree. C., or is substantially soluble in a polar organic solvent or aqueous alkaline solution. Thermoplastic copolymers containing the crosslinked lignin are also described. Methods for producing the crosslinked lignin and thermoplastic copolymers are also described.

  7. Comparative analysis of lignin peroxidase and manganese peroxidase activity on coniferous and deciduous wood using ToF-SIMS.

    Science.gov (United States)

    MacDonald, Jacqueline; Goacher, Robyn E; Abou-Zaid, Mamdouh; Master, Emma R

    2016-09-01

    White-rot fungi are distinguished by their ability to efficiently degrade lignin via lignin-modifying type II peroxidases, including manganese peroxidase (MnP) and lignin peroxidase (LiP). In the present study, time-of flight secondary ion mass spectrometry (ToF-SIMS) was used to evaluate lignin modification in three coniferous and three deciduous wood preparations following treatment with commercial preparations of LiP and MnP from two different white-rot fungi. Percent modification of lignin was calculated as a loss of intact methoxylated lignin over nonfunctionalized aromatic rings, which is consistent with oxidative cleavage of methoxy moieties within the lignin structure. Exposure to MnP resulted in greater modification of lignin in coniferous compared to deciduous wood (28 vs. 18 % modification of lignin); and greater modification of G-lignin compared to S-lignin within the deciduous wood samples (21 vs. 12 %). In contrast, exposure to LiP resulted in similar percent modification of lignin in all wood samples (21 vs 22 %), and of G- and S-lignin within the deciduous wood (22 vs. 23 %). These findings suggest that the selected MnP and LiP may particularly benefit delignification of coniferous and deciduous wood, respectively. Moreover, the current analysis further demonstrates the utility of ToF-SIMS for characterizing enzymatic modification of lignin in wood fibre along with potential advantages over UV and HPCL-MS detection of solubilized delignification products.

  8. Density functional theory study of spirodienone stereoisomers in lignin

    Science.gov (United States)

    Thomas Elder; Laura Berstis; Gregg T. Beckham; Michael F. Crowley

    2017-01-01

    The spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ∼3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a β-1 bond, has been proposed to be a precursor for acyclic β-1 linkages in...

  9. Lignin Characterization of Triploid Clones of Populus tomentosa Carr.

    Institute of Scientific and Technical Information of China (English)

    Jin Xiao-juan; Pu Jun-wen; Xie Yi-min; Takeshi Furuno; Liu Xin-yu

    2005-01-01

    In order to understand the structural characteristics of lignin in triploid clones ofPopulus tomentosa and its changes in the processes of pulping and bleaching, milled wood lignin (MWL), lignin carbohydrate complex (LCC) and the residual lignin from kraft pulp (KP) and sulfite pulp (SP) were isolated and analyzed by Fourier transform infrared (FTIR) spectrum and 13C nuclear magnetic resonance (NMR). The most diagnostic peaks were assigned and the differences were discussed. The spectral patterns reveal that triploid P. tomentosa shows the specific features of hardwood from temperate areas, but in the spectrum of FTIR, the strength ratio of A1270 cm-1 to A1226 cm-1 is 0.88, higher than the average of hardwood from temperate areas, which will make the lignin delignification more difficult during pulping and bleaching. The LCC from triploid P. tomentosa is mainly composed of xyloglucan and glucuronic acid, and other glucides have much lower ratio. In LCC FTIR, there are three peaks at 1 427, 1 329 and 1046 cm--1, indicating that both semi-cellulose and cellulose could exist in LCC, and that there might be relationships between cellulose and lignin. Compared with the residual lignin from KP and SP, the condensed structure in KP is more than that in SP.

  10. Lignin biodegradation and industrial implications

    Directory of Open Access Journals (Sweden)

    Adam B Fisher

    2014-12-01

    Full Text Available Lignocellulose, which comprises the cell walls of plants, is the Earth’s most abundant renewable source of convertible biomass. However, in order to access the fermentable sugars of the cellulose and hemicellulose fraction, the extremely recalcitrant lignin heteropolymer must be hydrolyzed and removed—usually by harsh, costly thermochemical pretreatments. Biological processes for depolymerizing and metabolizing lignin present an opportunity to improve the overall economics of the lignocellulosic biorefinery by facilitating pretreatment, improving downstream cellulosic fermentations or even producing a valuable effluent stream of aromatic compounds for creating value-added products. In the following review we discuss background on lignin, the enzymology of lignin degradation, and characterized catabolic pathways for metabolizing the by-products of lignin degradation. To conclude we survey advances in approaches to identify novel lignin degrading phenotypes and applications of these phenotypes in the lignocellulosic bioprocess.

  11. Lignin as renewable raw material.

    Science.gov (United States)

    Calvo-Flores, Francisco García; Dobado, José A

    2010-11-22

    Lignin is by far the most abundant substance based on aromatic moieties in nature, and the largest contributor to soil organic matter. Millions of tonnes of several lignin preparations are produced by the paper industry every year, and a minimal amount of lignin is isolated by direct extraction of lignin from plants. Lignin is used either directly or chemically modified, as a binder, dispersant agent for pesticides, emulsifier, heavy metal sequestrant, or component for composites and copolymers. For value-added applications of lignin to be improved, medium- and long-term conversion technologies must be developed, especially for the preparation of low-molecular-weight compounds as an alternative to the petrochemical industry.

  12. On the propensity of lignin to associate: a size exclusion chromatography study with lignin derivatives isolated from different plant species.

    Science.gov (United States)

    Guerra, Anderson; Gaspar, Armindo R; Contreras, Sofía; Lucia, Lucian A; Crestini, Claudia; Argyropoulos, Dimitris S

    2007-10-01

    Despite evidence that lignin associates under both aqueous and organic media, the magnitude and nature of the underlying driving forces are still a matter of discussion. The present paper addresses this issue by examining both solution properties and size exclusion behaviour of lignins isolated from five different species of softwoods, as well as from the angiosperms Eucalyptus globulus and wheat straw. This investigation has used the recently described protocol for isolating enzymatic mild acidolysis lignin (EMAL), which offers lignin samples highly representative of the overall lignin present in the wood cell wall. The molecular weight distributions of these EMALs were found to be dependent upon the wood species from which they were isolated and upon the incubation conditions used prior to size exclusion chromatography. While the chromatograms of EMALs isolated from softwoods displayed a bimodal behaviour, the elution profiles of EMAL from E. globulus and straw were nearly unimodal. A marked tendency to dissociate prevailed under incubation at room temperature for all examined species with the exception of the straw lignin preparation; furthermore, lignin solutions incubated at 4 degrees C showed an associative behaviour manifested by an increase in the weight and number average molecular weights for some species. The extent of such association/dissociation, as well as the time needed for the process to reach completion, was also found to depend upon the wood species, i.e. lignins from softwoods were found to associate/dissociate to a greater extent than lignins from E. globulus and straw. The origin of such effects within the lignin structure is also discussed.

  13. SEPARATION AND PURIFICATION OF LIGNIN BY MEANS OF ION EXCHANGE PROCESS

    Institute of Scientific and Technical Information of China (English)

    XUHede; LIANGHao; 等

    1993-01-01

    The effect of resin structure on desalination of lignin solution was investigated,the optimal structure of resin is as follows;cross linking degree as 4%,ratio of cationogen to anionogen is near 1.with such resin the desalination of lignin was produced very well because the resin has both molecule sieving and ion retardation properties.The sulfonation degress of lignin and total salt content of lignin solution were determinred with ion exchange technique,the relative error less than 1%.The salt content of small molecule in the lignin solution was calculated from sulfonation degree of lignin and total salt.Among gel and macroporous resins the best separation of lignin from reducing sugar was achieved with interpenetrating sulfonated resin 2×1.5×1.The separation of lignin with interpenetrating resin was carried out simultaneously with fractionation of lignin,the effect of fractionation with macroporous sulfonated resin is better than that with interpenetrating resin,but the former has a definite sorption of lignin which decreased the recovery of lignin.

  14. CHARACTERIZATION OF ALKALINE LIGNINS FOR USE IN PHENOL-FORMALDEHYDE AND EPOXY RESINS

    Directory of Open Access Journals (Sweden)

    Nour Eddine El Mansouri

    2011-05-01

    Full Text Available Besides polyurethanes and polyesters, phenolic and epoxy resins are the most prominent applications for technical lignins in thermosetting materials. To evaluate the potential application of lignin raw materials in phenol formaldehyde and epoxy resins, three types of alkaline lignins were characterized in terms of their structures and thermal properties. The lignin samples analyzed were kraft lignin (LIG-1, soda–rice straw lignin (LIG-2, and soda-wheat straw lignin (LIG-3. FTIR and 1H-NMR methods were used to determine their structure. Gel permeation chromatography (GPC was used to determine the molecular weight distribution (MWD. Differential scanning calorimetry (DSC was used to measure the glass transition temperature (Tg, and thermogravimetric analysis (TGA to determine the thermal stability of lignin samples. Results showed that kraft lignin (LIG-1 has moderate hydroxyl-group content, is rich in G-type units, and has good thermal stability. These properties make it more suitable for direct use in phenol formaldehyde resins, and it is therefore a good raw material for this purpose. The alkaline soda-rice straw lignin (LIG-2 with a high hydroxyl-group content and excellent thermal stability is most suited to preparing lignin-based epoxy resins.

  15. Microwave-assisted extraction of lignin from triticale straw: optimization and microwave effects.

    Science.gov (United States)

    Monteil-Rivera, Fanny; Huang, Guang Hai; Paquet, Louise; Deschamps, Stéphane; Beaulieu, Chantale; Hawari, Jalal

    2012-01-01

    Presently lignin is used as fuel but recent interests in biomaterials encourage the use of this polymer as a renewable feedstock in manufacturing. The present study was undertaken to explore the potential applicability of microwaves to isolate lignin from agricultural residues. A central composite design (CCD) was used to optimize the processing conditions for the microwave (MW)-assisted extraction of lignin from triticale straw. Maximal lignin yield (91%) was found when using 92% EtOH, 0.64 N H(2)SO(4), and 148 °C. The yield and chemical structure of MW-extracted lignin were compared to those of lignin extracted with conventional heating. Under similar conditions, MW irradiation led to higher lignin yields, lignins of lower sugar content, and lignins of smaller molecular weights. Except for these differences the lignins resulting from both types of heating exhibited comparable chemical structures. The present findings should provide a clean source of lignin for potential testing in manufacturing of biomaterials. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

  16. Fractionation of enzymatic hydrolysis lignin by sequential extraction for enhancing antioxidant performance.

    Science.gov (United States)

    An, Liangliang; Wang, Guanhua; Jia, Hongyu; Liu, Cuiyun; Sui, Wenjie; Si, Chuanling

    2017-06-01

    The heterogeneity of lignin chemical structure and molecular weight results in the lignin inhomogeneous properties which also covers the antioxidant performance. In order to evaluate the effects of lignin heterogeneity on its antioxidant activity, four lignin fractions from enzymatic hydrolysis lignin were classified by sequential organic solvent extraction and further evaluated by DPPH (1,1-Diphenyl-2-Picrylhydrazyl) free radical scavenging capacity and reducing power analysis. The characterization including FTIR, (1)H NMR and GPC showed that the fractionation process could effectively separate lignin fractions with distinctly different molecular weight and weaken the heterogeneity of unfractionated lignin. The antioxidant performance comparison of lignin fractions indicated that the dichloromethane fraction (F1) with lowest molecular weight (4585g/mol) and highest total phenolics content (246.13mg GAE/g) exhibited the highest antioxidant activity whose value was close to commercial antioxidant BHT (butylated hydroxytoluene). Moreover, the relationship between the antioxidant activity and the structure of lignin was further discussed to elucidate the mechanism of antioxidant activity improvement of lignin fractionation. Consequently, this study suggested that the sequential extraction was an effective way to obtain relatively homogeneous enzymatic hydrolysis lignin fractions which showed the potential for the value-added antioxidant application. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Lignin Sulfonation - A different Approach

    DEFF Research Database (Denmark)

    Bjørkmann, Anders

    2001-01-01

    . It was found that lignin is very reactive, that is why the sulfonation chemistry alone does not necessarily determine its dissolution rate. It became evident that the ultrastructure dispersion of lignin in wood is beneficial for its dissolution. For W, the rate was much higher at pH 1.5 than at 6. MW lignin....... Methylation had also a small rate effect for W, but again a large decrease for MWL....

  18. A facile method for processing lignin reinforced chitosan biopolymer microfibres: optimising the fibre mechanical properties through lignin type and concentration

    Science.gov (United States)

    Wang, K.; Loo, L. S.; Goh, K. L.

    2016-03-01

    A chitosan biopolymer microfibre—reinforced by lignin—has been processed by a wet-spinning method. To optimise the fibre mechanical and structural properties two types of lignin, with molecular weights 28 000 g mol-1 and 60 000 g mol-1, were examined and the chitosan fibre was blended with the respective lignin type at 1, 3, 5, 7 and 8 wt% lignin concentrations. The main effects of lignin type and concentration, as well as the interaction between the two parameters, on the fibre tensile stiffness, extensibility, strength and toughness were evaluated using the two-factor analysis of variance. Significant variations in the respective mechanical properties were observed with varying lignin concentrations (P results were related to the dispersion of lignin in the fibre and the nature of the bonds between lignin and chitosan, based on findings from scanning electron microscopy and Fourier transform infrared spectroscopy. This new method for the fabrication of chitosan biopolymer microfibre is inexpensive and versatile and could lend itself to the production of high performance biocomposite structures.

  19. Modifying lignin to improve bioenergy feedstocks: strengthening the barrier against pathogens?

    Directory of Open Access Journals (Sweden)

    Scott eSattler

    2013-04-01

    Full Text Available Lignin is a ubiquitous polymer present in cell walls of all vascular plants, where it rigidifies and strengthens the cell wall structure through covalent cross-linkages to cell wall polysaccharides. The presence of lignin makes the cell wall recalcitrant to conversion into fermentable sugars for bioenergy uses. Therefore, reducing lignin content and modifying its linkages have become major targets for bioenergy feedstock development through either biotechnology or traditional plant breeding. In addition, lignin synthesis has long been implicated as an important plant defense mechanism against pathogens, because lignin synthesis is often induced at the site of pathogen attack. This article explores the impact of lignin modifications on the susceptibility of a range of plant species to their associated pathogens, and the implications for development of feedstocks for the second-generation biofuels industry. Surprisingly, there are some instances where plants modified in lignin synthesis may display increased resistance to associated pathogens, which is explored in this article.

  20. Characterization of the lignin polymer in Brassicaceae family

    Directory of Open Access Journals (Sweden)

    S. Hemmati

    2017-04-01

    Full Text Available Background and objectives: Residues of medicinal plants after extraction and weeds are suitable candidates for bioethanol production. Significant barriers exist to make the conversion of lignocellulosic feedstock to biofuel cost effective and environmentally friendly; one of which is the lignin polymer. Brassicaceae family is one of the potential targets for biofuel production. The structural characteristics of lignin from Hirschfeldia incana, Sisymbrium altissimum and Cardaria draba were studied in comparison to that of Brassica napus. Methods: Lignin deposition was observed by phloroglucinol and Mäule staining. The total lignin content was determined by Klason method. Maximum UV absorbance and FT-IR spectra were compared. Ratio of syringyl to guaiacyl lignin (S/G ratio as a metric of lignin digestibility was determined by DFRC followed by GC-MS analysis. 1H-NMR spectra of the total lignin was compared with other spectroscopic methods. Results: Staining of thestem cross sections of C. draba showed higher G units in contrast to the higher S units in S. altissimum which was in agreement with 1H-NMR analysis. Total lignin content for H. incana, C. draba and S. altissimum was 27.10%, 23.8% and 24.5%, respectively. The specific maximum UV absorbance appeared between 230-260 nm. FT-IR analysis confirmed the presence of more aromatic structures in the seed maturation stage than the flowering stage. S/G ratio was 0.26, 0.10 and 0.22 for H. incana, C. draba and S. altissimum, respectively.  Conclusion: Except Cardaria draba with the predominance of G subunits in lignin polymer, Hirschfeldia incana and Sisymbrium altissimum are suitable candidates for bioethanol production.

  1. Ammonia Pretreatment of Corn Stover Enables Facile Lignin Extraction

    Energy Technology Data Exchange (ETDEWEB)

    Mittal, Ashutosh; Katahira, Rui; Donohoe, Bryon S.; Pattathil, Sivakumar; Kandemkavil, Sindhu; Reed, Michelle L.; Biddy, Mary J.; Beckham, Gregg T.

    2017-01-30

    Thermochemical pretreatment of lignocellulose is often employed to render polysaccharides more digestible by carbohydrate-active enzymes to maximize sugar yields. The fate of lignin during pretreatment, however, is highly dependent on the chemistry employed and must be considered in cases where lignin valorization is targeted alongside sugar conversion - an important feature of future biorefinery development. Here, a two-step process is demonstrated in which anhydrous ammonia (AA) pretreatment is followed by mild NaOH extraction on corn stover to solubilize and fractionate lignin. As known, AA pretreatment simultaneously alters the structure of cellulose with enhanced digestibility while redistributing lignin. The AA-pretreated residue is then extracted with dilute NaOH at mild conditions to maximize lignin separation, resulting in a digestible carbohydrate-rich solid fraction and a solubilized lignin stream. Lignin removal of more than 65% with over 84% carbohydrate retention is achieved after mild NaOH extraction of AA-pretreated corn stover with 0.1 M NaOH at 25 degrees C. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AA-pretreated residue shows that ammonolysis of ester bonds occurs to partially liberate hydroxycinnamic acids, and the AA-pretreated/NaOH-extracted residue exhibits a global reduction of all lignin moieties caused by reduced lignin content. A significant reduction (~70%) in the weight-average molecular weight (Mw) of extracted lignin is also achieved. Imaging of AA-pretreated/NaOH extracted residues show extensive delamination and disappearance of coalesced lignin globules from within the secondary cell walls. Glycome profiling analyses demonstrates ultrastructural level cell wall modifications induced by AA pretreatment and NaOH extraction, resulting in enhanced extractability of hemicellulosic glycans, indicating enhanced polysaccharide accessibility. The glucose and xylose yields from enzymatic hydrolysis of AA

  2. Characteristics of Lignin from Flax Shives as Affected by Extraction Conditions

    Directory of Open Access Journals (Sweden)

    Kelly Ross

    2010-10-01

    Full Text Available Lignin, a polyphenolic molecule, is a major constituent of flax shives. This polyphenolic molecular structure renders lignin a potential source of a variety of commercially viable products such as fine chemicals. This work compares the performance of different lignin isolation methods. Lignin from flax shive was isolated using both conventional alkaline extraction method and a novel experimental pressurized low polarity water (PLPW extraction process. The lignin yields and chemical composition of the lignin fractions were determined. The conventional alkali treatment with 1.25 M NaOH, heated at 80 °C for 5 h, extracted 92 g lignin per kg flax shives, while lignin yields from the PLPW extracts ranged from 27 to 241 g lignin per kg flax shives. The purity and monomeric composition of the lignins obtained from the different extraction conditions was assessed via UV spectroscopy and alkaline nitrobenzene oxidation. Lignin obtained from conventional alkali treatment with 1.25 M NaOH, heated at 80 °C for 5 h was of low purity and exhibited the lowest yields of nitrobenzene oxidation products. With respect to alkali assisted PLPW extractions, temperature created an opposing effect on lignin yield and nitrobenzene oxidation products. More lignin was extracted as temperature increased, yet the yield of nitrobenzene oxidation products decreased. The low yield of nitrobenzene oxidation products may be attributed to either the formation of condensed structures or the selective dissolution of condensed structures of lignin during the pressurized alkaline high temperature treatment. Analytical pyrolysis, using pyroprobe GC-MS, was used to investigate the molecular composition of the lignin samples. The total yield of pyrolysis lignin products was 13.3, 64.7, and 30.5% for the 1.25 M NaOH extracted lignin, alkaline assisted PLPW extracted lignin, and the unprocessed flax shives, respectively. Key lignin derived compounds such as guaiacol, 4-vinyl guaiacol, 4

  3. [Phenolic foam prepared by lignin from a steam-explosion derived biorefinery of corn stalk].

    Science.gov (United States)

    Wang, Guanhua; Chen, Hongzhang

    2014-06-01

    To increase the integral economic effectiveness, biorefineries of lignocellulosic materials should not only utilize carbohydrates hydrolyzed from cellulose and hemicellulose but also use lignin. We used steam-exploded corn stalk as raw materials and optimized the temperature and alkali concentration in the lignin extraction process to obtain lignin liquor with higher yield and purity. Then the concentrated lignin liquor was used directly to substitute phenol for phenolic foam preparation and the performances of phenolic foam were characterized by microscopic structure analysis, FTIR, compression strength and thermal conductivity detection. The results indicated that, when steam-exploded corn stalk was extracted at 120 degrees C for 2 h by 1% NaOH with a solid to liquid ratio of 1:10, the extraction yield of lignin was 79.67%. The phenolic foam prepared from the concentrated lignin liquor showed higher apparent density and compression strength with the increasing substitution rate of lignin liquor. However, there were not significant differences of thermal conductivity and flame retardant properties by the addition of lignin, which meant that the phenolic foam substituted by lignin liquor was approved for commercial application. This study, which uses alkali-extracted lignin liquor directly for phenolic foam preparation, provides a relatively simple way for utilization of lignin and finally increases the overall commercial operability ofa lignocellulosic biorefinery derived by steam explosion.

  4. Recovery and Utilization of Lignin Monomers as Part of the Biorefinery Approach

    Directory of Open Access Journals (Sweden)

    Kirsten M. Davis

    2016-10-01

    Full Text Available Lignin is a substantial component of lignocellulosic biomass but is under-utilized relative to the cellulose and hemicellulose components. Historically, lignin has been burned as a source of process heat, but this heat is usually in excess of the process energy demands. Current models indicate that development of an economically competitive biorefinery system requires adding value to lignin beyond process heat. This addition of value, also known as lignin valorization, requires economically viable processes for separating the lignin from the other biomass components, depolymerizing the lignin into monomeric subunits, and then upgrading these monomers to a value-added product. The fact that lignin’s biological role is to provide biomass with structural integrity means that this heteropolymer can be difficult to depolymerize. However, there are chemical and biological routes to upgrade lignin from its native form to compounds of industrial value. Here we review the historical background and current technology of (thermo chemical depolymerization of lignin; the natural ability of microbial enzymes and pathways to utilize lignin, the current prospecting work to find novel microbial routes to lignin degradation, and some applications of these microbial enzymes and pathways; and the current chemical and biological technologies to upgrade lignin-derived monomers.

  5. Effects of lignin modification on wheat straw cell wall deconstruction by Phanerochaete chrysosporium.

    Science.gov (United States)

    Zeng, Jijiao; Singh, Deepak; Gao, Difeng; Chen, Shulin

    2014-01-01

    A key focus in sustainable biofuel research is to develop cost-effective and energy-saving approaches to increase saccharification of lignocellulosic biomass. Numerous efforts have been made to identify critical issues in cellulose hydrolysis. Aerobic fungal species are an integral part of the carbon cycle, equip the hydrolytic enzyme consortium, and provide a gateway for understanding the systematic degradation of lignin, hemicelluloses, and cellulose. This study attempts to reveal the complex biological degradation process of lignocellulosic biomass by Phanerochaete chrysosporium in order to provide new knowledge for the development of energy-efficient biorefineries. In this study, we evaluated the performance of a fungal biodegradation model, Phanerochaete chrysosporium, in wheat straw through comprehensive analysis. We isolated milled straw lignin and cellulase enzyme-treated lignin from fungal-spent wheat straw to determine structural integrity and cellulase absorption isotherms. The results indicated that P. chrysosporium increased the total lignin content in residual biomass and also increased the cellulase adsorption kinetics in the resulting lignin. The binding strength increased from 117.4 mL/g to 208.7 mL/g in milled wood lignin and from 65.3 mL/g to 102.4 mL/g in cellulase enzyme lignin. A detailed structural dissection showed a reduction in the syringyl lignin/guaiacyl lignin ratio and the hydroxycinnamate/lignin ratio as predominant changes in fungi-spent lignin by heteronuclear single quantum coherence spectroscopy. P. chrysosporium shows a preference for degradation of phenolic terminals without significantly destroying other lignin components to unzip carbohydrate polymers. This is an important step in fungal growth on wheat straw. The phenolics presumably locate at the terminal region of the lignin moiety and/or link with hemicellulose to form the lignin-carbohydrate complex. Findings may inform the development of a biomass hydrolytic enzyme

  6. Ultrafine microporous and mesoporous activated carbon fibers from alkali lignin

    OpenAIRE

    2013-01-01

    A facile and sustainable approach has been successfully devised to fabricate ultrafine (100-500 nm) highly porous activated carbon fibers (ACFs) by electrospinning of aqueous solutions of predominantly alkali lignin (low sulfonate content) followed by simultaneous carbonization and activation at 850 °C under N2. Incorporating a polyethylene oxide (PEO) carrier with only up to one ninth of lignin not only enabled efficient electrospinning into fibers but also retained fibrous structures during...

  7. Unique low-molecular-weight lignin with high purity extracted from wood by deep eutectic solvents (DES): a source of lignin for valorization

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez-Vasco, Carlos; Ma, Ruoshui; Quintero, Melissa; Guo, Mond; Geleynse, Scott; Ramasamy, Karthikeyan K.; Wolcott, Michael; Zhang, Xiao

    2016-01-01

    This paper reports a new method of applying Deep Eutectic Solvents (DES) for extracting lignin from woody biomass with high yield and high purity. DES mixtures prepared from Choline Chloride (ChCl) and four hydrogen-bond donors–acetic acid, lactic acid, levulinic acid and glycerol–were evaluated for treatment of hardwood (poplar) and softwood (D. fir). It was found that these DES treatments can selectively extract a significant amount of lignin from wood with high yields: 78% from poplar and 58% from D. fir. The extracted lignin has high purity (95%) with unique structural properties. We discover that DES can selectively cleave ether linkages in wood lignin and facilitate lignin removal from wood. The mechanism of DES cleavage of ether bonds between phenylpropane units was investigated. The results from this study demonstrate that DES is a promising solvent for wood delignification and the production of a new source of lignin with promising potential applications.

  8. Effect of liquid hot water pretreatment severity on properties of hardwood lignin and enzymatic hydrolysis of cellulose.

    Science.gov (United States)

    Ko, Ja Kyong; Kim, Youngmi; Ximenes, Eduardo; Ladisch, Michael R

    2015-02-01

    Lignin, one of the major components of lignocellulosic biomass, plays an inhibitory role on the enzymatic hydrolysis of cellulose. This work examines the role of lignin in pretreated hardwood, where extents of cellulose hydrolysis decrease, rather than increase with increasing severity of liquid hot water pretreatment. Hardwood pretreated with liquid hot water at severities ranging from log Ro  = 8.25 to 12.51 resulted in 80-90% recovery of the initial lignin in the residual solids. The ratio of acid insoluble lignin (AIL) to acid soluble lignin (ASL) increased and the formation of spherical lignin droplets on the cell wall surface was observed as previously reported in the literature. When lignins were isolated from hardwoods pretreated at increasing severities and characterized based on glass transition temperature (Tg ), the Tg of isolated lignins was found to increase from 171 to 180°C as the severity increased from log Ro  = 10.44 to 12.51. The increase in Tg suggested that the condensation reactions of lignin molecules occurred during pretreatment and altered the lignin structure. The contribution of the changes in lignin properties to enzymatic hydrolysis were examined by carrying out Avicel hydrolysis in the presence of isolated lignins. Lignins derived from more severely pretreated hardwoods had higher Tg values and showed more pronounced inhibition of enzymatic hydrolysis. © 2014 Wiley Periodicals, Inc.

  9. Mechanism of the catalytic ozonization of lignin in the presence of Mn(II) ions

    Science.gov (United States)

    Mitrofanova, A. N.; Khudoshin, A. G.; Lunin, V. V.

    2013-07-01

    The reaction between ozone and lignin in aqueous solutions catalyzed by Mn(II) ions is studied. The rate of destruction for aromatic structures of lignin is found to increase in the presence of Mn(II) ions. However, the greatest catalytic effect is observed upon the transformation of aliphatic acids that are difficult to oxidize with ozone. The introduction of catalyst raises the total consumption of ozone from 3 to 7 mol per each structural unit of lignin. A scheme is proposed for the transformation of phenol fragments of lignin using ozone with the participation of Mn(II) ions: at the initial stage, we observe the ozone oxidation of lignin and Mn(II) to Mn(III) ions stabilized with products of lignin oxidation and accompanied by the formation of chelate complexes, and the Mn(III) chelate complexes act as low-molecular mediators, attacking phenol structures and initiating radical processes.

  10. Cellulase-lignin interactions in the enzymatic hydrolysis of lignocellulose

    Energy Technology Data Exchange (ETDEWEB)

    Rahikainen, J.

    2013-11-01

    Today, the production of transportation fuels and chemicals is heavily dependent on fossil carbon sources, such as oil and natural gas. Their limited availability and the environmental concerns arising from their use have driven the search for renewable alternatives. Lignocellulosic plant biomass is the most abundant, but currently underutilised, renewable carbon-rich resource for fuel and chemical production. Enzymatic degradation of structural polysaccharides in lignocellulose produces soluble carbohydrates that serve as ideal precursors for the production of a vast amount of different chemical compounds. The difficulty in full exploitation of lignocellulose for fuel and chemical production lies in the complex and recalcitrant structure of the raw material. Lignocellulose is mainly composed of structural polysaccharides, cellulose and hemicellulose, but also of lignin, which is an aromatic polymer. Enzymatic degradation of cellulose and hemicellulose is restricted by several substrate- and enzyme-related factors, among which lignin is considered as one of the most problematic issues. Lignin restricts the action of hydrolytic enzymes and enzyme binding onto lignin has been identified as a major inhibitory mechanism preventing efficient hydrolysis of lignocellulosic feedstocks. In this thesis, the interactions between cellulase enzymes and lignin-rich compounds were studied in detail and the findings reported in this work have the potential to help in controlling the harmful cellulase-lignin interactions, and thus improve the biochemical processing route from lignocellulose to fuels and chemicals.

  11. Transition metal catalyzed oxidation of Alcell lignin, soda lignin, and lignin model compounds in ionic liquids

    NARCIS (Netherlands)

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Jongerius, A.L.|info:eu-repo/dai/nl/325840202; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2013-01-01

    Lignin is a component of lignocellulosic biomass from which important aromatic compounds can potentially be obtained. In the present work, Alcell and soda lignin were dissolved in the ionic liquid 1-ethyl-3-methylimidazolium diethylphosphate (EMIM DEP) and subsequently oxidized using several transit

  12. Transition metal catalyzed oxidation of Alcell lignin, soda lignin, and lignin model compounds in ionic liquids

    NARCIS (Netherlands)

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Jongerius, A.L.|info:eu-repo/dai/nl/325840202; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2013-01-01

    Lignin is a component of lignocellulosic biomass from which important aromatic compounds can potentially be obtained. In the present work, Alcell and soda lignin were dissolved in the ionic liquid 1-ethyl-3-methylimidazolium diethylphosphate (EMIM DEP) and subsequently oxidized using several

  13. Lignin valorization: lignin nanoparticles as high-value bio-additive for multifunctional nanocomposites.

    Science.gov (United States)

    Tian, Dong; Hu, Jinguang; Bao, Jie; Chandra, Richard P; Saddler, Jack N; Lu, Canhui

    2017-01-01

    Although conversion of low value but high-volume lignin by-product to its usable form is one of the determinant factors for building an economically feasible integrated lignocellulose biorefinery, it has been challenged by its structural complexity and inhomogeneity. We and others have shown that uniform lignin nanoparticles can be produced from a wide range of technical lignins, despite the varied lignocellulosic biomass and the pretreatment methods/conditions applied. This value-added nanostructure lignin enriched with multifunctional groups can be a promising versatile material platform for various downstream utilizations especially in the emerging nanocomposite fields. Inspired by the story of successful production and application of nanocellulose biopolymer, two types of uniform lignin nanoparticles (LNPs) were prepared through self-assembling of deep eutectic solvent (DES) and ethanol-organosolv extracted technical lignins derived from a two-stage fractionation pretreatment approach, respectively. Both LPNs exhibited sphere morphology with unique core-shell nanostructure, where the DES-LNPs showed a more uniform particle size distribution. When incorporated into the traditional polymeric matrix such as poly(vinyl alcohol), these LPN products displayed great potential to formulate a transparent nanocomposite film with additional UV-shielding efficacy (reached ~80% at 400 nm with 4 wt% of LNPs) and antioxidant functionalities (reached ~160 μm mol Trolox g(-1) with 4 wt% of LNPs). At the same time, the abundant phenolic hydroxyl groups on the shell of LNPs also provided good interfacial adhesion with PVA matrix through the formation of hydrogen bonding network, which further improved the mechanical and thermal performances of the fabricated LNPs/PVA nanocomposite films. Both LNPs are excellent candidates for producing multifunctional polymer nanocomposites using facile technical route. The prepared transparent and flexible LNPs/PVA composite films with

  14. Composition of Lignin-to-Liquid Solvolysis Oils from Lignin Extracted in a Semi-Continuous Organosolv Process

    Science.gov (United States)

    Løhre, Camilla; Vik Halleraker, Hilde; Barth, Tanja

    2017-01-01

    The interest and on-going research on utilisation of lignin as feedstock for production of renewable and sustainable aromatics is expanding and shows great potential. This study investigates the applicability of semi-continuously organosolv extracted lignin in Lignin-to-Liquid (LtL) solvolysis, using formic acid as hydrogen donor and water as solvent under high temperature–high pressure (HTHP) conditions. The high purity of the organosolv lignin provides high conversion yields at up to 94% based on lignin mass input. The formic acid input is a dominating parameter in lignin conversion. Carbon balance calculations of LtL-solvolysis experiments also indicate that formic acid can give a net carbon contribution to the bio-oils, in addition to its property as hydrogenation agent. Compound specific quantification of the ten most abundant components in the LtL-oils describe up to 10% of the bio-oil composition, and reaction temperature is shown to be the dominating parameter for the structures present. The structural and quantitative results from this study identify components of considerable value in the LtL-oil, and support the position of this oil as a potentially important source of building blocks for the chemical and pharmaceutical industry. PMID:28124994

  15. Fast Pyrolysis of Four Lignins from Different Isolation Processes Using Py-GC/MS

    Directory of Open Access Journals (Sweden)

    Xiaona Lin

    2015-06-01

    Full Text Available Pyrolysis is a promising approach that is being investigated to convert lignin into higher value products including biofuels and phenolic chemicals. In this study, fast pyrolysis of four types of lignin, including milled Amur linden wood lignin (MWL, enzymatic hydrolysis corn stover lignin (EHL, wheat straw alkali lignin (AL and wheat straw sulfonate lignin (SL, were performed using pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS. Thermogravimetric analysis (TGA showed that the four lignins exhibited widely different thermolysis behaviors. The four lignins had similar functional groups according to the FTIR analysis. Syringyl, guaiacyl and p-hydroxyphenylpropane structural units were broken down during pyrolysis. Fast pyrolysis product distributions from the four lignins depended strongly on the lignin origin and isolation process. Phenols were the most abundant pyrolysis products from MWL, EHL and AL. However, SL produced a large number of furan compounds and sulfur compounds originating from kraft pulping. The effects of pyrolysis temperature and time on the product distributions from corn stover EHL were also studied. At 350 °C, EHL pyrolysis mainly produced acids and alcohols, while phenols became the main products at higher temperature. No obvious influence of pyrolysis time was observed on EHL pyrolysis product distributions.

  16. Peracetic Acid Depolymerization of Biorefinery Lignin for Production of Selective Monomeric Phenolic Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Ruoshui [Voiland School of Chemical Engineering and Bioengineering, Bioproducts, Science & Engineering Laboratory, Washington State University, 2710 Crimson Way Richland WA 99354 USA; Guo, Mond [Voiland School of Chemical Engineering and Bioengineering, Bioproducts, Science & Engineering Laboratory, Washington State University, 2710 Crimson Way Richland WA 99354 USA; Lin, Kuan-ting [Voiland School of Chemical Engineering and Bioengineering, Bioproducts, Science & Engineering Laboratory, Washington State University, 2710 Crimson Way Richland WA 99354 USA; Hebert, Vincent R. [Food and Environmental Laboratory, Washington State, University-TriCities, 2710 Crimson Way Richland WA 99354 USA; Zhang, Jinwen [Wood Materials and Engineering Laboratory, Washington State University, Pullman WA 99164 USA; Wolcott, Michael P. [Wood Materials and Engineering Laboratory, Washington State University, Pullman WA 99164 USA; Quintero, Melissa [Voiland School of Chemical Engineering and Bioengineering, Bioproducts, Science & Engineering Laboratory, Washington State University, 2710 Crimson Way Richland WA 99354 USA; Ramasamy, Karthikeyan K. [Chemical and Biological Process Development Group, Pacific Northwest National Laboratory, Richland WA 99354 USA; Chen, Xiaowen [National Bioenergy Center, National Renewable Energy Lab, 1617 Cole Blvd Golden CO 80127 USA; Zhang, Xiao [Voiland School of Chemical Engineering and Bioengineering, Bioproducts, Science & Engineering Laboratory, Washington State University, 2710 Crimson Way Richland WA 99354 USA

    2016-07-04

    Lignin is the largest source of renewable material with an aromatic skeleton. However, due to the recalcitrant and heterogeneous nature of the lignin polymer as well as its complex side chain structures, it has been a challenge to effectively depolymerize lignin and produce high value chemicals with high selectivity. In this study, a highly efficient lignin-to-monomeric phenolic compounds (MPC) conversion method based on peracetic acid (PAA) treatment was reported. PAA treatment of two biorefinery lignin samples, diluted acid pretreated corn stover lignin (DACSL) and steam exploded spruce lignin (SESPL), led to complete solubilization and production of selective hydroxylated monomeric phenolic compounds (MPC-H) and monomeric phenolic acid compounds (MPC-A) inclduing 4-hydroxy-2-methoxyphenol, p-hydroxybenzoic acid, vanillic acid, syringic acid, and 3,4-dihydroxybenzoic acid. The maximized MPCs yields obtained were 18% and 22% based on the initial weight of the lignin in SESPL and DACSL respectively. However, we found that the addition of niobium pentoxide catalyst to PAA treatment of lignin can significantly improve the MPC yields up to 47%. The key reaction steps and main mechanisms involved in this new lignin-to-MPC valorization pathway were investigated and elucidated.

  17. KNOX1 genes regulate lignin deposition and composition in monocots and dicots.

    Directory of Open Access Journals (Sweden)

    Brad T Townsley

    2013-05-01

    Full Text Available Plant secondary cell walls are deposited mostly in vascular tissues such as xylem vessels, tracheids, and fibers. These cell walls are composed of a complex matrix of compounds including cellulose, hemicellulose, and lignin. Lignin functions primarily to maintain the structural and mechanical integrity of both the transport vessel and the entire plant itself. Since lignin has been identified as a major source of biomass for biofuels, regulation of secondary cell wall biosynthesis has been a topic of much recent investigation. Biosynthesis and patterning of lignin involves many developmental and environmental cues including evolutionarily conserved transcriptional regulatory modules and hormonal signals. Here, we investigate the role of the class I KNOX genes and gibberellic acid in the lignin biosynthetic pathway in a representative monocot and a representative eudicot. Knotted1 overexpressing mutant plants showed a reduction in lignin content in both maize and tobacco. Expression of four key lignin biosynthesis genes was analyzed and revealed that KNOX1 genes regulate at least two steps in the lignin biosynthesis pathway. The negative regulation of lignin both in a monocot and a eudicot by the maize Kn1 gene suggests that lignin biosynthesis may be preserved across large phylogenetic distances. The evolutionary implications of regulation of lignification across divergent species are discussed.

  18. Preparation and characterization of lignin based macromonomer and its copolymers with butyl methacrylate.

    Science.gov (United States)

    Liu, Xiaohuan; Wang, Jifu; Yu, Juan; Zhang, Mingming; Wang, Chunpeng; Xu, Yuzhi; Chu, Fuxiang

    2013-09-01

    Copolymerization of butyl methacrylate (BMA) with biobutanol lignin (BBL) was achieved by free-radical polymerization (FRP) using a lignin-based macromonomer. The lignin-based macromonomer containing acrylic groups was prepared by reacting acryloyl chloride with biobutanol lignin using triethylamine (TEA) as absorb acid agentin. From the results of elemental analysis and GPC, the average degree of polymerization (DP) of BBL was estimated to be five. A detailed molecular characterization has been performed, including techniques such as (1)H NMR, (13)C NMR and UV-vis spectroscopies, which provided quantitative information about the composition of the copolymers. The changes in the solubility of lignin-g-poly(BMA) copolymers in ethyl ether were dependent on the length of poly(BMA) side chain. TGA analysis indicated that the lignin-containing poly(BMA) graft copolymers exhibited high thermal stability. The bulky aromatic group of lignin increased the glass-transition temperature of poly(BMA). In order to confirm the main structure of copolymer, (AC-g-BBL)-co-BMA copolymer was also synthesized by atom transfer radical polymerization (ATRP), and the results revealed that the copolymer prepared by ATRP had the same solution behavior as that prepared by FRP, and the lignin-based macromonomer showed no homopolymerizability due to the steric hindrance. In addition, the lignin-co-BMA copolymer had a surprisingly higher molecular weight than poly(BMA) under the same reaction condition, suggesting that a branched lignin based polymer could be formed.

  19. Kraft lignin biorefinery: A proposal.

    Science.gov (United States)

    Hu, Jianjun; Zhang, Quanguo; Lee, Duu-Jong

    2017-09-01

    Lignin is a huge energy and carbon reserve but owing to its highly biologically recalcitrant nature it is commonly regarded as a waste in lignocellulosic biomass biorefinery. To realize the lignin biorefinery, it is proposed to use Kraft lignin, isolated from black liquor from Kraft pulping mills, as starting material to be fragmented by fast pyrolysis or selective catalysis to aromatic sub-units and to be post-refining with additional cleavage reaction and separation/purification as commodity aromatics pool in chemical industries. This Note calls for research efforts on detailed investigation of the feasibility of this proposed scenario. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Enzymatic Specific Production and Chemical Functionalization of Phenylpropanone Platform Monomers from Lignin

    OpenAIRE

    Ohta, Yukari; Hasegawa, Ryoichi; Kurosawa, Kanako; Maeda, Allyn H.; Koizumi, Toshio; Nishimura,Hiroshi; Okada, Hitomi; Qu, Chen; Saito, Kaori; Watanabe, Takashi; Hatada, Yuji

    2016-01-01

    Abstract Enzymatic catalysis is an ecofriendly strategy for the production of high‐value low‐molecular‐weight aromatic compounds from lignin. Although well‐definable aromatic monomers have been obtained from synthetic lignin‐model dimers, enzymatic‐selective synthesis of platform monomers from natural lignin has not been accomplished. In this study, we successfully achieved highly specific synthesis of aromatic monomers with a phenylpropane structure directly from natural lignin using a casca...

  1. Roles of silica and lignin in horsetail (Equisetum hyemale), with special reference to mechanical properties

    Science.gov (United States)

    Yamanaka, Shigeru; Sato, Kanna; Ito, Fuyu; Komatsubara, Satoshi; Ohata, Hiroshi; Yoshino, Katsumi

    2012-02-01

    This research deals with detailed analyses of silica and lignin distribution in horsetail with special reference to mechanical strength. Scanning electron images of a cross-section of an internode showed silica deposited densely only around the outer epidermis. Detailed histochemical analyses of lignin showed no lignin deposition in the silica-rich outer internodes of horsetail, while a characteristic lignin deposition was noticed in the vascular bundle in inner side of internodes. To analyze the structure of horsetail from a mechanical viewpoint, we calculated the response of a model structure of horsetail to a mechanical force applied perpendicularly to the long axis by a finite element method. We found that silica distributed in the outer epidermis may play the major structural role, with lignin's role being limited ensuring that the vascular bundle keep waterproof. These results were in contrast to more modern tall trees like gymnosperms, for which lignin provides mechanical strength. Lignin has the advantage of sticking to cellulose, hemicellulose, and other materials. Such properties make it possible for plants containing lignin to branch. Branching of tree stems aids in competing for light and other atmospheric resources. This type of branching was impossible for ancient horsetails, which relied on the physical properties of silica. From the evolutional view points, over millennia in trees with high lignin content, true branching, and many chlorophyll-containing leaves developed.

  2. Lignin-Furfural Based Adhesives

    Directory of Open Access Journals (Sweden)

    Prajakta Dongre

    2015-07-01

    Full Text Available Lignin recovered from the hot-water extract of sugar maple (Acer saccharum is used in this study to synthesize adhesive blends to replace phenol-formaldehyde (PF resin. Untreated lignin is characterized by lignin content and nuclear magnetic resonance (NMR analysis. The molecular weight distribution of the lignin and the blends are characterized by size exclusion chromatography (SEC. The effect of pH (0.3, 0.65 and 1, ex situ furfural, and curing conditions on the tensile properties of adhesive reinforced glass fibers is determined and compared to the reinforcement level of commercially available PF resin. The adhesive blend prepared at pH = 0.65 with no added furfural exhibits the highest tensile properties and meets 90% of the PF tensile strength.

  3. Sorption of polycyclic aromatic hydrocarbons (PAHs) to lignin: effects of hydrophobicity and temperature.

    Science.gov (United States)

    Zhang, Ming; Ahmad, Mahtab; Lee, Sang Soo; Xu, Li Heng; Ok, Yong Sik

    2014-07-01

    The study of the sorption of contaminants to lignin is significant for understanding the migration of contaminants in the environment as well as developing low cost sorbent. In this study, sorption of three polycyclic aromatic hydrocarbons (PAHs), naphthalene, acenaphthene and phenanthrene, to lignin was investigated. Sorption isotherms were well described by both linear and Freundlich sorption models. Sorption coefficients of PAHs to lignin from water obtained from regression of both linear model (K d) and Freundlich model (K f) were highly positively correlated with hydrophobicity of PAHs. The amorphous structure of lignin provided sufficient sorption domain for partitioning of PAHs, and the attraction between PAHs molecules and aromatic fractions in lignin via π-π electron-donor-acceptor (π-π EDA) interaction is hypothesized to provide a strong sorption force. Thermodynamic modeling revealed that sorption of PAHs to lignin was a spontaneous and exothermic process.

  4. Biomass pretreatments capable of enabling lignin valorization in a biorefinery process.

    Science.gov (United States)

    Narron, Robert H; Kim, Hoyong; Chang, Hou-Min; Jameel, Hasan; Park, Sunkyu

    2016-04-01

    Recent techno-economic studies of proposed lignocellulosic biorefineries have concluded that creating value from lignin will assist realization of biomass utilization into valuable fuels, chemicals, and materials due to co-valorization and the new revenues beyond carbohydrates. The pretreatment step within a biorefinery process is essential for recovering carbohydrates, but different techniques and intensities have a variety of effects on lignin. Acidic and alkaline pretreatments have been shown to produce diverse lignins based on delignification chemistry. The valorization potential of pretreated lignin is affected by its chemical structure, which is known to degrade, including inter-lignin condensation under high-severity pretreatment. Co-valorization of lignin and carbohydrates will require dampening of pretreatment intensities to avoid such effects, in spite of tradeoffs in carbohydrate production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Optimizing Noncovalent Interactions Between Lignin and Synthetic Polymers to Develop Effective Compatibilizers

    Energy Technology Data Exchange (ETDEWEB)

    Henry, Nathan [University of Tennessee, Knoxville (UTK); Harper, David [University of Tennessee, Knoxville (UTK), Center for Renewable Carbon; Dadmun, Mark D [ORNL

    2012-01-01

    Experiments are designed and completed to identify an effective polymeric compatibilizer for lignin polystyrene blends. Copolymers of styrene and vinylphenol are chosen as the structure of the compatibilizer as the VPh unit can readily form intermolecular hydrogen bonds with the lignin molecule. Electron microscopy, thermal analysis, and neutron refl ectivity results demonstrate that among these compatibilizers, a copolymer of styrene and VPh with 20% 30% VPh most readily forms intermolecular interactions with the lignin molecule and results in the most well-dispersed blends with lignin. This behavior is explained by invoking the competition of intra- and intermolecular hydrogen bonding and functional group accessibility in forming intermolecular interactions.

  6. Study of structural characterization of sulfomethylated wheat straw lignin%麦草碱木质素磺甲基化反应及性能的研究

    Institute of Scientific and Technical Information of China (English)

    梁文学; 邱学青; 欧阳新平; 杨东杰

    2007-01-01

    针对麦草碱木质素水溶性差、分子质量低、难以工业利用的问题,采用Fenton试剂为氧化剂,以亚硫酸钠为磺化剂对麦草浆碱木质素进行氧化再进行磺甲基化反应,得到质量分数为33%(Wt)的氧化磺甲基化碱木质素的溶液.红外光谱(FTIR)测试表明产物中具有磺酸基的特征吸收峰.利用凝胶渗透色谱(GPC)测得其重均分子质量达到6653 g·mol-1.通过紫外吸收光谱(UV)测得其最大吸收波长在276 nm处.通过碱木质素磺化反应前后的核磁共振(13CNMR)测得磺甲基接入碱木质素中芳环的C-5位.当溶液质量浓度为30 g·L-1时,溶液表面张力为45.3 mN·m-1.%It is hard to utilize the wheat straw grass lignin as resource due to its in solubility in neutral aqueous and low molecular weight. In order to promote the utilization of it, sulfomethylation of wheat straw grass lignin is studied using Fenton reagent as oxidation reagent, sodium sulfite anhydrous and formaldehyde as sulfomethylation agent. The characterization of oxided and sulfometylated wheat straw grass lignin (OSWSL) is determined using FTIR, GPC,13C-NMR and UV. The results show that the average molecular weight of OSWSL (-Mw) is 6653 g·mol-1 which is greater than that of wheat strew lignin of 2828g·mol-1. 13C-NMR spectrum exhibits that the position of sulfomethylation reaction is C-5 in Guaiacyl suit, and the maximum absorption peak of UV is at 276 nm. When the solution concentration of OSWSL is 30 g·L-1, the surface tension is 45.3 mN·m-1.

  7. Pyrolysis of agricultural residues. Part II. Yield and chemical composition of tars and oils produced from cotton stalks, and assessment of lignin structure

    Energy Technology Data Exchange (ETDEWEB)

    Fahmy, Y.; Mobarak, F.; Schweers, W.

    1982-01-01

    The pyrolysis of cotton stalks at 400-600 degrees resulted in the production of char and tar in highest yield, and the increase of temperature within this range decreased the yield of tar and phenolic compounds in the tar but increased the ratio of neutrals to acids in the tar. On decreasing the particle size of stalks, the total yield of tar remained almost constant regardless of pyrolysis temperature but that of phenols increased while that of neutrals and acids decreased. The distribution of syringol and guaiacol in phenolic products indicated that lignin in stalks belongs to the guaiacyl-syringyl type.

  8. Progress and obstacles in the production and application of recombinant lignin-degrading peroxidases.

    Science.gov (United States)

    Lambertz, Camilla; Ece, Selin; Fischer, Rainer; Commandeur, Ulrich

    2016-04-01

    Lignin is 1 of the 3 major components of lignocellulose. Its polymeric structure includes aromatic subunits that can be converted into high-value-added products, but this potential cannot yet been fully exploited because lignin is highly recalcitrant to degradation. Different approaches for the depolymerization of lignin have been tested, including pyrolysis, chemical oxidation, and hydrolysis under supercritical conditions. An additional strategy is the use of lignin-degrading enzymes, which imitates the natural degradation process. A versatile set of enzymes for lignin degradation has been identified, and research has focused on the production of recombinant enzymes in sufficient amounts to characterize their structure and reaction mechanisms. Enzymes have been analyzed individually and in combinations using artificial substrates, lignin model compounds, lignin and lignocellulose. Here we consider progress in the production of recombinant lignin-degrading peroxidases, the advantages and disadvantages of different expression hosts, and obstacles that must be overcome before such enzymes can be characterized and used for the industrial processing of lignin.

  9. Chemical Changes of Raw Materials and Manufactured Binderless Boards during Hot Pressing: Lignin Isolation and Characterization

    Directory of Open Access Journals (Sweden)

    Yong-Chang Sun

    2014-01-01

    Full Text Available Thermomechanical pulp (TMP is used for fiber production in binderless boards industries. Milled wood lignin (MWL and enzymatic mild acidolysis lignin (EMAL isolated from raw material and from binderless boards (BB were comparatively analyzed to investigate the effects of chemical changes on the bonding performance in BB. The results showed that acid-insoluble lignin of the BB were increased during the sodium silicate solution pretreatment after hot-pressing. The lignin fractions obtained were characterized by gel permeation chromatography (GPC, Fourier transform infrared (FT-IR spectroscopy, and 1H-13C correlation heteronuclear single-quantum coherence (HSQC nuclear magnetic resonance (NMR spectroscopy. Results showed that 31.1% of EMAL (based on Klason lignin with low molecular weight (Mw=1630 g/mol was isolated from the BB. The increased total phenolic OH groups (3.97 mmol/g of EMAL from sodium silicate solution pretreated BB indicated that there was degradation of lignin and cleavage of lignin-carbohydrate linkages during hot-pressing. In addition, the content of β-O-4' aryl ether linkages of EMAL from the BB increased to 69.2%, which was higher than that of the untreated sample (60.1%. It was found that S units (syringyl-like lignin structures were preferentially condensed by hot pressing over G (guaiacyl-like lignin structures units, and the S/G ratio increased after the hot-pressing process.

  10. Lignin biosynthesis and its molecular regulation

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Lignin biosynthesis has become increasingly highlighted because it plays an important role in the growth and development of plant, in the systematic evolution of plant and in the human life. Due to the progress in the field of lignin studies in recent years, the lignin biosynthesis pathway has been 修订日期:. Here we discuss some genetic engineering approaches on lignin biosynthesis, and conceive strategy to regulate lignin biosynthesis in order to use lignin resource more efficiently in agricultural and industrial productions.

  11. Characterization of lignin extracted from birch wood by a modified hydrotropic process.

    Science.gov (United States)

    Gabov, Konstantin; Gosselink, Richard J A; Smeds, Annika I; Fardim, Pedro

    2014-11-05

    In this work an environmentally friendly hydrotropic process was used to extract lignin from industrial birch wood chips. Two hydrotropic treatments were performed, a conventional and a modified process. The lignins were characterized using FTIR, pyrolysis-gas chromatography-mass spectrometry (pyrolysis-GC-MS), (31)P and (1)H-(13)C HSQC NMR, and size exclusion chromatography (SEC). The chemical (carbohydrates, extractives, etc.) and elemental compositions of the lignins were also determined. The yields of both lignins were 16.1% (dry wood basis), and the obtained lignins had very low contents of non-lignin compounds. The treatments resulted in significant changes of the structure of the lignins, a decrease in aliphatic hydroxyls and an increase in phenolic ones. The lignin isolated by the modified treatment underwent more substantial change than the reference one. It is believed that the data presented will facilitate utilization of hydrotropic lignin and promote the adoption of the hydrotropic process in the pulp and biorefinery industry.

  12. Biomass-derived Lignin to Jet Fuel Range Hydrocarbons via Aqueous Phase Hydrodeoxygenation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang; Ruan, Hao; Pei, Haisheng; Wang, Huamin; Chen, Xiaowen; Tucker, Melvin P.; Cort, John R.; Yang, Bin

    2015-09-14

    A catalytic process, involving the hydrodeoxygenation (HDO) of the dilute alkali extracted corn stover lignin catalysed by noble metal catalyst (Ru/Al2O3) and acidic zeolite (H+-Y), to produce lignin-substructure-based hydrocarbons (C7-C18), primarily C12-C18 cyclic structure hydrocarbons in the jet fuel range, was demonstrated.

  13. Preparation and Analysis of Biomass Lignins

    Science.gov (United States)

    Compere, Alicia L.; Griffith, William L.

    Lignin, comprised primarily of three randomly polymerized phenylpropenyl monomers, is, arguably, the second most common organic molecule on earth. In current biorefinery applications, lignin is burned, usually in concentrated pulping or hydrolysis liquor, as a source of process steam and both internal and exported electricity. The aromatic content of lignin makes it a potentially attractive feedstock for high-value aromatic chemicals, polymers, and carbon products (graphite, activated carbon, and carbon fiber). Revenue from production of lignin-based chemicals could play a major role in biorefinery profitability if cost-effective methods for lignin separation and purification can be developed. This chapter presents descriptions of methods for assessing and purifying biorefinery lignins so that they can be evaluated for use as feedstock for production of chemical products. Areas covered are: (1) initial evaluations of as-received lignin samples (visual, microscopic, separable organics); (2) analysis of common contaminants (bulk and filterable ash and particulate contaminants in liquid and dry lignin samples); (3) preparation of lignins for experimental use as chemical feedstock (prefiltration, filtration using bench-scale chemical apparatus and larger scale bag filters, one-step lignin precipitation, two-step carbohydrate and lignin precipitation, desalting of dry powdered or precipitated lignin, and lyophilization). These methods have been used successfully at the bench scale to produce the 1-50 kg amounts of wood and grass lignins typically required for bench-scale assessment as chemical feedstocks.

  14. Does elevated N make lignin more recalcitrant?

    Science.gov (United States)

    Weintraub, M. N.; Rinkes, Z. L.; Grandy, S.; Wickings, K.; Bertrand, I.

    2014-12-01

    Increases in nitrogen (N) availability are often found to reduce decomposition rates of lignin-rich plant litter. However, the biological and chemical mechanisms that cause this inhibitory effect are still unclear. Our goal was to determine why increased N availability inhibits lignin decomposition. We tested two competing hypotheses: 1) decomposers degrade lignin to obtain protected N compounds and stop producing lignin-degrading enzymes if mineral N is available; or 2) chemical reactions between lignin and mineral N make lignin more recalcitrant, thereby limiting the ability of decomposers to break it down. To test these hypotheses, we followed changes in carbon (C) mineralization, microbial biomass and enzyme activities, litter chemistry, and lignin monomer concentrations over a 478-day laboratory incubation of three genotypes of maize stem internodes varying in litter quality. They were factorially combined with either an acidic or neutral pH sandy soil, with and without added N. Adding N reduced C mineralization, microbial biomass, and lignin-degrading enzyme activities in all treatments. Furthermore, our data on litter chemistry and lignin monomers indicate that N addition did not significantly alter the quantity or quality of lignin in any treatment. These results suggest that abiotic interactions between N and lignin compounds did not alter the ability of decomposers to breakdown lignin. Thus, we conclude that mineral N alters microbial enzyme and biomass dynamics, but not lignin chemistry during maize decomposition.

  15. Degradation of carbohydrates and lignins in buried woods

    Science.gov (United States)

    Hedges, John I.; Cowie, Gregory L.; Ertel, John R.; James Barbour, R.; Hatcher, Patrick G.

    1985-03-01

    Spruce, alder, and oak woods deposited in coastal sediments were characterized versus their modern counterparts by quantification of individual neutral sugars and lignin-derived phenols as well as by scanning electron microscopy, 13C NMR, and elemental analysis. The buried spruce wood from a 2500 yr old deposit was unaltered whereas an alder wood from the same horizon and an oak wood from an open ocean sediment were profoundly degraded. Individual sugar and lignin phenol analyses indicate that at least 90 and 98 wt% of the initial total polysaccharides in the buried alder and oak woods, respectively, have been degraded along with 15-25 wt% of the lignin. At least 75% of the degraded biopolymer has been physically lost from these samples. This evidence is supported by the SEM, 13C NMR and elemental analyses, all of which indicate selective loss of the carbohydrate moiety. The following order of stability was observed for the major biochemical constituents of both buried hardwoods: vanillyl and p- hydroxyl lignin structural units > syringyl lignin structural units > pectin > α-cellulose > hemicellulose. This sequence can be explained by selective preservation of the compound middle lamella regions of the wood cell walls. The magnitude and selectivity of the indicated diagenetic reactions are sufficient to cause major changes in the chemical compositions of wood-rich sedimentary organic mixtures and to provide a potentially large in situ nutrient source.

  16. Degradation of carbohydrates and lignins in buried woods

    Science.gov (United States)

    Hedges, J.I.; Cowie, G.L.; Ertel, J.R.; James, Barbour R.; Hatcher, P.G.

    1985-01-01

    Spruce, alder, and oak woods deposited in coastal sediments were characterized versus their modern counterparts by quantification of individual neutral sugars and lignin-derived phenols as well as by scanning electron microscopy, 13C NMR, and elemental analysis. The buried spruce wood from a 2500 yr old deposit was unaltered whereas an alder wood from the same horizon and an oak wood from an open ocean sediment were profoundly degraded. Individual sugar and lignin phenol analyses indicate that at least 90 and 98 wt% of the initial total polysaccharides in the buried alder and oak woods, respectively, have been degraded along with 15-25 wt% of the lignin. At least 75% of the degraded biopolymer has been physically lost from these samples. This evidence is supported by the SEM, 13C NMR and elemental analyses, all of which indicate selective loss of the carbohydrate moiety. The following order of stability was observed for the major biochemical constituents of both buried hardwoods: vanillyl and p-hydroxyl lignin structural units > syringyl lignin structural units > pectin > ??-cellulose > hemicellulose. This sequence can be explained by selective preservation of the compound middle lamella regions of the wood cell walls. The magnitude and selectivity of the indicated diagenetic reactions are sufficient to cause major changes in the chemical compositions of wood-rich sedimentary organic mixtures and to provide a potentially large in situ nutrient source. ?? 1985.

  17. Tailoring lignin biosynthesis for efficient and sustainable biofuel production.

    Science.gov (United States)

    Liu, Chang-Jun; Cai, Yuanheng; Zhang, Xuebin; Gou, Mingyue; Yang, Huijun

    2014-12-01

    Increased global interest in a bio-based economy has reinvigorated the research on the cell wall structure and composition in plants. In particular, the study of plant lignification has become a central focus, with respect to its intractability and negative impact on the utilization of the cell wall biomass for producing biofuels and bio-based chemicals. Striking progress has been achieved in the last few years both on our fundamental understanding of lignin biosynthesis, deposition and assembly, and on the interplay of lignin synthesis with the plant growth and development. With the knowledge gleaned from basic studies, researchers are now able to invent and develop elegant biotechnological strategies to sophisticatedly manipulate the quantity and structure of lignin and thus to create economically viable bioenergy feedstocks. These concerted efforts open an avenue for the commercial production of cost-competitive biofuel to meet our energy needs.

  18. Structural analysis of lignin by pyrolysis-gas chromatography. 7. Conditions for acid hydrolysis of wood pulp and characteristics of acid-insoluble residues; Netsubunkai gas chromatography ni yoru lignin no kozo kaiseki. 7. Mokuzai pulp no sankasuibunkai joken to sanfuyosei zansa no seijo

    Energy Technology Data Exchange (ETDEWEB)

    Oi, H.; Ju, Y.; Kuroda, K. [The University of Tsukuba, Tsukuba (Japan)

    1997-10-01

    In order to simply analyze lignin present in wood/pulp and the carbohydrate composition, an attempt was made to improve hydrolysis conditions. The tests used pulp samples from degreased akamatsu (Pinus densiflora) meals, akamatsu holocellulose and akamatsu chips. Four methods were tested for acid hydrolysis; the Klason lignin, Yoshiwara, carbohydrate composition and modified carbohydrate composition methods. The acid-insoluble residues were analyzed by pyrolysis-gas chromatography, and the pyrograms prepared under different hydrolysis conditions were compared with each other. The test results indicate that the lignin and composition methods need 2.5h of the primary hydrolysis treatment with 72% sulfuric acid, time of this treatment should be increased to 2.5h for the carbohydrate composition method, and the modified carbohydrate method can quantitatively analyze lignin present in many wood and pulp samples. 7 refs., 6 figs., 3 tabs.

  19. Conversion of lignin precursors to carbon fibers with nanoscale graphitic domains

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Sabornie [ORNL; Jones, Eric B [ORNL; Clingenpeel, Amy [National High Magnetic Field Laboratory (Magnet Lab), Florida; McKenna, Amy [National High Magnetic Field Laboratory (Magnet Lab), Florida; Rios, Orlando [ORNL; McNutt, Nicholas W [ORNL; Keffer, David J. [University of Tennessee, Knoxville (UTK); Johs, Alexander [ORNL

    2014-08-04

    Lignin is one of the most abundant and inexpensive natural biopolymers. It can be efficiently converted to low cost carbon fiber, monolithic structures or powders that could be used directly in the production of anodes for lithium-ion batteries. In this work, we report processing parameters relevant for the conversion of lignin precursors into electrochemically active carbon fibers, the impact of lignin precursor modification on melt processing and the microstructure of the final carbon material. The conversion process encompasses melt spinning of the lignin precursor, oxidative stabilization and a low temperature carbonization step in a nitrogen/hydrogen atmosphere. To assess electrochemical performance, we determined resistivities of individual carbon fiber samples and characterized the microstructure by scanning electron microscopy and neutron diffraction. The chemical modification and subsequent thermomechanical processing methods reported here are effective for conversion into carbon fibers while preserving the macromolecular backbone structure of lignin. Modification of softwood lignin produced functionalities and rheological properties that more closely resemble hardwood lignin thereby enabling the melt processing of softwood lignin in oxidative atmospheres (air). Structural characterization of the carbonized fibers reveals nanoscale graphitic domains that are linked to enhanced electrochemical performance.

  20. Highly acylated (acetylated and/or p-coumaroylated) native lignins from diverse herbaceous plants.

    Science.gov (United States)

    del Río, José C; Rencoret, Jorge; Marques, Gisela; Gutiérrez, Ana; Ibarra, David; Santos, J Ignacio; Jiménez-Barbero, Jesús; Zhang, Liming; Martínez, Angel T

    2008-10-22

    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.

  1. Lignin analysis by FT-Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, U.P.; Obst, J.R.; Cannon, A.B. [USDA Forest Products Lab., Madison, WI (United States)

    1996-10-01

    Traditional methods of lignin analysis, such as Klason (acid insoluble) lignin determinations, give satisfactory results, are widely accepted, and often are considered as standard analyses. However, the Klason lignin method is laborious and time consuming; it also requires a fairly large-amount of isolated analyte. FT-Raman spectroscopy offers an opportunity to simplify and speed up lignin analyses. FT-Raman data for a number of hardwoods (angiosperms) and softwoods (gymnosperms) are compared with data obtained using other analytical methods, including Klason lignin (with corrections for acid soluble lignin), acetyl bromide, and FT-IR determinations. In addition, 10 different specimens of Nothofagus dombeyii (chosen because of the widely varying syringyl:guaiacyl monomer compositions of their lignins) were also analyzed. Lignin monomer compositions were determined by thioacidolysis of by nitrobenzene oxidation.

  2. Lignin poly(lactic acid) copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Olsson, Johan Vilhelm; Chung, Yi-Lin; Li, Russell Jingxian; Waymouth, Robert; Sattely, Elizabeth; Billington, Sarah; Frank, Curtis W.

    2017-02-14

    Provided herein are graft co-polymers of lignin and poly(lactic acid) (lignin-g-PLA copolymer), thermoset and thermoplastic polymers including them, methods of preparing these polymers, and articles of manufacture including such polymers.

  3. Evaluation of lignins from side-streams generated in an olive tree pruning-based biorefinery: Bioethanol production and alkaline pulping.

    Science.gov (United States)

    Santos, José I; Fillat, Úrsula; Martín-Sampedro, Raquel; Eugenio, María E; Negro, María J; Ballesteros, Ignacio; Rodríguez, Alejandro; Ibarra, David

    2017-07-06

    In modern lignocellulosic-based biorefineries, carbohydrates can be transformed into biofuels and pulp and paper, whereas lignin is burned to obtain energy. However, a part of lignin could be converted into value-added products including bio-based aromatic chemicals, as well as building blocks for materials. Then, a good knowledge of lignin is necessary to define its valorisation procedure. This study characterized different lignins from side-streams produced from olive tree pruning bioethanol production (lignins collected from steam explosion pretreatment with water or phosphoric acid as catalysts, followed by simultaneous saccharification and fermentation process) and alkaline pulping (lignins recovered from kraft and soda-AQ black liquors). Together with the chemical composition, the structure of lignins was investigated by FTIR, (13)C NMR, and 2D NMR. Bioethanol lignins had clearly distinct characteristics compared to pulping lignins; a certain number of side-chain linkages (mostly alkyl-aryl ether and resinol) accompanied with lower phenolic hydroxyls content. Bioethanol lignins also showed a significant amount of carbohydrates, mainly glucose and protein impurities. By contrast, pulping lignins revealed xylose together with a dramatical reduction of side-chains (some resinol linkages survive) and thereby higher phenol content, indicating rather severe lignin degradation during alkaline pulping processes. All lignins showed a predominance of syringyl units. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Fractionation and physicochemical characterization of lignin from waste jute bags: Effect of process parameters on yield and thermal degradation.

    Science.gov (United States)

    Ahuja, Dheeraj; Kaushik, Anupama; Chauhan, Ghanshyam S

    2017-04-01

    In this work lignin was extracted from waste jute bags using soda cooking method and effect of varying alkali concentration and pH on yield, purity, structure and thermal degradation of lignin were studied. The Lignin yield, chemical composition and purity were assessed using TAPPI method and UV-vis spectroscopy. Yield and purity of lignin ranged from 27 to 58% and 50-94%, respectively for all the samples and was maximum for 8% alkali concentration and at pH 2 giving higher thermal stability. Chemical structure, thermal stability and elementary analysis of lignin were studied using FTIR, (H)NMR, thermo gravimetric analysis (TGA) and Elemental analyzer. FTIR and (H)NMR results showed that core structure of lignin starts breaking beyond 10% alkali concentration. S/G ratio shows the dominance of Syringyl unit over guaiacyl unit. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Redox Catalysis Facilitates Lignin Depolymerization.

    Science.gov (United States)

    Bosque, Irene; Magallanes, Gabriel; Rigoulet, Mathilde; Kärkäs, Markus D; Stephenson, Corey R J

    2017-06-28

    Lignin is a recalcitrant and underexploited natural feedstock for aromatic commodity chemicals, and its degradation generally requires the use of high temperatures and harsh reaction conditions. Herein we present an ambient temperature one-pot process for the controlled oxidation and depolymerization of this potent resource. Harnessing the potential of electrocatalytic oxidation in conjugation with our photocatalytic cleavage methodology, we have developed an operationally simple procedure for selective fragmentation of β-O-4 bonds with excellent mass recovery, which provides a unique opportunity to expand the existing lignin usage from energy source to commodity chemicals and synthetic building block source.

  6. Lignin biopolymer based triboelectric nanogenerators

    Science.gov (United States)

    Bao, Yukai; Wang, Ruoxing; Lu, Yunmei; Wu, Wenzhuo

    2017-07-01

    Ongoing research in triboelectric nanogenerators (TENGs) focuses on increasing power generation, but obstacles concerning economical and eco-friendly utilization of TENGs continue to prevail. Being the second most abundant biopolymer on earth, lignin offers a valuable opportunity for low-cost TENG applications in biomedical devices, benefitting from its biodegradability and biocompatibility. Here, we develop for the first time a lignin biopolymer based TENGs for harvesting mechanical energy in the environment, which shows great potential for self-powered biomedical devices among other applications and opens doors to new technologies that utilize otherwise wasted materials for economically feasible and ecologically friendly production of energy devices.

  7. Liquid Fuels from Lignins: Annual Report

    Energy Technology Data Exchange (ETDEWEB)

    Chum, H. L.; Johnson, D. K.

    1986-01-01

    This task was initiated to assess the conversion of lignins into liquid fuels, primarily of lignins relevant to biomass-to-ethanol conversion processes. The task was composed of a literature review of this area and an experimental part to obtain pertinent data on the conversion of lignins germane to biomass-to-ethanol conversion processes.

  8. Lignin Valorization using Heterogenous Catalytic Oxidation

    DEFF Research Database (Denmark)

    Melián Rodríguez, Mayra; Shunmugavel, Saravanamurugan; Kegnæs, Søren

    is complex so different model compounds are often used to study lignin valorization. These model compounds contain the linkages present in lignin, simplifying catalytic analysis and present analytical challenges related to the study of the complicated lignin polymer and the plethora of products that could...

  9. Lignin pyrolysis for profitable lignocellulosic biorefineries

    NARCIS (Netherlands)

    Wild, de P.J.; Gosselink, R.J.A.; Huijgen, W.J.J.

    2014-01-01

    Bio-based industries (pulp and paper and biorefineries) produce > 50 Mt/yr of lignin that results from fractionation of lignocellulosic biomass. Lignin is world's second biopolymer and a major potential source for production of performance materials and aromatic chemicals. Lignin valorization is

  10. Disinfection byproduct formation from lignin precursors.

    Science.gov (United States)

    Hua, Guanghui; Kim, Junsung; Reckhow, David A

    2014-10-15

    Lignin is the most abundant aromatic plant component in terrestrial ecosystems. This study was conducted to determine the contribution of lignin residues in natural water to the formation of disinfection byproducts (DBPs) in drinking water. We investigated the formation of different classes of DBPs from lignin model compounds, lignin polymers, and humic substances using two common disinfection techniques, chlorination and chloramination. The contributions of lignin to the overall formation of DBPs from these organic products were determined based on the observed abundances of individual lignin phenols and their DBP yields. Model lignin phenols generally produced higher trichloroacetic acid (TCAA) yields than chloroform and dichloroacetic acid (DCAA) during chlorination. Lignin phenols generally produced higher DBP yields but lower percentages of unknown total organic halogen compared to bulk humic substances and lignin polymers. The relative significance of lignin phenols as chlorination DBP precursors generally follows the order of TCAA > DCAA&chloroform. The relative significance of lignin phenols to DBP formation by chloramination follows the order: TCAA > DCAA&DCAN > chloroform. Overall, lignin phenols are more important as TCAA precursors than as chloroform and DCAA precursors.

  11. An insight into the lignin peroxidase of Macrophomina phaseolina.

    Science.gov (United States)

    Akbar, Mohammed Touaha; Habib, Abdul Musaweer; Chowdhury, Dil Umme Salma; Bhuiyan, Md Iqbal Kaiser; Mostafa, Kazi Md Golam; Mondol, Sobuj; Mosleh, Ivan Mhai

    2013-01-01

    Macrophomina phaseolina is one of the deadliest necrotrophic fungal pathogens that infect more than 500 plant species including major food, fiber, and oil crops all throughout the globe. It secretes a cocktail of ligninolytic enzymes along with other hydrolytic enzymes for degrading the woody lignocellulosic plant cell wall and penetrating into the host tissue. Among them, lignin peroxidase has been reported only in Phanerochaete chrysosporium so far. But interestingly, a recent study has revealed a second occurrence of lignin peroxidase in M. phaseolina. However, lignin peroxidases are of much significance biotechnologically because of their potential applications in bio-remedial waste treatment and in catalyzing difficult chemical transformations. Besides, this enzyme also possesses agricultural and environmental importance on account of their role in lignin biodegradation. In the present work, different properties of the lignin peroxidase of M. phaseolina along with predicting the 3-D structure and its active sites were investigated by the use of various computational tools. The data from this study will pave the way for more detailed exploration of this enzyme in wet lab and thereby facilitating the strategies to be designed against such deadly weapons of Macrophomina phaseolina. Furthermore, the insight of such a ligninolytic enzyme will contribute to the assessment of its potentiality as a bioremediation tool.

  12. Characterization of Lignins Isolated from Alkali Treated Prehydrolysate of Corn Stover

    Institute of Scientific and Technical Information of China (English)

    LEI Mingliu; ZHANG Hongman; ZHENG Hongbo; LI Yuanyuan; HUANG He; XU Rong

    2013-01-01

    Lignins were isolated and purified from alkali treated prehydrolysate of corn stover.The paper presents the structural features of lignins in a series purification processes.Fourier transform infrared spectroscopy,ultraviolet-vis spectroscopy and proton nuclear magnetic resonance spectroscopy were used to analyze the chemical structure.Thermogravimetric analysis was applied to follow the thermal degradation,and wet chemical method was used to determine the sugar content.The results showed that the crude lignin from the prehydrolysate of corn stover was a heterogeneous material of syringyl,guaiacyl and p-hydroxyphenyl units,containing associated polysaccharides,lipids,and melted salts.Some of the crude lignin was chemically linked to hemicelluloses (mainly xylan).The lipids in crude lignin were probably composed of saturated and/or unsaturated long carbon chains,fatty acids,triterpenols,waxes,and derivatives of aromatic.The sugar content of purified lignin was less than 2.11%,mainly composed of guaiacyl units.DTGmax of purified lignin was 359 ℃.The majority of the hydroxyl groups were phenolic hydroxyl groups.The main type of linkages in purified lignin was β-O-4.Other types of linkages includedβ-5,β-β and α-O-4.

  13. Probing native lignin macromolecular configuration in Arabidopsis thaliana in specific cell wall types: further insights into limited substrate degeneracy and assembly of the lignins of ref8, fah 1-2 and C4H::F5H lines.

    Science.gov (United States)

    Patten, Ann M; Jourdes, Michaël; Cardenas, Claudia L; Laskar, Dhrubojyoti D; Nakazawa, Yoshihisa; Chung, Byung-Yeoup; Franceschi, Vincent R; Davin, Laurence B; Lewis, Norman G

    2010-03-01

    The interest in renewable, plant-derived, bioenergy/biofuels has resulted in a renaissance of plant cell-wall/lignin research. Herein, effects of modulating lignin monomeric compositions in a single plant species, Arabidopsis, are described. The earliest stage of putative "AcBr/Klason lignin" deposition was apparently unaffected by modulating p-coumarate 3-hydroxylase or ferulate 5-hydroxylase activities. This finding helps account for the inability of many other studies to fully suppress the reported putative levels of lignin deposition through monolignol biosynthesis manipulation, and also underscores limitations in frequently used lignin analytical protocols. The overall putative lignin content was greatly reduced (circa 62%) in a plant line harboring an H-(p-hydroxyphenyl) enriched lignin phenotype. This slightly increased H-monomer deposition level apparently occurred in cell-wall domains normally harboring guaiacyl (G) and/or syringyl (S) lignin moieties. For G- and S-enriched lignin phenotypes, the overall lignification process appeared analogous to wild type, with only xylem fiber and interfascicular fiber cells forming the S-enriched lignins. Laser microscope dissection of vascular bundles and interfascicular fibers, followed by pyrolysis GC/MS, supported these findings. Some cell types, presumably metaxylem and possibly protoxylem, also afforded small amounts of benzodioxane (sub)structures due to limited substrate degeneracy (i.e. utilizing 5-hydroxyconiferyl alcohol rather than sinapyl alcohol). For all plant lines studied, the 8-O-4' inter-unit frequency of cleavable H, G and/or S monomers was essentially invariant of monomeric composition for a given (putative) lignin content. These data again underscore the need for determination of lignin primary structures and identification of all proteins/enzymes involved in control of lignin polymer assembly/macromolecular configuration.

  14. Final Report: Investigation of Catalytic Pathways for Lignin Breakdown into Monomers and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Gluckstein, Jeffrey A [ORNL; Hu, Michael Z. [ORNL; Kidder, Michelle [ORNL; McFarlane, Joanna [ORNL; Narula, Chaitanya Kumar [ORNL; Sturgeon, Matthew R [ORNL

    2010-12-01

    Lignin is a biopolymer that comprises up to 35% of woody biomass by dry weight. It is currently underutilized compared to cellulose and hemicellulose, the other two primary components of woody biomass. Lignin has an irregular structure of methoxylated aromatic groups linked by a suite of ether and alkyl bonds which makes it difficult to degrade selectively. However, the aromatic components of lignin also make it promising as a base material for the production of aromatic fuel additives and cyclic chemical feed stocks such as styrene, benzene, and cyclohexanol. Our laboratory research focused on three methods to selectively cleave and deoxygenate purified lignin under mild conditions: acidolysis, hydrogenation and electrocatalysis. (1) Acidolysis was undertaken in CH2Cl2 at room temperature. (2) Hydrogenation was carried out by dissolving lignin and a rhodium catalyst in 1:1 water:methoxyethanol under a 1 atm H2 environment. (3) Electrocatalysis of lignin involved reacting electrically generated hydrogen atoms at a catalytic palladium cathode with lignin dissolved in a solution of aqueous methanol. In all of the experiments, the lignin degradation products were identified and quantified by gas chromatography mass spectroscopy and flame ionization detection. Yields were low, but this may have reflected the difficulty in recovering the various fractions after conversion. The homogeneous hydrogenation of lignin showed fragmentation into monomers, while the electrocatalytic hydrogenation showed production of polyaromatic hydrocarbons and substituted benzenes. In addition to the experiments, promising pathways for the conversion of lignin were assessed. Three conversion methods were compared based on their material and energy inputs and proposed improvements using better catalyst and process technology. A variety of areas were noted as needing further experimental and theoretical effort to increase the feasibility of lignin conversion to fuels.

  15. Lignin based controlled release coatings

    NARCIS (Netherlands)

    Mulder, W.J.; Gosselink, R.J.A.; Vingerhoeds, M.H.; Harmsen, P.F.H.; Eastham, D.

    2011-01-01

    Urea is a commonly used fertilizer. Due to its high water-solubility, misuse easily leads to excess nitrogen levels in the soil. The aim of this research was to develop an economically feasible and biodegradable slow-release coating for urea. For this purpose, lignin was selected as coating material

  16. Lignin based controlled release coatings

    NARCIS (Netherlands)

    Mulder, W.J.; Gosselink, R.J.A.; Vingerhoeds, M.H.; Harmsen, P.F.H.; Eastham, D.

    2011-01-01

    Urea is a commonly used fertilizer. Due to its high water-solubility, misuse easily leads to excess nitrogen levels in the soil. The aim of this research was to develop an economically feasible and biodegradable slow-release coating for urea. For this purpose, lignin was selected as coating

  17. Lignin based controlled release coatings

    NARCIS (Netherlands)

    Mulder, W.J.; Gosselink, R.J.A.; Vingerhoeds, M.H.; Harmsen, P.F.H.; Eastham, D.

    2011-01-01

    Urea is a commonly used fertilizer. Due to its high water-solubility, misuse easily leads to excess nitrogen levels in the soil. The aim of this research was to develop an economically feasible and biodegradable slow-release coating for urea. For this purpose, lignin was selected as coating material

  18.  The application of computational chemistry to lignin

    Science.gov (United States)

    Thomas Elder; Laura Berstis; Nele Sophie Zwirchmayr; Gregg T. Beckham; Michael F. Crowley

    2017-01-01

    Computational chemical methods have become an important technique in the examination of the structure and reactivity of lignin. The calculations can be based either on classical or quantum mechanics, with concomitant differences in computational intensity and size restrictions. The current paper will concentrate on results developed from the latter type of calculations...

  19. Lignin depolymerization/repolymerization and its critical role for delignification of aspen wood by steam explosion.

    Science.gov (United States)

    Li, Jiebing; Henriksson, Gunnar; Gellerstedt, Göran

    2007-11-01

    Steam explosion is an important process for the fractionation of biomass components. In order to understand the behaviour of lignin under the conditions encountered in the steam explosion process, as well as in other types of steam treatment, aspen wood and isolated lignin from aspen were subjected to steam treatment under various conditions. The lignin portion was analyzed using NMR and size exclusion chromatography as major analytical techniques. Thereby, the competition between lignin depolymerization and repolymerization was revealed and the conditions required for these two types of reaction identified. Addition of a reactive phenol, 2-naphthol, was shown to inhibit the repolymerization reaction strongly, resulting in a highly improved delignification by subsequent solvent extraction and an extracted lignin of uniform structure.

  20. Influence of RANEY Nickel on the Formation of Intermediates in the Degradation of Lignin

    Directory of Open Access Journals (Sweden)

    Daniel Forchheim

    2012-01-01

    Full Text Available Lignin forms an important part of lignocellulosic biomass and is an abundantly available residue. It is a potential renewable source of phenol. Liquefaction of enzymatic hydrolysis lignin as well as catalytical hydrodeoxygenation of the main intermediates in the degradation of lignin, that is, catechol and guaiacol, was studied. The cleavage of the ether bonds, which are abundant in the molecular structure of lignin, can be realised in near-critical water (573 to 673 K, 20 to 30 MPa. Hydrothermal treatment in this context provides high selectivity in respect to hydroxybenzenes, especially catechol. RANEY Nickel was found to be an adequate catalyst for hydrodeoxygenation. Although it does not influence the cleavage of ether bonds, RANEY Nickel favours the production of phenol from both lignin and catechol. The main product from hydrodeoxygenation of guaiacol with RANEY Nickel was cyclohexanol. Reaction mechanism and kinetics of the degradation of guaiacol were explored.

  1. Pleurotus ostreatus decreases cornstalk lignin content, potentially improving its suitability for animal feed.

    Science.gov (United States)

    Chen, Ying; Fan, Huan; Meng, Fanrui

    2017-03-01

    The capacity of Pleurotus ostreatus to degrade lignin was investigated in the fermentation of cornstalk. Cornstalk was incubated with P. ostreatus for 30 days, and acid-soluble and acid-insoluble lignins were assessed. The microscopic structure of cornstalk samples was studied by scanning electron microscopy (SEM), and spectroscopic characteristics were measured by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance ((13) C NMR) spectroscopy. During fermentation of cornstalk, the proportion of acid-soluble lignin did not vary significantly (P > 0.05), but that of acid-insoluble lignin decreased gradually from 17.8% on day 0 to 7.6% on day 30 (P ostreatus within 30 days. Pleurotus ostreatus decreases cornstalk lignin content, potentially improving its suitability for animal feed. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  2. Occurrence of naturally acetylated lignin units.

    Science.gov (United States)

    Del Río, José C; Marques, Gisela; Rencoret, Jorge; Martínez, Angel T; Gutiérrez, Ana

    2007-07-11

    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.

  3. A multi-analytical study of degradation of lignin in archaeological waterlogged wood.

    Science.gov (United States)

    Colombini, Maria P; Lucejko, Jeannette J; Modugno, Francesca; Orlandi, Marco; Tolppa, Eeva-Liisa; Zoia, Luca

    2009-11-15

    Historical or archaeological wooden objects are generally better conserved in wet environments than in other contexts. Nevertheless, anaerobic erosion bacteria can slowly degrade waterlogged wood, causing a loss of cellulose and hemicellulose and leading to the formation of water-filled cavities. During this process, lignin can also be altered. The result is a porous and fragile structure, poor in polysaccharides and mainly composed of residual lignin, which can easily collapse during drying and needs specific consolidation treatments. For this reason, the chemical characterization of archaeological lignin is of primary importance in the diagnosis and conservation of waterlogged wood artifacts. Current knowledge of the lignin degradation processes in historical and archaeological wood is extremely inadequate. In this study lignin extracted from archaeological waterlogged wood was examined using both Py-GC/MS, NMR spectroscopy and GPC analysis. The samples were collected from the Site of the Ancient Ships of San Rossore (Pisa, Italy), where since 1998 31 shipwrecks, dating from 2nd century BC to 5th century AD, have been discovered. The results, integrated by GPC analysis, highlight the depolymerization of lignin with cleavage of ether bonds, leading to an higher amount of free phenol units in the lignin from archaeological waterlogged wood, compared to sound lignin from reference wood of the same species.

  4. A Novel Partially Biobased PAN-Lignin Blend as a Potential Carbon Fiber Precursor

    Directory of Open Access Journals (Sweden)

    M. Özgür Seydibeyoğlu

    2012-01-01

    Full Text Available Blends of polyacrylonitrile (PAN and lignin were prepared with three different lignin types by solution blending and solution casting. Among three types of lignin, one type was chosen and different blend concentrations were prepared and casted. The casted blend films were characterized chemically with fourier transform infrared spectroscopy (FTIR, and thermally with thermogravimetric analysis (TGA. The mechanical properties of the blends were measured using dynamic mechanical analysis (DMA. FTIR analysis shows an excellent interaction of PAN and lignin. The interaction of the lignins and PAN was confirmed by TGA analysis. The DMA results reveal that the lignin enhance the mechanical properties of PAN at room temperature and elevated temperatures. The blend structure and morphology were observed using scanning electron microscopy (SEM. SEM images show that excellent polymer blends were prepared. The results show that it is possible to develop a new precursor material with a blend of lignin and PAN. These studies show that the side product of paper and cellulosic bioethanol industries, namely, lignin can be used for new application areas.

  5. Synthesis and characterization of new 5-linked pinoresinol lignin models.

    Science.gov (United States)

    Yue, Fengxia; Lu, Fachuang; Sun, Runcang; Ralph, John

    2012-12-14

    Pinoresinol structures, featuring a β-β'-linkage between lignin monomer units, are important in softwood lignins and in dicots and monocots, particularly those that are downregulated in syringyl-specific genes. Although readily detected by NMR spectroscopy, pinoresinol structures largely escaped detection by β-ether-cleaving degradation analyses presumably due to the presence of the linkages at the 5 positions, in 5-5'- or 5-O-4'-structures. In this study, which is aimed at helping better understand 5-linked pinoresinol structures by providing the required data for NMR characterization, new lignin model compounds were synthesized through biomimetic peroxidase-mediated oxidative coupling reactions between pre-formed (free-phenolic) coniferyl alcohol 5-5'- or 5-O-4'-linked dimers and a coniferyl alcohol monomer. It was found that such dimers containing free-phenolic coniferyl alcohol moieties can cross-couple with the coniferyl alcohol producing pinoresinol-containing trimers (and higher oligomers) in addition to other homo- and cross-coupled products. Eight new lignin model compounds were obtained and characterized by NMR spectroscopy, and one tentatively identified cross-coupled β-O-4'-product was formed from a coniferyl alcohol 5-O-4'-linked dimer. It was demonstrated that the 5-5'- and 5-O-4'-linked pinoresinol structures could be readily differentiated by using heteronuclear multiple-bond correlation (HMBC) NMR spectroscopy. With appropriate modification (etherification or acetylation) to the newly obtained model compounds, it would be possible to identify the 5-5'- or 5-O-4'-linked pinoresinol structures in softwood lignins by 2D HMBC NMR spectroscopic methods. Identification of the cross-coupled dibenzodioxocin from a coniferyl alcohol 5-5'-linked moiety suggested that thioacidolysis or derivatization followed by reductive cleavage (DFRC) could be used to detect and identify whether the coniferyl alcohol itself undergoes 5-5'-cross-linking during

  6. Density Functional Theory Study of Spirodienone Stereoisomers in Lignin

    Energy Technology Data Exchange (ETDEWEB)

    Elder, Thomas [USDA-Forest; Berstis, Laura [National; Biosciences; Beckham, Gregg T. [National; Crowley, Michael F. [National; Biosciences

    2017-07-10

    The spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ~3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a ..beta..-1 bond, has been proposed to be a precursor for acyclic ..beta..-1 linkages in lignin. Previous analytical work has revealed the presence, but not the absolute configuration, of two stereoisomeric forms of spirodienone. The objective of the current work was to determine if there are thermodynamic differences that could help identify the experimentally observed stereoisomers. Results from density functional theory calculations reveal the presence of clusters of stereoisomers with varying stability that may be of use in narrowing the list of possible structures. Furthermore, the bond dissociation enthalpy of the cyclic ring exhibited a particularly high value for the C-O cleavage reaction relative to more conventional ether bonds in lignin, perhaps due to limited electron delocalization possibilities.

  7. Characterization of lignin and Mn peroxidases from Phanerochaete chrysosporium

    Energy Technology Data Exchange (ETDEWEB)

    1991-01-01

    Long-term objectives are to elucidate the role and mechanism of the various isozymes in lignin biodegradation. Work is described on electrochemical studies on lignin and Mn peroxidases. This study was performed to investigate the structural aspects which confer the lignin and Mn peroxidases with their high reactivity. The experimentally determined redox potential of the Fe{sup 3+}/Fe{sup 2+} couple for the lignin peroxidase isozymes H1, H2, H8 and H10 are very similar, near-130 mV. The redox potential for the Mn peroxidase isozymes H3 and H4 are similar to each other ({minus}88 mV and {minus}95 mV, respectively) and are more positive than the lignin peroxidases. The higher redox potential for the Fe{sup 3+}/Fe{sup 2+} couple is consistent with the heme active site of these fungal peroxidases being more electron deficient. To investigate the accessibility of the heme active site to the substrate which is oxidized (veratryl alcohol and Mn (II)), we investigated whether these substrates had any affect on the redox potential of the heme. The E{sub m7} value for lignin and Mn peroxidases are not affected by their respective substrates, veratryl alcohol and Mn (II). These results suggest that substrates do not directly interact with the ferric heme-iron as axial ligands. This is consistent with the present model for peroxidase catalysis. Suicide inhibitor (1) and nmr studies (2) indicate that the heme-iron of horseradish peroxidase (HRP) is not fully accessible to bulky substrates occur at the periphery of the heme.

  8. Rapid, microscale, acetyl bromide-based method for high-throughput determination of lignin content in Arabidopsis thaliana.

    Science.gov (United States)

    Chang, Xue Feng; Chandra, Richard; Berleth, Thomas; Beatson, Rodger P

    2008-08-27

    The acetyl bromide method has been modified to enable the rapid microscale determination of lignin content in Arabidopsis with the goal of determining the genes that control lignin in plants. Modifications include reduction in sample size, use of a microball mill, adoption of a modified rapid method of extraction, use of an ice-bath to stabilize solutions and reduction in the volume of solutions. The microscale method was shown to be rapid, accurate and precise with values in agreement with those determined by the full-scale acetyl bromide method. The extinction coefficient for Arabidopsis lignin, dissolved using acetyl bromide, was determined to be 23.35 g(-1) L cm(-1) at 280 nm. This value is independent of the Arabidopsis accession, environmental growth conditions and is insensitive to lignin structure. The newly developed method can be used to determine lignin content in the inflorescence stems of Arabidopsis for mapping of lignin-related genes.

  9. Evaluating Lignin-Rich Residues from Biochemical Ethanol Production of Wheat Straw and Olive Tree Pruning by FTIR and 2D-NMR

    Directory of Open Access Journals (Sweden)

    José I. Santos

    2015-01-01

    Full Text Available Lignin-rich residues from the cellulose-based industry are traditionally incinerated for internal energy use. The future biorefineries that convert cellulosic biomass into biofuels will generate more lignin than necessary for internal energy use, and therefore value-added products from lignin could be produced. In this context, a good understanding of lignin is necessary prior to its valorization. The present study focused on the characterization of lignin-rich residues from biochemical ethanol production, including steam explosion, saccharification, and fermentation, of wheat straw and olive tree pruning. In addition to the composition and purity, the lignin structures (S/G ratio, interunit linkages were investigated by spectroscopy techniques such as FTIR and 2D-NMR. Together with the high lignin content, both residues contained significant amounts of carbohydrates, mainly glucose and protein. Wheat straw lignin showed a very low S/G ratio associated with p-hydroxycinnamates (p-coumarate and ferulate, whereas a strong predominance of S over G units was observed for olive tree pruning lignin. The main interunit linkages present in both lignins were β-O-4′ ethers followed by resinols and phenylcoumarans. These structural characteristics determine the use of these lignins in respect to their valorization.

  10. Lignin peroxidase functionalities and prospective applications

    OpenAIRE

    Falade, Ayodeji O.; Nwodo, Uchechukwu U.; Iweriebor, Benson C.; Green, Ezekiel; Leonard V. Mabinya; Okoh, Anthony I.

    2016-01-01

    Abstract Ligninolytic extracellular enzymes, including lignin peroxidase, are topical owing to their high redox potential and prospective industrial applications. The prospective applications of lignin peroxidase span through sectors such as biorefinery, textile, energy, bioremediation, cosmetology, and dermatology industries. The litany of potentials attributed to lignin peroxidase is occasioned by its versatility in the degradation of xenobiotics and compounds with both phenolic and non‐phe...

  11. 木质素基酚醛树脂泡沫塑料的结构与性能研究%Structure and Properties of Lignin Based Phenolic Foam

    Institute of Scientific and Technical Information of China (English)

    吴强林; 方红霞; 丁运生; 刘东银; 郑雨; 晏秀男

    2012-01-01

    The structure and performances of lignin based phenolic resin ( LPF ) and LPF foam were studied. Results showed that LPF had lower free formaldehyde content of 0.35%, and lower free phenol content of 0.59% compared with the traditional type of phenolic resin ( PF ). Phenolic of lignin and resinic reactions of LPF foam were conformed by FTIR analyses. Stereoscopic microscope observation results showed that LPF foam had more closed-cell foam with fine cell structures than that of PF foam. The results of TGA and oxygen index determination showed that LPF foam had better thermostability and flame retardance. The results of determination of compressive strength, thermal conductivity and water absorption also indicated that LPF foam had improved mechanical property, thermal insulation property and waterproof performance as well. Compared with the traditional PF foam, LPF foam prepared by thermo-chemical phenolic reactions had better mechanical property, thermal insulation property, waterproof and fireproof performances. It was also more economical, environmentally friendly and safer.%研究了木质素基可发性酚醛树脂(LPF)及LPF泡沫塑料的结构与性能.结果表明,采用酚化木质素制备的LPF具有比酚醛树脂(PF)更低的游离甲醛(质量分数为0.35%)和更低的游离苯酚(质量分数为0.59%);傅立叶变换红外光谱(FTIR)分析证明了木质素的酚化及参与树脂固化反应;体视显微镜观测结果表明,LPF泡沫塑料具有比PF泡沫塑料更高的闭孔结构;热重分析及氧指数分析结果表明,LPF泡沫塑料具有更好的热稳定性和阻燃性能;压缩强度、导热系数和吸水率测定结果表明,LPF泡沫塑料具有更好的力学性能、保温性能和防水性能.相比于传统的PF泡沫塑料,采用热化学酚化技术制备的LPF泡沫塑料,具有更加优良的力学、保温、防火、防水性能,且更加安全、环保、经济.

  12. Recovering hydrocarbons with surfactants from lignin

    Energy Technology Data Exchange (ETDEWEB)

    Naae, D.G.; Whittington, L.E.; Ledoux, W.A.; Debons, F.E.

    1988-11-29

    This patent describes a method of recovering hydrocarbons from an underground hydrocarbon formation penetrated by at least one injection well and at least one production well, which comprises: injecting into the formation through an injection well a surfactant slug comprising about 0.1% to about 10% by weight of surfactants produced from lignin, the surfactants produced by placing lignin in contact with water, converting the lignin into low molecular weight lignin phenols by reducing the lignin in the presence of a reducing agent of carbon monoxide or hydrogen creating a reduction reaction mixture comprising oil soluble lignin phenols, the reduction occurring at a temperature greater than about 200/sup 0/C and a pressure greater than about 100 psi, recovering the oil soluble lignin phenols from the reduction mixture, and converting the lignin phenols into lignin surfactants by a reaction selected from the group consisting of alkoxylation, sulfonation, sulfation, aklylation, sulfomethylation, and alkoxysulfation; injecting into the formation through the injection well a drive fluid to push the surfactant slug towards a production well; and recovering hydrocarbons at the production well.

  13. Cytocompatible cellulose hydrogels containing trace lignin.

    Science.gov (United States)

    Nakasone, Kazuki; Kobayashi, Takaomi

    2016-07-01

    Sugarcane bagasse was used as a cellulose resource to prepare transparent and flexible cellulose hydrogel films. On the purification process from bagasse to cellulose, the effect of lignin residues in the cellulose was examined for the properties and cytocompatibility of the resultant hydrogel films. The cellulose was dissolved in lithium chloride/N,N-dimethylacetamide solution and converted to hydrogel films by phase inversion. In the purification process, sodium hydroxide (NaOH) treatment time was changed from 1 to 12h. This resulted in cellulose hydrogel films having small amounts of lignin from 1.62 to 0.68%. The remaining lignin greatly affected hydrogel properties. Water content of the hydrogel films was increased from 1153 to 1525% with a decrease of lignin content. Moreover, lower lignin content caused weakening of tensile strength from 0.80 to 0.43N/mm(2) and elongation from 45.2 to 26.5%. Also, similar tendency was observed in viscoelastic behavior of the cellulose hydrogel films. Evidence was shown that the lignin residue was effective for the high strength of the hydrogel films. In addition, scanning probe microscopy in the morphological observation was suggested that the trace lignin in the cellulose hydrogel affected the cellulose fiber aggregation in the hydrogel network. The trace of lignin in the hydrogels also influenced fibroblast cell culture on the hydrogel films. The hydrogel film containing 1.68% lignin showed better fibroblast compatibility as compared to cell culture polystyrene dish used as reference.

  14. Environmental effects on the lignin model monomer, vanillyl alcohol, studied by raman spectroscopy

    DEFF Research Database (Denmark)

    Larsen, Kiki Lyster; Barsberg, Søren Talbro

    2011-01-01

    units, respectively. Raman spectroscopy gives valuable knowledge on lignin and has a large potential for further developments. Thus in the present work we show how the use of electronic structure theory can support the study of environmental effects on lignin Raman bands. Raman spectra of the lignin...... model monomer, vanillyl alcohol (G type), dissolved in different solvents were compared to investigate such effects on the Raman band shapes and positions. Density functional theory combined with the polarizable continuum model were applied to assign the observed bands and tested for prediction accuracy...

  15. Preparation and Characterization of Novel PVC/Silica–Lignin Composites

    Directory of Open Access Journals (Sweden)

    Łukasz Klapiszewski

    2015-09-01

    Full Text Available An advanced SiO2–lignin hybrid material was obtained and tested as a novel poly(vinyl chloride (PVC filler. The processing of compounds of poly(vinyl chloride in the form of a dry blend with silica–lignin hybrid material and, separately, with the two components from which that material was prepared, was performed in a Brabender mixing chamber. An analysis was made of processing (mass melt flow rate, MFR, thermal (thermogravimetric analysis, Congo red and Vicat softening temperature test and tensile properties of the final PVC composites with fillers in a range of concentrations between 2.5 wt % and 10 wt %. Additionally, the effects of filler content on the fusion characteristics of PVC composites were investigated. The homogeneity of dispersion of the silica–lignin hybrid material in the PVC matrix was determined by optical microscopy and SEM. Finally, it should be noted that it is possible to obtain a PVC composite containing up to 10 wt % of silica–lignin filler using a melt processing method. The introduction of hybrid filler into the PVC matrix results in a homogeneous structure of the composites and positive processing and functional properties, especially thermal stability and Vicat softening temperature.

  16. Base-catalyzed depolymerization of lignin : separation of monomers

    Energy Technology Data Exchange (ETDEWEB)

    Vigneault, A. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; Johnson, D.K. [National Renewable Energy Laboratory, Golden, CO (United States); Chornet, E. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; National Renewable Energy Laboratory, Golden, CO (United States)

    2007-12-15

    Biofuels produced from residual lignocellulosic biomass range from ethanol to biodiesel. The use of lignin for the production of alternate biofuels and green chemicals has been studied with particular emphasis on the structure of lignin and its oxyaromatic nature. In an effort to fractionate lignocellulosic biomass and valorize specific constitutive fractions, the authors developed a strategy for the separation of 12 added value monomers produced during the hydrolytic base catalyzed depolymerization (BCD) of a Steam Exploded Aspen Lignin. The separation strategy was similar to vanillin purification to obtain pure monomers, but combining more steps after the lignin depolymerization such as acidification, batch liquid-liquid-extraction (LLE), followed by vacuum distillation, liquid chromatography (LC) and crystallization. The purpose was to develop basic data for an industrial size process flow diagram, and to evaluate both the monomer losses during the separation and the energy requirements. Experimentally testing of LLE, vacuum distillation and flash LC in the laboratory showed that batch vacuum distillation produced up to 4 fractions. Process simulation revealed that a series of 4 vacuum distillation columns could produce 5 distinct monomer streams, of which 3 require further chromatography and crystallization operations for purification. 22 refs., 4 tabs., 8 figs.

  17. Identifying acetylated lignin units in non-wood fibers using pyrolysis-gas chromatography/mass spectrometry.

    Science.gov (United States)

    del Río, José C; Gutiérrez, Ana; Martínez, Angel T

    2004-01-01

    A series of non-wood plant fibers, namely kenaf, jute, sisal and abaca, have been analyzed upon pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of the whole material. The pyrolysis products mainly arise from the carbohydrate and lignin moieties of the fibers. The lignin-derived phenols belonged to the p-hydroxyphenylpropanoid (H), guaiacylpropanoid (G) and syringylpropanoid (S) structures, and showed a high S/G ratio of between 2.0 and 5.4, the highest corresponding to kenaf. Among the lignin-derived phenols released, small amounts of sinapyl and coniferyl acetates (in both cis- and trans-forms) were identified for the first time upon Py-GC/MS of lignocellulosic materials. Acetylation of the sinapyl and coniferyl alcohols was at the gamma-position of the side chain. The release of these alcohols derived from intact acetylated lignin units upon pyrolysis seems to indicate that the native lignin in the fibers selected for this study is at least partially acetylated. Sinapyl (and coniferyl) acetates have recently been suggested to be authentic lignin precursors involved in the polymerization of lignin along with the normal sinapyl and coniferyl alcohols. Py-GC/MS will offer a convenient and rapid tool for analyzing naturally acetylated lignins, as well as to screen plant materials for the presence of acetylated units in lignin.

  18. Deconstruction of lignin linked p-coumarates, ferulates and xylan by NaOH enhances the enzymatic conversion of glucan

    NARCIS (Netherlands)

    Murciano Martínez, Patricia; Punt, Arjen M.; Kabel, Mirjam A.; Gruppen, Harry

    2016-01-01

    Thermo-assisted NaOH pretreatment to deconstruct xylan and lignin in sugar cane bagasse (SCB) is poorly understood. Hence, in this research it is was aimed to study the effect of NaOH pretreatment on the insoluble remaining lignin structures. Hereto, SCB milled fibres were pretreated using differ

  19. Selective carbon 13 enrichment of side chain carbons of ginkgo lignin traced by carbon 13 nuclear magnetic resonance

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Y. (Nagoya Univ. (Japan). Faculty of Agriculture); Robert, D.R. (CEA Centre d' Etudes de Grenoble, 38 (France). Dept. de Recherche Fondamentale sur la Matiere Condensee); Terashima, N. (Forest Products Lab., Madison, WI (United States))

    Although carbon 13 nuclear magnetic resonance spectroscopy ([sup 13]C-NMR) is widely used in lignin structural studies, serious difficulties are encountered in the assignments of [sup 13]C signals because of their extensive overlaps resulting from the complex structure of lignin and of delicate detection of minor structures. To overcome these difficulties, specifically [sup 13]C-enriched precursors of lignin biosynthesis, coniferin-[side chain-[beta]-[sup 13]C] and coniferin-[side chain-[gamma]-[sup 13]C], were administered to growing stems of ginkgo (Ginkgo biloba). The NMR analysis of the milled wood lignins isolated from the newly formed xylem showed that selective enrichment of specific carbons of protolignin in the cell wall was achieved without seriously disturbing the lignin biosynthesis. The presence of saturated methylene side chains in the protolignin was shown for the first time by this selective enrichment technique in combination with NMR analysis. (authors). 23 refs., 3 figs., 1 tab.

  20. Hydrogen peroxide sensing and cytotoxicity activity of Acacia lignin stabilized silver nanoparticles.

    Science.gov (United States)

    Aadil, Keshaw Ram; Barapatre, Anand; Meena, Avtar Singh; Jha, Harit

    2016-01-01

    The study is aimed at detection of hydrogen peroxide (H2O2) using Acacia lignin mediated silver nanoparticles (AGNPs). The synthesis of AGNPs was achieved at conditions optimized as, 3 ml of 0.02% lignin and 1mM silver nitrate incubated for 30 min at 80°C and pH 9. Initial screening of AGNPs was performed by measuring the surface plasmon resonance peak at 410-430 nm using UV-vis spectrophotometer. Transmission electron microscopy, atomic force microscopy, X-ray diffraction and particle size analysis confirmed the spherical shaped face centered cubic structure and 10-50 nm size of AGNPs. The infrared spectroscopy study further revealed that the active functional groups present in lignin were responsible for the reduction of silver ions (Ag(+)) to metallic silver (Ag(0)). Lignin stabilized silver nanoparticles showed good sensitivity and a linear response over wide concentrations of H2O2 (10(-1) to 10(-6)M). Further, the in vitrocytotoxicity activity of the lignin mediated AGNPs (5-500 μg/ml) demonstrated toxicity effects in MCF-7 and A375 cell lines. Thus, lignin stabilized silver nanoparticles based optical sensor for H2O2 could be potentially applied in the determination of reactive oxygen species and toxic chemicals which further expands the importance of lignin stabilized silver nanoparticles.

  1. Enzymatic Transesterification of Kraft Lignin with Long Acyl Chains in Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Lise Hulin

    2015-09-01

    Full Text Available Valorization of lignin is essential for the economic viability of the biorefinery concept. For example, the enhancement of lignin hydrophobicity by chemical esterification is known to improve its miscibility in apolar polyolefin matrices, thereby helping the production of bio-based composites. To this end and due to its many reactive hydroxyl groups, lignin is a challenging macromolecular substrate for biocatalyzed esterification in non-conventional media. The present work describes for the first time the lipase-catalyzed transesterification of Kraft lignin in ionic liquids (ILs. Three lipases, three 1-butyl-3-methylimidazolium based ILs and ethyl oleate as long chain acyl donor were selected. Best results were obtained with a hydrophilic/hydrophobic binary IL system (1-butyl-3-methylimidazolium trifluoromethanesulfonate/1-butyl-3-methylimidazolium hexafluoro- phosphate, 1/1 v/v and the immobilized lipase B from Candida antarctica (CALB that afforded a promising transesterification yield (ca. 30%. Similar performances were achieved by using 1-butyl-3-methylimidazolium hexafluorophosphate as a coating agent for CALB rather than as a co-solvent in 1-butyl-3-methylimidazolium trifluoromethane-sulfonate thus limiting the use of hydrophobic IL. Structural characterization of lignin oleate was performed by spectroscopic studies (FTIR and 1H-NMR. The synthesized lignin oleate exhibited interesting thermal and textural properties, different from those of the original Kraft lignin.

  2. Recent Progress in Producing Lignin-Based Carbon Fibers for Functional Applications

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Ryan [GrafTech International Holdings Inc.; Burwell, Deanna [GrafTech International Holdings Inc.; Dai, Xuliang [GrafTech International Holdings Inc.; Naskar, Amit [Oak Ridge National Laboratory; Gallego, Nidia [Oak Ridge National Laboratory; Akato, Kokouvi [Oak Ridge National Laboratory

    2015-10-29

    Lignin, a biopolymer, has been investigated as a renewable and low-cost carbon fiber precursor since the 1960s. Although successful lab-scale production of lignin-based carbon fibers has been reported, there are currently not any commercial producers. This paper will highlight some of the known challenges with converting lignin-based precursors into carbon fiber, and the reported methods for purifying and modifying lignin to improve it as a precursor. Several of the challenges with lignin are related to its diversity in chemical structure and purity, depending on its biomass source (e.g. hardwood, softwood, grasses) and extraction method (e.g. organosolv, kraft). In order to make progress in this field, GrafTech and Oak Ridge National Laboratory are collaborating to develop lignin-based carbon fiber technology and to demonstrate it in functional applications, as part of a cooperative agreement with the DOE Advanced Manufacturing Office. The progress made to date with producing lignin-based carbon fiber for functional applications, as well as developing and qualifying a supply chain and value proposition, are also highlighted.

  3. Fractionation of hemp hurds by organosolv pretreatment and its effect on production of lignin and sugars.

    Science.gov (United States)

    Gandolfi, Stefano; Ottolina, Gianluca; Consonni, Roberto; Riva, Sergio; Patel, Ilabahen

    2014-07-01

    Fractionation of hemp hurds into its three main components, cellulose, hemicellulose, and lignin, was carried out using organosolv pretreatment. The effect of processing parameters, such as temperature, catalyst concentration, reaction time, and methanol (MeOH) concentration, on the dissolution and recovery of hemicellulose and lignin was determined. More than 75% of total hemicellulose and 75% of total lignin was removed in a single step with low amounts of degradation products under the following conditions: 165 °C, 3% H2 SO4 , 20 min reaction time, and 45% MeOH. Enzymatic hydrolysis of the residual pretreated biomass yielded up to 60% of cellulose-to-glucose conversion. The maximum recovery of the main components was obtained at a combined severity factor value of around one. Characterization of pretreated biomass and isolated lignin was carried out with FTIR and 2D (13) C-(1) H correlation HSQC NMR spectroscopy, the latter technique providing detailed structural information about the obtained methanol organosolv lignin (MOSL). Results suggested that xylopyranoside is the major carbohydrate associated with hemp lignin. The chemical properties of MOSL samples in terms of their phenolic group content and antioxidant capacity were also investigated. The results showed that MOSL samples have a high phenolic group content and antioxidant capacity relative to Klason lignin.

  4. Enzymatic Specific Production and Chemical Functionalization of Phenylpropanone Platform Monomers from Lignin.

    Science.gov (United States)

    Ohta, Yukari; Hasegawa, Ryoichi; Kurosawa, Kanako; Maeda, Allyn H; Koizumi, Toshio; Nishimura, Hiroshi; Okada, Hitomi; Qu, Chen; Saito, Kaori; Watanabe, Takashi; Hatada, Yuji

    2017-01-20

    Enzymatic catalysis is an ecofriendly strategy for the production of high-value low-molecular-weight aromatic compounds from lignin. Although well-definable aromatic monomers have been obtained from synthetic lignin-model dimers, enzymatic-selective synthesis of platform monomers from natural lignin has not been accomplished. In this study, we successfully achieved highly specific synthesis of aromatic monomers with a phenylpropane structure directly from natural lignin using a cascade reaction of β-O-4-cleaving bacterial enzymes in one pot. Guaiacylhydroxylpropanone (GHP) and the GHP/syringylhydroxylpropanone (SHP) mixture are exclusive monomers from lignin isolated from softwood (Cryptomeria japonica) and hardwood (Eucalyptus globulus). The intermediate products in the enzymatic reactions show the capacity to accommodate highly heterologous substrates at the substrate-binding sites of the enzymes. To demonstrate the applicability of GHP as a platform chemical for bio-based industries, we chemically generate value-added GHP derivatives for bio-based polymers. Together with these chemical conversions for the valorization of lignin-derived phenylpropanone monomers, the specific and enzymatic production of the monomers directly from natural lignin is expected to provide a new stream in "white biotechnology" for sustainable biorefineries.

  5. Characterization of the radical scavenging activity of lignins--natural antioxidants.

    Science.gov (United States)

    Dizhbite, Tatiana; Telysheva, Galina; Jurkjane, Vilhelmina; Viesturs, Uldis

    2004-12-01

    The present work is devoted to studies of the radical scavenging properties of lignins, which are recognized as efficient antioxidants of natural origin. Radical scavenging efficiency of a series of lignins isolated from deciduous and coniferous wood species and 10 lignin related monomeric compounds were examined against 1,1-diphenyl-2-picrylhydrazyl (DPPH*) radical in homogeneous conditions using ESR and spectrophotometry methods. Some structure-activity relationships are proposed, pointing out the importance of the non-etherified OH phenolic groups, ortho-methoxy groups, hydroxyl groups and the double bond between the outermost carbon atoms in the side chain for increasing scavenger activity. Analysis of rate constants for the lignins-DPPH* interaction revealed the contribution of polymer molecular weight and pi-polyconjugation systems. The pi-conjugation systems of lignins operate as catalysts/activators of the interaction with DPPH*. Heterogeneity in terms of component composition (carbohydrate admixtures) and polydispersity is the factor which can decrease drastically the antioxidant efficiency of isolated lignins. The connection of the antibacterial effect of kraft lignin with radical scavenging activity of its soluble fraction was assumed.

  6. Insights into cellulase-lignin non-specific binding revealed by computational redesign of the surface of green fluorescent protein: Protein Redesign to Lower Protein-lignin Binding

    Energy Technology Data Exchange (ETDEWEB)

    Haarmeyer, Carolyn N. [Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing Michigan 48824; Smith, Matthew D. [Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing Michigan 48824; Chundawat, Shishir P. S. [Great Lakes Bioenergy Research Center (GLBRC), Michigan State University, East Lansing Michigan; Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, Piscataway New Jersey; Sammond, Deanne [Biosciences Center, National Renewable Energy Laboratory, Golden Colorado; Whitehead, Timothy A. [Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing Michigan 48824; Department of Biosystems and Agricultural Engineering, Michigan State University, East Lansing Michigan 48824

    2016-11-07

    Biological-mediated conversion of pretreated lignocellulosic biomass to biofuels and biochemicals is a promising avenue towards energy sustainability. However, a critical impediment to the commercialization of cellulosic biofuel production is the high cost of cellulase enzymes needed to deconstruct biomass into fermentable sugars. One major factor driving cost is cellulase adsorption and inactivation in the presence of lignin, yet we currently have a poor understanding of the protein structure-function relationships driving this adsorption. In this work, we have systematically investigated the role of protein surface potential on lignin adsorption using a model monomeric fluorescent protein. We have designed and experimentally characterized 16 model protein variants spanning the physiological range of net charge (-24 to +16 total charges) and total charge density (0.28 to 0.40 charges per sequence length) typical for natural proteins. Protein designs were expressed, purified, and subjected to in silico and in vitro biophysical measurements to evaluate the relationship between protein surface potential and lignin adsorption properties. The designs were comparable to model fluorescent protein in terms of thermostability and heterologous expression yield, although the majority of the designs unexpectedly formed homodimers. Protein adsorption to lignin was studied at two different temperatures using Quartz Crystal Microbalance with Dissipation Monitoring and a subtractive mass balance assay. We found a weak correlation between protein net charge and protein-binding capacity to lignin. No other single characteristic, including apparent melting temperature and 2nd virial coefficient, showed correlation with lignin binding. Analysis of an unrelated cellulase dataset with mutations localized to a family I carbohydrate-binding module showed a similar correlation between net charge and lignin binding capacity. Overall, our study provides strategies to identify highly active

  7. Performance characterization of rigid polyurethane foam with refined alkali lignin and modified alkali lignin

    Institute of Scientific and Technical Information of China (English)

    LIU Zhi-ming; YU Fei; FANG Gui-zhen; YANG Hui-jun

    2009-01-01

    The two kinds of rigid polyurethane (PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight. The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams. The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples. The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently. Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples. The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.

  8. Bacterial enzymes involved in lignin degradation

    NARCIS (Netherlands)

    de Gonzalo, Gonzalo; Colpa, Dana I; Habib, Mohamed H M; Fraaije, Marco W

    2016-01-01

    Lignin forms a large part of plant biomass. It is a highly heterogeneous polymer of 4-hydroxyphenylpropanoid units and is embedded within polysaccharide polymers forming lignocellulose. Lignin provides strength and rigidity to plants and is rather resilient towards degradation. To improve the (bio)p

  9. Effects of lignin on nitrification in soil

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The effects of two lignins isolated from black liquor from pulping process on nitrification in soils after addition of urea, (NH4)2SO4 and (NH4)2HPO4 were investigated by incubation at 20 or 30℃ for 7 or 14d. The effects of lignin on nitrous oxide emissions from soil were also determined. Results showed that both lignins were more effective for inhibiting nitrification of NH4+-N as (NH4)2SO4 or (NH4)2HPO4 as compared to urea-N. The effectiveness of lignin on nitrification was markedly affected by different soil type and temperature. Nitrous oxide emissions from soil declined when lignin was used. Urea plus 20 and 50 g/kg lignin reduced N2O emissions by about 83% and 96%, respectively, while (NH4)2HPO4 plus 20 and 50 g/kg lignin respectively reduced emissions by 83% and 93%. Because of its low cost and nonhazardous characteristics, lignin has potential value as a fertilizer amendment to improve N fertilizer efficiency.

  10. Fabrication of Environmentally Biodegradable Lignin Nanoparticles

    NARCIS (Netherlands)

    Frangville, C.; Rutkevicius, M.; Richter, A.P.; Velev, O.D.; Stoyanov, S.D.; Paunov, V.N.

    2012-01-01

    We developed a method for the fabrication of novel biodegradable nanoparticles (NPs) from lignin which are apparently non-toxic for microalgae and yeast. We compare two alternative methods for the synthesis of lignin NPs which result in particles of very different stability upon change of pH. The fi

  11. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand

    2015-01-01

    Modification of lignin is recognized as an important aspect of the successful refining of lignocellulosic biomass, and enzyme-assisted processing and upcycling of lignin is receiving significant attention in the literature. Laccases (EC 1.103.2) are taking the centerstage of this attention, since...... is proposed. (C) 2015 Elsevier Inc. All rights reserved....

  12. Bacterial enzymes involved in lignin degradation

    NARCIS (Netherlands)

    de Gonzalo, Gonzalo; Colpa, Dana I; Habib, Mohamed H M; Fraaije, Marco W

    2016-01-01

    Lignin forms a large part of plant biomass. It is a highly heterogeneous polymer of 4-hydroxyphenylpropanoid units and is embedded within polysaccharide polymers forming lignocellulose. Lignin provides strength and rigidity to plants and is rather resilient towards degradation. To improve the

  13. Biodegradation of lignin by Agaricus Bisporus

    Energy Technology Data Exchange (ETDEWEB)

    Vane, C.H.; Abbott, G.D.; Head, I.M. [Univ. of Newcastle upon Tyne (United Kingdom)

    1996-12-31

    The lignolytic activity of Agaricus bisporus will be addressed in this paper. Sound and fungally degraded lignins were characterized by Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC-MS), Fourier Transform Infrared Spectroscopy (FnR) and elemental analysis. Fungally degraded lignins displayed increased wt%N, wt%H and wt%O content and decreased wt%C content The FTIR spectrum of decayed lignin showed an increase in the relative intensity of absorption bands assigned to carbonyl and carboxyl functional groups located on the aliphatic side chain and a decrease in absorption bands assigned to aromatic skeletal vibration modes. Semiquantitative Py-GC-MS revealed an 82% decrease in lignin derived pyrolysis products upon biodegradation. No significant increase in pyrolysis products with an oxygenated aliphatic side chain were detected in the fungally degraded lignin however shortening of the aliphatic side chain via cleavage at the {alpha}, {beta} and {gamma} positions was observed.

  14. Recent Advances in Characterization of Lignin Polymer by Solution-State Nuclear Magnetic Resonance (NMR Methodology

    Directory of Open Access Journals (Sweden)

    Run-Cang Sun

    2013-01-01

    Full Text Available The demand for efficient utilization of biomass induces a detailed analysis of the fundamental chemical structures of biomass, especially the complex structures of lignin polymers, which have long been recognized for their negative impact on biorefinery. Traditionally, it has been attempted to reveal the complicated and heterogeneous structure of lignin by a series of chemical analyses, such as thioacidolysis (TA, nitrobenzene oxidation (NBO, and derivatization followed by reductive cleavage (DFRC. Recent advances in nuclear magnetic resonance (NMR technology undoubtedly have made solution-state NMR become the most widely used technique in structural characterization of lignin due to its versatility in illustrating structural features and structural transformations of lignin polymers. As one of the most promising diagnostic tools, NMR provides unambiguous evidence for specific structures as well as quantitative structural information. The recent advances in two-dimensional solution-state NMR techniques for structural analysis of lignin in isolated and whole cell wall states (in situ, as well as their applications are reviewed.

  15. Opportunities and challenges in biological lignin valorization.

    Science.gov (United States)

    Beckham, Gregg T; Johnson, Christopher W; Karp, Eric M; Salvachúa, Davinia; Vardon, Derek R

    2016-12-01

    Lignin is a primary component of lignocellulosic biomass that is an underutilized feedstock in the growing biofuels industry. Despite the fact that lignin depolymerization has long been studied, the intrinsic heterogeneity of lignin typically leads to heterogeneous streams of aromatic compounds, which in turn present significant technical challenges when attempting to produce lignin-derived chemicals where purity is often a concern. In Nature, microorganisms often encounter this same problem during biomass turnover wherein powerful oxidative enzymes produce heterogeneous slates of aromatics compounds. Some microbes have evolved metabolic pathways to convert these aromatic species via 'upper pathways' into central intermediates, which can then be funneled through 'lower pathways' into central carbon metabolism in a process we dubbed 'biological funneling'. This funneling approach offers a direct, biological solution to overcome heterogeneity problems in lignin valorization for the modern biorefinery. Coupled to targeted separations and downstream chemical catalysis, this concept offers the ability to produce a wide range of molecules from lignin. This perspective describes research opportunities and challenges ahead for this new field of research, which holds significant promise towards a biorefinery concept wherein polysaccharides and lignin are treated as equally valuable feedstocks. In particular, we discuss tailoring the lignin substrate for microbial utilization, host selection for biological funneling, ligninolytic enzyme-microbe synergy, metabolic engineering, expanding substrate specificity for biological funneling, and process integration, each of which presents key challenges. Ultimately, for biological solutions to lignin valorization to be viable, multiple questions in each of these areas will need to be addressed, making biological lignin valorization a multidisciplinary, co-design problem.

  16. Opportunities and challenges in biological lignin valorization

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T.; Johnson, Christopher W.; Karp, Eric M.; Salvachúa, Davinia; Vardon, Derek R.

    2016-12-01

    Lignin is a primary component of lignocellulosic biomass that is an underutilized feedstock in the growing biofuels industry. Despite the fact that lignin depolymerization has long been studied, the intrinsic heterogeneity of lignin typically leads to heterogeneous streams of aromatic compounds, which in turn present significant technical challenges when attempting to produce lignin-derived chemicals where purity is often a concern. In Nature, microorganisms often encounter this same problem during biomass turnover wherein powerful oxidative enzymes produce heterogeneous slates of aromatics compounds. Some microbes have evolved metabolic pathways to convert these aromatic species via ‘upper pathways’ into central intermediates, which can then be funneled through ‘lower pathways’ into central carbon metabolism in a process we dubbed ‘biological funneling’. This funneling approach offers a direct, biological solution to overcome heterogeneity problems in lignin valorization for the modern biorefinery. Coupled to targeted separations and downstream chemical catalysis, this concept offers the ability to produce a wide range of molecules from lignin. This perspective describes research opportunities and challenges ahead for this new field of research, which holds significant promise towards a biorefinery concept wherein polysaccharides and lignin are treated as equally valuable feedstocks. In particular, we discuss tailoring the lignin substrate for microbial utilization, host selection for biological funneling, ligninolytic enzyme–microbe synergy, metabolic engineering, expanding substrate specificity for biological funneling, and process integration, each of which presents key challenges. Ultimately, for biological solutions to lignin valorization to be viable, multiple questions in each of these areas will need to be addressed, making biological lignin valorization a multidisciplinary, co-design problem.

  17. Transition-metal catalyzed valorization of lignin: the key to a sustainable carbon-neutral future.

    Science.gov (United States)

    Kärkäs, Markus D; Matsuura, Bryan S; Monos, Timothy M; Magallanes, Gabriel; Stephenson, Corey R J

    2016-02-14

    The development of a sustainable, carbon-neutral biorefinery has emerged as a prominent scientific and engineering goal of the 21st century. As petroleum has become less accessible, biomass-based carbon sources have been investigated for utility in fuel production and commodity chemical manufacturing. One underutilized biomaterial is lignin; however, its highly crosslinked and randomly polymerized composition have rendered this biopolymer recalcitrant to existing chemical processing. More recently, insight into lignin's molecular structure has reinvigorated chemists to develop catalytic methods for lignin depolymerization. This review examines the development of transition-metal catalyzed reactions and the insights shared between the homogeneous and heterogeneous catalytic systems towards the ultimate goal of valorizing lignin to produce value-added products.

  18. Biopolymer-based nanocomposites: effect of lignin acetylation in cellulose triacetate films

    Science.gov (United States)

    Nevárez, Laura Alicia Manjarrez; Casarrubias, Lourdes Ballinas; Celzard, Alain; Fierro, Vanessa; Muñoz, Vinicio Torres; Davila, Alejandro Camacho; Lubian, José Román Torres; Sánchez, Guillermo González

    2011-01-01

    We have prepared all-biopolymer nanocomposite films using lignin as a filler and cellulose triacetate (CTA) as a polymer matrix, and characterized them by several analytical methods. Three types of lignin were tested: organosolv, hydrolytic and kraft, with or without acetylation. They were used in the form of nanoparticles incorporated at 1 wt% in CTA. Self-supported films were prepared by vapor-induced phase separation at controlled temperature (35–55 °C) and relative humidity (10–70%). The efficiency of acetylation of each type of lignin was studied and discussed, as well as its effects on film structure, homogeneity and mechanical properties. The obtained results are explained in terms of intermolecular filler-matrix interaction at the nanometer scale, for which the highest mechanical resistance was reached using hydrolytic lignin in the nanocomposite. PMID:27877425

  19. Lignin plays a negative role in the biochemical process for producing lignocellulosic biofuels.

    Science.gov (United States)

    Zeng, Yining; Zhao, Shuai; Yang, Shihui; Ding, Shi-You

    2014-06-01

    A biochemical platform holds the most promising route toward lignocellulosic biofuels, in which polysaccharides are hydrolyzed by cellulase enzymes into simple sugars and fermented to ethanol by microbes. However, these polysaccharides are cross-linked in the plant cell walls with the hydrophobic network of lignin that physically impedes enzymatic deconstruction. A thermochemical pretreatment process is often required to remove or delocalize lignin, which may also generate inhibitors that hamper enzymatic hydrolysis and fermentation. Here we review recent advances in understanding lignin structure in the plant cell walls and the negative roles of lignin in the processes of converting biomass to biofuels. Perspectives and future directions to improve the biomass conversion process are also discussed. Copyright © 2013. Published by Elsevier Ltd.

  20. 磺化木质素系聚合物的结构及其在氧化铝上的吸附特性%THE STRUCTURE CHARACTERISTICS OF SULFONATED LIGNIN-BASED POLYMER AND ITS ADSORPTION PROPERTIES ON ALUMINA

    Institute of Scientific and Technical Information of China (English)

    郭闻源; 杨东杰; 李荣; 邱学青

    2012-01-01

    以造纸黑液中的碱木质素为主要原料,通过磺化和缩聚反应制备了磺化木质素高分子聚合物SBAL.TEM和1H-NMR测试结果表明SBAL是以木质素的疏水骨架为中心,以磺酸基和羧基组成亲水性侧链的球形结构.GPC测试结果表明其重均分子量达到了 24880 Da,是碱木质素的7.38倍,电位滴定测试结果表明,其磺化度达到2.70 mmol·g -1.通过流变曲线、吸附等温线、zeta电位、XPS测试研究了其对氧化铝在水中的分散机理及其吸附特性.掺SBAL的氧化铝浆体,在pH=3~ 12范围内SBAL对其具有良好的分散降黏作用.溶液pH对SBAL的分子构型和吸附特性有较大的影响,随pH增加,SBAL中磺酸基、羧基和酚羟基逐渐电离,分子的伸展程度逐渐增大.随pH增加,SBAL在氧化铝上的吸附质量减少,吸附层由致密逐渐变得疏松,pH小于等电点时以静电吸附为主,pH大于等电点时以非静电的特性吸附为主.当SBAL的用量小于临界值(0.5 wt%)时,其在氧化铝表面形成单分子层吸附,在颗粒间起到静电排斥作用;当用量大于临界值时,其在颗粒表面形成聚集体吸附而起到空间位阻作用.%A sulfonated lignin-based polymer, SBAL, was prepared by sulfomethylation, etherification and polycondensation reaction using alkali lignin from the alkaline pulping spent liquor of bamboo as main material. TEM and H-NMR results showed that the structure of SBAL was loose spherical, the center of which was the hydrophobic skeletons of lignin, the long side chains with sulfonic and carboxyl groups were distributed on its surface. GPC and potentiometric titration results showed that the Mw of SBAL reached 24880 Da, 7.38 times of the alkali lignin, and the sulfonic group content was 2.70 mmol·g-1. The adsorption properties and the dispersion efficiencies of SBAL were investigated by means of isothermal adsorption, XPS, zeta potential and rheological experiments. At pH 3 ~ 12, the SBAL as

  1. Atomic-Level Structure Characterization of Biomass Pre- and Post-Lignin Treatment by Dynamic Nuclear Polarization-Enhanced Solid-State NMR.

    Science.gov (United States)

    Perras, Frédéric A; Luo, Hao; Zhang, Ximing; Mosier, Nathan S; Pruski, Marek; Abu-Omar, Mahdi M

    2017-01-26

    Lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear (13)C-(13)C correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic-level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determine structure-function relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.

  2. CHEMICAL AND THERMAL CHARACTERIZATION OF THREE INDUSTRIAL LIGNINS AND THEIR CORRESPONDING LIGNIN ESTERS

    Directory of Open Access Journals (Sweden)

    Stephen Carter Fox

    2010-04-01

    Full Text Available Corn stover and rice straw lignin samples received from ethanol pilot plants, along with softwood kraft lignin samples, were characterized using pyrolysis GC-MS, 13C CP/MAS NMR spectroscopy, and permanganate oxidation degradation. The lignins were then esterified using 1-methylimidazole as a catalyst in a pyridine-free reaction, and the thermal properties of the products were evaluated. Solid state NMR showed the rice straw lignin contained 18% residual polysaccharides. Pyrolysis GC-MS showed the softwood kraft, corn stover, and rice straw lignins to be G – type, H/G/S – type, and G/S – type, respectively. However, some discrepancy was apparent between the pyrolysis and permanganate oxidation studies as to the ratios of the monomeric make-up of the lignins. The kraft and rice straw lignins were determined to have high degrees of condensation, while the corn stover lignin was uncondensed. Little to no increase in solubility was noticed for corn stover or rice straw lignin esters in organic solvents. Glass transition temperatures (Tg of the lignin derivatives were determined by a combination of differential scanning calorimetry, dynamic mechanical analysis, and parallel plate rheometry.

  3. Comparative evaluation of three lignin isolation protocols for various wood species.

    Science.gov (United States)

    Guerra, Anderson; Filpponen, Ilari; Lucia, Lucian A; Argyropoulos, Dimitris S

    2006-12-27

    Milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and enzymatic mild acidolysis lignin (EMAL) were isolated from different wood species and characterized by various techniques. The EMAL protocol offered gravimetric lignin yields 2-5 times greater than those of the corresponding MWL and CEL. The purities of the EMALs were 3.75-10.6% higher than those of their corresponding CELs, depending upon the wood species from which they were isolated. Molecular weight analyses showed that the EMAL protocol isolates lignin fractions that are not accessed by the other procedures evaluated, while 31P NMR spectroscopy revealed that MWL is more condensed and bears more phenolic hydroxyl groups than EMAL and CEL. The yields and purities of EMAL, MWL, and CEL from hardwood were greater than those obtained for the examined softwoods. Structural details obtained by DFRC (derivatization followed by reductive cleavage)/31P NMR revealed different contents of condensed and uncondensed beta-O-aryl ether structures, dibenzodioxocins, and condensed and uncondensed phenolic hydroxyl and carboxylic acid groups within lignins isolated from different wood species.

  4. Extraction and characterization of original lignin and hemicelluloses from wheat straw.

    Science.gov (United States)

    Sun, Xiao-Feng; Sun, RunCang; Fowler, Paul; Baird, Mark S

    2005-02-23

    Original lignin and hemicelluloses were sequentially extracted with high yield/purity, using acidic dioxane/water solution and dimethyl sulfoxide, from ball-milled wheat straw. The acidic dioxane lignin fraction is distinguished by high beta-O-4' structures and by low amounts of condensed units (beta-5', 5-5', and beta-1'). Hemicelluloses contain arabinoxylans as the major polysaccharides, which are substituted by alpha-l-arabinofuranose, 4-O-methylglucuronic acid, acetyl group (DS = 0.1), and xylose at O-3 and/or O-2 of xylans. It was found that arabinoxylans form cross-links with lignins through ferulates via ether bonds, glucuronic acid via ester bonds, and arbinose/xylose via both ether and glycosidic bonds, respectively, in the cell walls of wheat straw. Diferulates are also incorporated into cross-links between lignin and hemicelluloses as well as lignification of wheat straw cell walls. The guaiacyl unit is considered to be a significant condensed structural constructor in extracted lignin and a connector between lignin and carbohydrates.

  5. Comparison of the pyrolysis behavior of lignins from different tree species.

    Science.gov (United States)

    Wang, Shurong; Wang, Kaige; Liu, Qian; Gu, Yueling; Luo, Zhongyang; Cen, Kefa; Fransson, Torsten

    2009-01-01

    Despite the increasing importance of biomass pyrolysis, little is known about the pyrolysis behavior of lignin--one of the main components of biomass--due to its structural complexity and the difficulty in its isolation. In the present study, we extracted lignins from Manchurian ash (Fraxinus mandschurica) and Mongolian Scots pine (Pinus sylvestris var. mongolica) using the Bjorkman procedure, which has little effect on the structure of lignin. Fourier transform infrared (FTIR) spectrometry was used to characterize the microstructure of the Bjorkman lignins, i.e., milled wood lignins (MWLs), from the different tree species. The pyrolysis characteristics of MWLs were investigated using a thermogravimetric analyzer, and the release of the main volatile and gaseous products of pyrolysis were detected by FTIR spectroscopy. During the pyrolysis process, MWLs underwent thermo-degradation over a wide temperature range. Manchurian ash MWL showed a much higher thermal degradation rate than Mongolian Scots pine MWL in the temperature range from 290-430 degrees C. High residue yields were achieved at 37 wt.% for Mongolian Scots pine MWL and 26 wt.% for Manchurian ash MWL. In order to further investigate the mechanisms of lignin pyrolysis, we also analyzed the FTIR profiles for the main pyrolysis products (CO(2), CO, methane, methanol, phenols and formaldehyde) and investigated the variation in pyrolysis products between the different MWLs.

  6. Lignin solubilisation and gentle fractionation in liquid ammonia

    NARCIS (Netherlands)

    Strassberger, Z.; Prinsen, P.; Klis, van der F.; Es, van D.S.; Tanase, S.; Rothenberg, G.

    2015-01-01

    We present a simple method for solubilising lignin using liquid ammonia. Unlike water, which requires harsh conditions, ammonia can solubilise technical lignins, in particular kraft lignin. A commercial pine wood Kraft lignin (Indulin AT) was solubilized instantaneously at room temperature and 7–11

  7. Lignin solubilisation and gentle fractionation in liquid ammonia

    NARCIS (Netherlands)

    Strassberger, Z.; Prinsen, P.; van der Klis, F.; van Es, D.S.; Tanase, S.; Rothenberg, G.

    2015-01-01

    We present a simple method for solubilizing lignin using liq. ammonia. Unlike water, which requires harsh conditions, ammonia can solubilize tech. lignins, in particular kraft lignin. A com. pine wood Kraft lignin (Indulin AT) was solubilized instantaneously at room temp. and 7-​11 bars autogenous

  8. Characterization of electrospun lignin based carbon fibers

    Science.gov (United States)

    Poursorkhabi, Vida; Mohanty, Amar; Misra, Manjusri

    2015-05-01

    The production of lignin fibers has been studied in order to replace the need for petroleum based precursors for carbon fiber production. In addition to its positive environmental effects, it also benefits the economics of the industries which cannot take advantage of carbon fiber properties because of their high price. A large amount of lignin is annually produced as the byproduct of paper and growing cellulosic ethanol industry. Therefore, finding high value applications for this low cost, highly available material is getting more attention. Lignin is a biopolymer making about 15 - 30 % of the plant cell walls and has a high carbon yield upon carbonization. However, its processing is challenging due to its low molecular weight and also variations based on its origin and the method of separation from cellulose. In this study, alkali solutions of organosolv lignin with less than 1 wt/v% of poly (ethylene oxide) and two types of lignin (hardwood and softwood) were electrospun followed by carbonization. Different heating programs for carbonization were tested. The carbonized fibers had a smooth surface with an average diameter of less than 5 µm and the diameter could be controlled by the carbonization process and lignin type. Scanning electron microscopy (SEM) was used to study morphology of the fibers before and after carbonization. Thermal conductivity of a sample with amorphous carbon was 2.31 W/m.K. The electrospun lignin carbon fibers potentially have a large range of application such as in energy storage devices and water or gas purification systems.

  9. Reconstitution of cellulose and lignin after [C2mim][OAc] pretreatment and its relation to enzymatic hydrolysis.

    Science.gov (United States)

    Yuan, Tong-Qi; Wang, Wei; Zhang, Li-Ming; Xu, Feng; Sun, Run-Cang

    2013-03-01

    Although the effects of cellulose crystallinity and lignin content as two major structural features on enzymatic hydrolysis have been extensively studied, debates regarding their effects still exist. In this study, reconstitution of cellulose and lignin after 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]) pretreatment was proposed as a new method to study their effects on enzymatic digestibility. Different mechanisms of lignin content for reduction of cellulose hydrolysis were found between the proposed method and the traditional method (mixing of cellulose and lignin). The results indicated that a slight change of the crystallinity of the reconstituted materials may play a minor role in the change of enzyme efficiency. In addition, the present study suggested that the lignin content does not significantly affect the digestibility of cellulose, whereas the conversion of cellulose fibers from the cellulose I to the cellulose II crystal phase plays an important role when an ionic liquid pretreatment of biomass was conducted. Copyright © 2012 Wiley Periodicals, Inc.

  10. Biobased Epoxy Nanocomposites Derived from Lignin-Based Monomers.

    Science.gov (United States)

    Zhao, Shou; Abu-Omar, Mahdi M

    2015-07-13

    Biobased epoxy nanocomposites were synthesized based on 2-methoxy-4-propylphenol (dihydroeugenol, DHE), a molecule that has been obtained from the lignin component of biomass. To increase the content of hydroxyl groups, DHE was o-demethylated using aqueous HBr to yield propylcatechol (DHEO), which was subsequently glycidylated to epoxy monomer. Optimal conditions in terms of yield and epoxy equivalent weight were found to be 60 °C with equal NaOH/phenolic hydroxyl molar ratio. The structural evolution from DHE to cured epoxy was followed by (1)H NMR and Fourier transform infrared spectroscopy. The nano-montmorillonite modified DHEO epoxy exhibited improved storage modulus and thermal stability as determined from dynamic mechanical analysis and thermogravimetric analysis. This study widens the synthesis routes of biobased epoxy thermosets from lignin-based molecules.

  11. EFFECT OF SOLVENT ON THE BETA-O-4 BOND CLEAVAGE OF A LIGNIN MODEL COMPOUND BY TERT-BUTOXIDE UNDER MILD CONDITIONS

    Directory of Open Access Journals (Sweden)

    Yuji Matsumoto

    2011-11-01

    Full Text Available The beta-O-4 bond cleavage of a non-phenolic β-O-4 type dimeric lignin model compound, 2-(2-methoxyphenoxy-1-(3,4-dimethoxyphenyl-ethanol (III, was examined in systems using potassium tert-butoxide as a base (0.5 mol/l and tert-butanol (tBuOH, dimethylsulfoxide, 1,4-dioxane, or tetrahydrofuran as a solvent. The β-O-4 bond of compound III was cleaved in any system at 30°C, and 2-methoxyphenol (II was liberated. The amount of compound II liberated was close to the quantitative yield on the basis of the amount of compound III that disappeared, except for the treatment in the t-BuOH system. The reaction rate was dependent on what solvent was used. Half-life periods for these systems were roughly about 6.0, 3.0, 0.7, and 0.2h, respectively. It seemed that the rates were very high when the polarity of the solvents was low. Two reaction products generated from the aromatic ring with two methoxyl groups of compound III, 4-acetyl-1,2-dimethoxybenzene and 3,4-dimethoxybenzoic acid, were detected in all the systems. A peculiar reaction product, 1,2-dimethoxybenzene, was detected in a fairly large quantity, only when the latter two solvents with low polarities were applied.

  12. High-value utilization of lignin to synthesize Ag nanoparticles with detection capacity for Hg²⁺.

    Science.gov (United States)

    Shen, Zuguang; Luo, Yuqiong; Wang, Qun; Wang, Xiaoying; Sun, Runcang

    2014-09-24

    This study reports the rapid preparation of silver nanoparticles (AgNPs) from Tollens' reagent under microwave irradiation. In the synthesis, lignin with reducing groups and spatial three-dimensional structure was used as reducing and stabilizing agents without other chemical reagents, and the effects of the ratio of lignin to Ag(+), reaction temperature, and heating time on the synthesis of AgNPs were investigated. The obtained AgNPs were further characterized by UV-vis, Malvern particle size, TEM, XRD, and XPS analyses. The structural changes of lignin before and after reaction were also studied by FT-IR, (1)H NMR, (13)C NMR, and GC-MS. The results revealed that the obtained AgNPs were mostly spherical with diameters of around 24 nm. The optimum reaction conditions were a ratio 50 mg of lignin to 0.3 mM of Ag(+), a microwave irradiation temperature of 60 °C, and a heating time of 10 min. Moreover, AgNPs redispersed well in water and ethanol after centrifugation for the removal of lignin. During the formation of AgNPs, lignin was oxidized, and the side chains of lignin were partly disrupted into small molecules, such as hydrocarbon and alcohol. The resultant lignin-AgNPs showed highly selective sensing detection for Hg(2+), and the color of the lignin-AgNP solution containing Hg(2+) decreased gradually with increasing amounts of Hg(2+) within seconds, but the other 19 metal ions had little effect on the color and surface plasmon absorption band of the lignin-AgNPs. Also, there was a linear relationship between the absorbance and Hg(2+) concentration, with a limit of detection concentration of 23 nM. This study provides not only a new way to take advantage of agricultural and forestry residues, but also a green and rapid method for the synthesis of AgNPs to detect the toxic ion Hg(2+) selectively and sensitively.

  13. Comparison of Antioxidant Activity Between Phenolic and Nonphenolic Alkaloids in Nelumbo Nucifera Gaertn in vitro%莲子心中酚性与非酚性生物碱体外抗氧化活性比较

    Institute of Scientific and Technical Information of China (English)

    杨小青; 宋金春; 谢顺岚; 郝好华

    2015-01-01

    Objective To compare the antioxidant activity between phenolic and nonphenolic alkaloids in Nelumbo Nucifera Gaertn.in vitro. Methods DPPH, ABTS, hydroxyl radical scavenging, super oxygen anion from oxidation, reducing power and beta carotene bleaching test methods were used to evaluate the antioxidant activity of the alkaloids. Results Half maximalinhibitory concentration ( IC50 ) of DPPH among total alkaloid, phenolic alkaloids and nonphenolic alkaloids was 21.89, 27.10 and 32.87 μg·mL-1 , respectively;IC50 of ABTS free radicals was 14.25, 20.55, 25.94μg·mL-1;The hydroxyl radical scavenging IC50 was 0.03, 0.03, 0.08 μg·mL-1; The auto-oxidation rate of super oxygen was 8.72×10-4, 5.87×10-4, 6.68× 10-4;The total alkaloid had the best reducing power, while the non-phennolic alakloids had the worst; Lipid inhibition rate of three alkaloids were 89.63%, 85.85% and 83.78% respectively. Conclusion Phenolic alkaloids are better than non-phenolic alkaloids in hydroxyl radical scavenging, reducing power and anti-lipid peroxidation, resulting in a promising prospect.%目的 比较莲子心中酚性生物碱与非酚性生物碱的体外抗氧化活性. 方法 采用1,1-二苯基-2-三硝基苯肼(DPPH)、2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)-二铵盐(ABTS)、羟基自由基清除、超氧阴离子自氧化,还原力及β-胡萝卜素漂白测试等方法评估莲子心中生物碱的抗氧化活性. 结果 总生物碱、酚性生物碱、非酚性生物碱对DPPH自由基的半数清除浓度( IC50 )分别为21.89, 27. 10, 32. 87 μg · mL-1;对 ABTS 自由基的 IC50分别为 14. 25, 20. 55, 25.94 μg·mL-1;对羟基自由基清除IC50分别为0.03,0.03,0.08 μg·mL-1;超氧阴离子自氧化速率分别为8.72×10-4, 5.87×10-4,6.68×10-4;还原力大小:总生物碱>酚性生物碱>非酚性生物碱;脂质抑制率分别为89.63%,85.85%,83.78%.结论 莲子心中酚性生物碱对自由基的清除活性、还原力、抗脂质过氧化活性强于

  14. Use of food and packaging model matrices to investigate the antioxidant properties of biorefinery grass lignins.

    Science.gov (United States)

    Aguié-Béghin, Véronique; Foulon, Laurence; Soto, Paola; Crônier, David; Corti, Elena; Legée, Frédéric; Cézard, Laurent; Chabbert, Brigitte; Maillard, Marie-Noëlle; Huijgen, Wouter J J; Baumberger, Stéphanie

    2015-11-18

    The antioxidant properties of grass lignins recovered from an alkaline industrial process and from different ethanol organosolv pretreatment processes were compared using two types of tests: (i) classical radical 2,2'-diphenyl-1-picrylhydrazyl (DPPH(•)) scavenging tests in dioxane/water or ethanol and (ii) tests involving multiphasic systems (lipid dispersion in water or cellulose film suspended in ethanol). These multiphasic systems were representative of food and packaging matrices in view of high-value applications. All lignins, in solution or in the film, effectively scavenged radicals. Moreover, they were competitive with a food commercial rosemary extract to protect linoleic acid against oxidation. Whereas the DPPH(•) test in dioxane was not discriminant, differences appeared between lignins when the test was performed in ethanol or with the multiphasic systems. Moreover, radical scavenging activity was preserved in the film even after its immersion in ethanol. Structural analysis of lignins revealed that low-molar-mass phenolics, namely p-hydroxycinnamic acids and lignin depolymerization products, governed lignin antioxidant properties in the multiphasic systems.

  15. Amination of biorefinery technical lignins using Mannich reaction synergy with subcritical ethanol depolymerization.

    Science.gov (United States)

    Wang, Bing; Chen, Tian-Ying; Wang, Han-Min; Li, Han-Yin; Liu, Chuan-Fu; Wen, Jia-Long

    2017-09-06

    The alcoholic depolymerization and Mannich reaction were conducted to improve the chemical activity of biorefinery technical lignins and introduce amino groups into lignins, respectively. To understand the chemical structural transformations and examine the reaction mechanism, GPC and solution-state NMR techniques were performed. Element analysis was also used to quantify the amount of amine groups. The NMR characterization the depolymerized lignins indicated of the depolymerization, demethoxylation, and bond cleavage of linkages occurred during the depolymerization process. Results showed that the depolymerization temperature instead of the addition of capping reagents was the main factor for improving the reactivity of lignin under the given conditions. The Mannich reaction was very selective, primarily occurred at H3,5 and G5 positions, and the H units present a higher chemical reactivity. It is believed that the understanding of the fundamental chemistry of lignin during depolymerization and Mannich reaction process will contribute to the extension of high value-added applications of biorefinery lignin. Copyright © 2017. Published by Elsevier B.V.

  16. Isolation and Physicochemical Characterization of Lignin from ...

    African Journals Online (AJOL)

    Muzakir

    2 Department of Chemistry, Faculty of Science, Gombe State University, P. M. B. 127, Gombe, Nigeria. .... remaining solid is the acid insoluble lignin (Toledano et al., 2012). .... dmso/licl system induced by microwave-assisted irradiation.

  17. Composition comprising lignin and antidi arrheal component

    DEFF Research Database (Denmark)

    2008-01-01

    The present invention relates to a composition comprising lignin and at least one compound selected from the group consisting of bromelain, papain, tannin, carvacrol, thymol, alliin, allicin, fenugreek seed, egg, poppy, poppy seeds, humic acid, roots, kaolin, catechu, cellulase, flavonoid...

  18. The impact of alterations in the lignin biosynthetic pathway on molecular architecture of the plant cell wall

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jiliang; Kim, Jeong IM; Cusumano, J C; Chapple, C; Venugopalan, Nagarajan; Fischetti, Robert F.; Makowski, Lee

    2016-06-17

    Background: Coordination of synthesis and assembly of the polymeric components of cell walls is essential for plant growth and development. Given the degree of co-mingling and cross-linking among cell wall components, cellulose organization must be dependent on the organization of other polymers such as lignin. Here we seek to identify aspects of that codependency by studying the structural organization of cellulose fibrils in stems from Arabidopsis plants harboring mutations in genes encoding enzymes involved in lignin biosynthesis. Plants containing high levels of G-lignin, S-lignin, H-lignin, aldehyde-rich lignin, and ferulic acid-containing lignin, along with plants with very low lignin content were grown and harvested and longitudinal sections of stem were prepared and dried. Scanning X-ray microdiffraction was carried out using a 5-micron beam that moved across the sections in 5-micron steps and complete diffraction patterns were collected at each raster point. Approximately, 16,000 diffraction patterns were analyzed to determine cellulose fibril orientation and order within the tissues making up the stems. Results: Several mutations-most notably those exhibiting (1) down-regulation of cinnamoyl CoA reductase which leads to cell walls deficient in lignin and (2) defect of cinnamic acid 4-hydroxylase which greatly reduces lignin content-exhibited significant decrease in the proportion of oriented cellulose fibrils in the cell wall. Distinctions between tissues were maintained in all variants and even in plants exhibiting dramatic changes in cellulosic order the trends between tissues (where apparent) were generally maintained. The resilience of cellulose to degradative processes was investigated by carrying out the same analysis on samples stored in water for 30 days prior to data collection. This treatment led to significant loss of cellulosic order in plants rich in aldehyde or H-lignin, less change in wild type, and essentially no change in samples with

  19. Use of lignin extracted from different plant sources as standards in the spectrophotometric acetyl bromide lignin method.

    Science.gov (United States)

    Fukushima, Romualdo S; Kerley, Monty S

    2011-04-27

    A nongravimetric acetyl bromide lignin (ABL) method was evaluated to quantify lignin concentration in a variety of plant materials. The traditional approach to lignin quantification required extraction of lignin with acidic dioxane and its isolation from each plant sample to construct a standard curve via spectrophotometric analysis. Lignin concentration was then measured in pre-extracted plant cell walls. However, this presented a methodological complexity because extraction and isolation procedures are lengthy and tedious, particularly if there are many samples involved. This work was targeted to simplify lignin quantification. Our hypothesis was that any lignin, regardless of its botanical origin, could be used to construct a standard curve for the purpose of determining lignin concentration in a variety of plants. To test our hypothesis, lignins were isolated from a range of diverse plants and, along with three commercial lignins, standard curves were built and compared among them. Slopes and intercepts derived from these standard curves were close enough to allow utilization of a mean extinction coefficient in the regression equation to estimate lignin concentration in any plant, independent of its botanical origin. Lignin quantification by use of a common regression equation obviates the steps of lignin extraction, isolation, and standard curve construction, which substantially expedites the ABL method. Acetyl bromide lignin method is a fast, convenient analytical procedure that may routinely be used to quantify lignin.

  20. Study of Antioxidant Effectiveness of Kraft Lignin in HDPE

    Directory of Open Access Journals (Sweden)

    I. Piña

    2015-01-01

    Full Text Available Polymers are subject to oxidative degradation during all steps of their useful cycle. This degradative process is prevented using stabilizers like antioxidant of the type sterically hindered phenols or amines. Lignin, due to the presence of phenolic groups in their structure, can present characteristic as antioxidant agent, in a similar way to the additives used in polymers. Therefore, in this work, the antioxidant capacity of the lignin in a sample of polyethylene is studied. For this reason, in this paper, a method based on nonisothermal differential scanning calorimetry (DSC to evaluate this property is used. The samples studied were subjected to heat treatment at different scan rates and in presence of oxygen to promote thermooxidation of the material. The antioxidant capacity of different formulations of lignin and additives in the polymer resin was determined from the temperature of onset of oxidation (Ti at different heating rates and adjusting Arrhenius model prediction. The results indicate that the procedure can predict the antioxidant capacity of antioxidant additives in HDPE with good reproducibility and accuracy, according to the Arrhenius model prediction.

  1. Understanding the Impact of Poly(ethylene oxide) on the Assembly of Lignin in Solution toward Improved Carbon Fiber Production.

    Science.gov (United States)

    Imel, Adam E; Naskar, Amit K; Dadmun, Mark D

    2016-02-10

    Carbon fiber produced from lignin has recently become an industrial scalable product with applications ranging from thermal insulation to reinforcing automobile bodies. Previous research has shown that mixing 1-2 wt %, of poly(ethylene oxide) (PEO) with the lignin before fiber formation can enhance the properties of the final carbon fibers. The research reported here determines the impact of adding PEO to a lignin solution on its assembly, focusing on the role of the lignin structure on this assembly process. Results indicate the addition of PEO anisotropically directs the self-assembly of the hardwood and softwood lignin by lengthening the cylindrical building blocks that make up the larger global aggregates. On the other hand, results from an annual lignin exhibit a shapeless, more complex structure with a unique dependence on the PEO loading. These results are consistent with improved carbon fibers from solutions of lignin that include PEO, as the local ordering and directed assembly will inhibit the formation of defects during the carbon fiber fabrication process.

  2. Characterization of electrospun lignin based carbon fibers

    Energy Technology Data Exchange (ETDEWEB)

    Poursorkhabi, Vida; Mohanty, Amar; Misra, Manjusri [School of Engineering, Thornbrough Building, University of Guelph, Guelph, N1G 2W1, Ontario (Canada); Bioproducts Discovery and Development Centre, Department of Plant Agriculture, Crop Science Building, University of Guelph, Guelph, N1G 2W1, Ontario (Canada)

    2015-05-22

    The production of lignin fibers has been studied in order to replace the need for petroleum based precursors for carbon fiber production. In addition to its positive environmental effects, it also benefits the economics of the industries which cannot take advantage of carbon fiber properties because of their high price. A large amount of lignin is annually produced as the byproduct of paper and growing cellulosic ethanol industry. Therefore, finding high value applications for this low cost, highly available material is getting more attention. Lignin is a biopolymer making about 15 – 30 % of the plant cell walls and has a high carbon yield upon carbonization. However, its processing is challenging due to its low molecular weight and also variations based on its origin and the method of separation from cellulose. In this study, alkali solutions of organosolv lignin with less than 1 wt/v% of poly (ethylene oxide) and two types of lignin (hardwood and softwood) were electrospun followed by carbonization. Different heating programs for carbonization were tested. The carbonized fibers had a smooth surface with an average diameter of less than 5 µm and the diameter could be controlled by the carbonization process and lignin type. Scanning electron microscopy (SEM) was used to study morphology of the fibers before and after carbonization. Thermal conductivity of a sample with amorphous carbon was 2.31 W/m.K. The electrospun lignin carbon fibers potentially have a large range of application such as in energy storage devices and water or gas purification systems.

  3. Estimativa por infravermelho da concentração da unidade estrutural b-O-4 em ligninas de angiospermas tropicais Infrared estimates of the concentration of the b-o-4 structural unit in lignins of tropical angiosperms

    Directory of Open Access Journals (Sweden)

    Heber dos Santos Abreu

    1997-12-01

    Full Text Available Five Björkman lignins, codified as AM, LL, GG, PP and AP, were isolated from wood species of Aspidosperma macrocarpum Mart., Lophanthera lactescens Ducke, Gallesia gorazema (Vell. Miq., Peltogyne paniculata Bth. and Aspidosperma polyneuron Muell. Arg., respectively. Analyses of the lignins were carried out by Fourier transformed infrared spectroscopy using an experimental technique, Diffusely Reflected Infrared Fourier Transformed (DRIFT, admitting in the original spectra a band at 1500 cm-1 as an internal reference. Application of a deconvolution technique made possible to estimate the percentage per mol of b-O-4 unit content around 65.5% to AM, 68.0% to LL, 71.0% to GG. 73.4% to PP and 75.0% to AP, toward AM

  4. Esterification and characterization of lignin aiming the synthesis of polymeric composite; Esterificacao e caracterizacao da lignina visando a sintese de compositos polimericos

    Energy Technology Data Exchange (ETDEWEB)

    Victor, Priscilla A.; Machado, Fabricio, E-mail: fmachado@unb.br [Universidade de Brasilia (UnB), DF (Brazil). Instituto de Quimica; Goncalves, Silvia B., E-mail: silvia.belem@embrapa.br [Embrapa Agroenergia, Parque Estacao Biologica (PqEB), Brasilia, DF (Brazil)

    2013-07-01

    Lignin is a natural polymer derived from lignocellulosic materials with high availability, presenting a huge potential for production of new materials. Due to its complex macromolecular structure, and its low compatibility with styrene, eucalyptus wood-extracted lignin method was esterified with methacrylic anhydride - exhibiting a yield of 64% - in order to ensure homogeneity in the organic phase into the reaction medium. The evaluation of both the natural and esterified lignin through infrared (IR) spectroscopy showed a decrease of the hydroxyl band, characteristic of natural lignin (3200-3400 cm{sup -1}) and an increase of the characteristic ester band (1720 to 1740 cm{sup -1}). According to nuclear magnetic resonance ({sup 1}H NMR) analysis on esterified lignin, intense peaks were observed in the range from 1.7 to 2.05 ppm (-CH{sub 3}) and 5.4 ppm to 6.2 ppm (=CH{sub 2}), related to methacrylic anhydride. According to the thermogravimetric analysis (TGA), the esterified lignin showed a decrease in its thermal stability when compared to natural lignin, exhibiting two main weight losses between 200 °C and 300 °C and in the interval from 550 °C to 800 °C. Comparatively, the esterified lignin also displayed an increase in its glass transition temperature (Tg = 98 °C) for, when compared to natural lignin, whose Tg value was determined to be equal to 91 °C. (author)

  5. Sorption of 2,4-dinitroanisole (DNAN) on lignin

    Institute of Scientific and Technical Information of China (English)

    Rabih Saad; Zorana Radovic-Hrapovic; Behzad Ahvazi; Sonia Thiboutot; Guy Ampleman; Jalal Hawari

    2012-01-01

    The present study describes the use of two commercially available lignins,namely,alkali and organosolv lignin,for the removal of 2,4-dinitroanisole (DNAN),a chemical widely used by the military and the dye industry,from water.Sorption of DNAN on both lignins reached equilibrium within 10 hr and followed pseudo second-order kinetics with sorption being faster with alkali than with organosolv lignin,i.e.k2 10.3 and 0.3 g/(mg.hr),respectively.In a separate study we investigated sorption of DNAN between 10 and 40℃ and found that the removal of DNAN by organosolv lignin increased from 0.8 to 7.5 mg/g but reduced slightly from 8.5 to 7.6 mg/g in the case of alkali lignin.Sorption isotherms for either alkali or organosolv lignin best fitted Freundlich equation with enthalpy of formation,△H0 equaled to 14 or 80 kJ/mol.To help understand DNAN sorption mechanisms we characterized the two lignins by elemental analysis,BET nitrogen adsorption-desorption and 31p NMR.Variations in elemental compositions between the two lignins indicated that alkali lignin should have more sites (O- and S-containing functionalities) for H-bonding.The BET surface area and calculated total pore volume of alkali lignin were almost 10 times greater than that of organosolv lignin suggesting that alkali lignin should provide more sites for sorption.31p NMR showed that organosolv lignin contains more phenolic -OH groups than alkali lignin,i.e.,70% and 45%,respectively.The variations in the type of OH groups between the two lignins might have affected the strength of H-bonding between DNAN and the type of lignin used.

  6. Sorption of 2,4-dinitroanisole (DNAN) on lignin.

    Science.gov (United States)

    Saad, Rabih; Radovic-Hrapovic, Zorana; Ahvazi, Behzad; Thiboutot, Sonia; Ampleman, Guy; Hawari, Jalal

    2012-01-01

    The present study describes the use of two commercially available lignins, namely, alkali and organosolv lignin, for the removal of 2,4-dinitroanisole (DNAN), a chemical widely used by the military and the dye industry, from water. Sorption of DNAN on both lignins reached equilibrium within 10 hr and followed pseudo second-order kinetics with sorption being faster with alkali than with organosolv lignin, i.e. k2 10.3 and 0.3 g/(mg x hr), respectively. In a separate study we investigated sorption of DNAN between 10 and 40 degrees C and found that the removal of DNAN by organosolv lignin increased from 0.8 to 7.5 mg/g but reduced slightly from 8.5 to 7.6 mg/g in the case of alkali lignin. Sorption isotherms for either alkali or organosolv lignin best fitted Freundlich equation with enthalpy of formation, deltaH0 equaled to 14 or 80 kJ/mol. To help understand DNAN sorption mechanisms we characterized the two lignins by elemental analysis, BET nitrogen adsorption-desorption and 31P NMR. Variations in elemental compositions between the two lignins indicated that alkali lignin should have more sites (O- and S-containing functionalities) for H-bonding. The BET surface area and calculated total pore volume of alkali lignin were almost 10 times greater than that of organosolv lignin suggesting that alkali lignin should provide more sites for sorption. 31P NMR showed that organosolv lignin contains more phenolic -OH groups than alkali lignin, i.e., 70% and 45%, respectively. The variations in the type of OH groups between the two lignins might have affected the strength of H-bonding between DNAN and the type of lignin used.

  7. Reductive Catalytic Fractionation of Corn Stover Lignin

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Eric M.; Katahira, Rui; Reed, Michelle; Resch, Michael G.; Karp, Eric M.; Beckham, Gregg T.; Román-Leshkov, Yuriy

    2016-12-05

    Reductive catalytic fractionation (RCF) has emerged as an effective biomass pretreatment strategy to depolymerize lignin into tractable fragments in high yields. We investigate the RCF of corn stover, a highly abundant herbaceous feedstock, using carbon-supported Ru and Ni catalysts at 200 and 250 degrees C in methanol and, in the presence or absence of an acid cocatalyst (H3PO4 or an acidified carbon support). Three key performance variables were studied: (1) the effectiveness of lignin extraction as measured by the yield of lignin oil, (2) the yield of monomers in the lignin oil, and (3) the carbohydrate retention in the residual solids after RCF. The monomers included methyl coumarate/ferulate, propyl guaiacol/syringol, and ethyl guaiacol/syringol. The Ru and Ni catalysts performed similarly in terms of product distribution and monomer yields. The monomer yields increased monotonically as a function of time for both temperatures. At 6 h, monomer yields of 27.2 and 28.3% were obtained at 250 and 200 degrees C, respectively, with Ni/C. The addition of an acid cocatalysts to the Ni/C system increased monomer yields to 32% for acidified carbon and 38% for phosphoric acid at 200 degrees C. The monomer product distribution was dominated by methyl coumarate regardless of the use of the acid cocatalysts. The use of phosphoric acid at 200 degrees C or the high temperature condition without acid resulted in complete lignin extraction and partial sugar solubilization (up to 50%) thereby generating lignin oil yields that exceeded the theoretical limit. In contrast, using either Ni/C or Ni on acidified carbon at 200 degrees C resulted in moderate lignin oil yields of ca. 55%, with sugar retention values >90%. Notably, these sugars were amenable to enzymatic digestion, reaching conversions >90% at 96 h. Characterization studies on the lignin oils using two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance and gel permeation chromatrography revealed

  8. Impact of Hot-Water Extraction on Acetone-Water Oxygen Delignification of Paulownia Spp. and Lignin Recovery

    Directory of Open Access Journals (Sweden)

    Chen Gong

    2014-02-01

    Full Text Available A hardwood-based biorefinery process starting with hot-water extraction (HWE is recommended in order to remove most of the hemicelluloses/xylans before further processing. HWE may be followed by delignification in acetone/water in the presence of oxygen (AWO for the production of cellulose and lignin. In this study, the HWE-AWO sequence was evaluated for its effectiveness at removing lignin from the fast-growing species Paulownia tomentosa (PT and Paulownia elongata (PE, in comparison with the reference species, sugar maple (Acer saccharum, SM. HWE might lead to a remarkable increase in lignin accessibility, and as a result, a greater AWO delignification degree was observed for extracted PT, PE, and SM than for unextracted ones. Organosolv lignin was recovered from the spent liquor of AWO delignification of PT with/without prior HWE and characterized to evaluate the benefits of HWE on the lignin structure and purity. The lignin recovered from the spent liquor of HWE-AWO sequence is of higher purity and lighter color than that recovered from the AWO spent liquor. These properties along with low sulfur content are desirable for lignin high-value applications.

  9. Increase in 4-coumaryl alcohol units during lignification in alfalfa (Medicago sativa) alters the extractability and molecular weight of lignin.

    Science.gov (United States)

    Ziebell, Angela; Gracom, Kristen; Katahira, Rui; Chen, Fang; Pu, Yunqiao; Ragauskas, Art; Dixon, Richard A; Davis, Mark

    2010-12-10

    The lignin content of biomass can impact the ease and cost of biomass processing. Lignin reduction through breeding and genetic modification therefore has potential to reduce costs in biomass-processing industries (e.g. pulp and paper, forage, and lignocellulosic ethanol). We investigated compositional changes in two low-lignin alfalfa (Medicago sativa) lines with antisense down-regulation of p-coumarate 3-hydroxylase (C3H) or hydroxycinnamoyl-CoA:shikimate hydroxycinnamoyltransferase (HCT). We investigated whether the difference in reactivity during lignification of 4-coumaryl alcohol (H) monomers versus the naturally dominant sinapyl alcohol and coniferyl alcohol lignin monomers alters the lignin structure. Sequential base extraction readily reduced the H monomer content of the transgenic lines, leaving a residual lignin greatly enriched in H subunits; the extraction profile highlighted the difference between the control and transgenic lines. Gel permeation chromatography of isolated ball-milled lignin indicated significant changes in the weight average molecular weight distribution of the control versus transgenic lines (CTR1a, 6000; C3H4a, 5500; C3H9a, 4000; and HCT30a, 4000).

  10. Increase in 4-Coumaryl Alcohol Units during Lignification in Alfalfa (Medicago sativa) Alters the Extractability and Molecular Weight of Lignin*

    Science.gov (United States)

    Ziebell, Angela; Gracom, Kristen; Katahira, Rui; Chen, Fang; Pu, Yunqiao; Ragauskas, Art; Dixon, Richard A.; Davis, Mark

    2010-01-01

    The lignin content of biomass can impact the ease and cost of biomass processing. Lignin reduction through breeding and genetic modification therefore has potential to reduce costs in biomass-processing industries (e.g. pulp and paper, forage, and lignocellulosic ethanol). We investigated compositional changes in two low-lignin alfalfa (Medicago sativa) lines with antisense down-regulation of p-coumarate 3-hydroxylase (C3H) or hydroxycinnamoyl-CoA:shikimate hydroxycinnamoyltransferase (HCT). We investigated whether the difference in reactivity during lignification of 4-coumaryl alcohol (H) monomers versus the naturally dominant sinapyl alcohol and coniferyl alcohol lignin monomers alters the lignin structure. Sequential base extraction readily reduced the H monomer content of the transgenic lines, leaving a residual lignin greatly enriched in H subunits; the extraction profile highlighted the difference between the control and transgenic lines. Gel permeation chromatography of isolated ball-milled lignin indicated significant changes in the weight average molecular weight distribution of the control versus transgenic lines (CTR1a, 6000; C3H4a, 5500; C3H9a, 4000; and HCT30a, 4000). PMID:20921228

  11. Epigallocatechin gallate incorporation into lignin enhances the alkaline delignification and enzymatic saccharification of cell walls

    Directory of Open Access Journals (Sweden)

    Elumalai Sasikumar

    2012-08-01

    Full Text Available Abstract Background Lignin is an integral component of the plant cell wall matrix but impedes the conversion of biomass into biofuels. The plasticity of lignin biosynthesis should permit the inclusion of new compatible phenolic monomers such as flavonoids into cell wall lignins that are consequently less recalcitrant to biomass processing. In the present study, epigallocatechin gallate (EGCG was evaluated as a potential lignin bioengineering target for rendering biomass more amenable to processing for biofuel production. Results In vitro peroxidase-catalyzed polymerization experiments revealed that both gallate and pyrogallyl (B-ring moieties in EGCG underwent radical cross-coupling with monolignols mainly by β–O–4-type cross-coupling, producing benzodioxane units following rearomatization reactions. Biomimetic lignification of maize cell walls with a 3:1 molar ratio of monolignols and EGCG permitted extensive alkaline delignification of cell walls (72 to 92% that far exceeded that for lignified controls (44 to 62%. Alkali-insoluble residues from EGCG-lignified walls yielded up to 34% more glucose and total sugars following enzymatic saccharification than lignified controls. Conclusions It was found that EGCG readily copolymerized with monolignols to become integrally cross-coupled into cell wall lignins, where it greatly enhanced alkaline delignification and subsequent enzymatic saccharification. Improved delignification may be attributed to internal trapping of quinone-methide intermediates to prevent benzyl ether cross-linking of lignin to structural polysaccharides during lignification, and to the cleavage of ester intra-unit linkages within EGCG during pretreatment. Overall, our results suggest that apoplastic deposition of EGCG for incorporation into lignin would be a promising plant genetic engineering target for improving the delignification and saccharification of biomass crops.

  12. Arogenate dehydratase isoenzymes profoundly and differentially modulate carbon flux into lignins.

    Science.gov (United States)

    Corea, Oliver R A; Ki, Chanyoung; Cardenas, Claudia L; Kim, Sung-Jin; Brewer, Sarah E; Patten, Ann M; Davin, Laurence B; Lewis, Norman G

    2012-03-30

    How carbon flux differentially occurs in vascular plants following photosynthesis for protein formation, phenylpropanoid metabolism (i.e. lignins), and other metabolic processes is not well understood. Our previous discovery/deduction that a six-membered arogenate dehydratase (ADT1-6) gene family encodes the final step in Phe biosynthesis in Arabidopsis thaliana raised the fascinating question whether individual ADT isoenzymes (or combinations thereof) differentially modulated carbon flux to lignins, proteins, etc. If so, unlike all other lignin pathway manipulations that target cell wall/cytosolic processes, this would be the first example of a plastid (chloroplast)-associated metabolic process influencing cell wall formation. Homozygous T-DNA insertion lines were thus obtained for five of the six ADTs and used to generate double, triple, and quadruple knockouts (KOs) in different combinations. The various mutants so obtained gave phenotypes with profound but distinct reductions in lignin amounts, encompassing a range spanning from near wild type levels to reductions of up to ∼68%. In the various KOs, there were also marked changes in guaiacyl:syringyl ratios ranging from ∼3:1 to 1:1, respectively; these changes were attributed to differential carbon flux into vascular bundles versus that into fiber cells. Laser microscope dissection/pyrolysis GC/MS, histochemical staining/lignin analyses, and pADT::GUS localization indicated that ADT5 preferentially affects carbon flux into the vascular bundles, whereas the adt3456 knock-out additionally greatly reduced carbon flux into fiber cells. This plastid-localized metabolic step can thus profoundly differentially affect carbon flux into lignins in distinct anatomical regions and provides incisive new insight into different factors affecting guaiacyl:syringyl ratios and lignin primary structure.

  13. Hydrogenolysis and Activation of Soda Lignin Using [BMIM]Cl as a Catalyst and Solvent

    Directory of Open Access Journals (Sweden)

    Shengming Zhang

    2017-07-01

    Full Text Available To improve the reactivity of the soda lignin, an acid ionic liquid 1-butyl-3-mthylimidazolium chloride ([BMIM]Cl was used as the catalyst and solvent to degrade the soda lignin through hydrogenolysis. Structural elucidation of the lignin samples was conducted by using a combination of analytical methods including chemical analysis, ultraviolet spectrophotometry (UV spectrophotometry, Fourier transform infrared spectroscopy (FT-IR spectra, two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR techniques, and gel permeation chromatography (GPC. The antioxidant activities of the lignin samples were evaluated using the diammonium 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate (ABTS+ radical scavenging and 1,1-diphenyl-2-picrylhydrazyl (DPPH radical scavenging methods. The degradation mechanism was proposed based on the characterization results. The optimal reaction condition was as follows: the concentration of [BMIM]Cl in the solution was 10 wt %, the hydrogen initial pressure was 3 MPa, and the solution was heated for 4 h at 90 °C. After the reaction, the total hydroxyl content of the soda lignin increased by 81.3%, while the phenolic hydroxyl content increased by 23.1%. At the same time, the weight-average molar mass of the soda lignin sample decreased from 8220 to 6450 g/mol with an improved antioxidant activity. In addition, approximately 56.7% of the β-O-4 linkages were degraded in the lreaction. The main effect of the acid ionic liquid [BMIM]C1 was related to the cleavage of β-O-4 linkages. This study has shown the potential of using the catalyzed soda lignin as a natural polymer antioxidant.

  14. Lignin from sugar cane bagasse: extraction, fabrication of nanostructured films, and application.

    Science.gov (United States)

    Pereira, A A; Martins, G F; Antunes, P A; Conrrado, R; Pasquini, D; Job, A E; Curvelo, A A S; Ferreira, M; Riul, A; Constantino, C J L

    2007-06-05

    Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels through impedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing

  15. Investigation of trace metal binding properties of lignin by diffusive gradients in thin films.

    Science.gov (United States)

    Hojaji, Elahe

    2012-09-01

    The binding behavior of lignin for Pb, Cu, Co, Mn, Cd and Ni was studied using the diffusive gradients in thin films technique (DGT). Samplers with different structures of diffusive gel were used in the well-stirred systems containing known concentrations of metals along with (a) 10, 20 and 40 μM lignin and; (b) 0.64 and 6.47 μM Suwannee river fulvic acid+40 μM lignin at an ionic strength of 0.01 M (NaNO(3)) and pH=7. Diffusion coefficients of lignin complexes in acrylamide gels were estimated and found to be less than 5% of the equivalent coefficients for the uncomplexed metal ions. These values were used to calculate concentrations of labile metals from DGT measurements in solutions, where lignin could discriminate metals in the order of Pb(+2)>Cu(+2)>Cd(+2)>Ni(+2)>Co(+2)>Mn(+2). Stability constants (LogK) were calculated using Visual MINTEQ II and WHAM V software. The K values were compared with the stability constants from titration of Pb and Cd with 10 μM lignin aqueous samples and with those of humic substances in natural waters. The constants obtained from measurement of complexing capacities might bias the real corresponding values unless two line regression analyses on titration data are considered. The DGT study of fractionation of metal species at varying ratios indicated that the proportion of organic complexes decreased with increasing ratios and gradually more metals were exchanged with inorganic phases. Speciation of Pb and Cd is affected by the concentrations of FA, Cd is dominantly bound with FA while Pb is evenly partitioned between the ligands. The comprehensive knowledge of metal-lignin complexes sheds some light on in situ operational speciation information that can be achieved by DGT.

  16. Fourier transform Raman assignment of guaiacyl and syringyl marker bands for lignin determination

    Science.gov (United States)

    Takayama, Miyuki; Johjima, Toru; Yamanaka, Takeshi; Wariishi, Hiroyuki; Tanaka, Hiroo

    1997-09-01

    A near infrared fourier transform Raman (NIR-FTR) spectroscopic technique was utilized to characterize lignin in wood. The Raman bands for CC stretching derived from 4-hydroxy-3-methoxyphenyl (guaiacyl) nuclei and from 3,5-dimethoxy-4-hydroxyphenyl (syringyl) nuclei exist independently. The NIR-FTR analysis of a series of lignin model compounds indicated that a syringyl band was shifted to a lower frequency compared to a guaiacyl band. This shift was also observed in chemically synthesized lignin (DHP). Syringyl DHP, in which all the aromatic nuclei consist of syringyl type, exhibited a CC stretching band at 1594 cm -1, while guaiacyl DHP exhibited the band at 1599 cm -1. These bands were designated as syringyl and guaiacyl marker bands, respectively. Chemical and physical treatment of hardwood and softwood exhibited different characteristics. One of the reasons is the chemical structure of lignin. Softwood mainly contains only guaiacyl lignin, while hardwood contains both guaiacyl and syringyl lignin, and the syringyl/guaiacyl ( S/G) ratio varies among species. Under high-resolution conditions (1 cm -1), the NIR-FTR spectra of 10 hardwoods (wood meal samples) revealed that both syringyl and guaiacyl marker bands existed. On the other hand, the spectra of softwoods contained only a guaiacyl marker bands existed. On the other hand, the spectra of softwoods contained only a guaiacyl marker band. The S/G ratio in hardwood calculated from the peak area intensity ratio of two marker bands shows a linear relationship with the S/G ratio obtained from conventional nitrobenzene oxidation analysis with the correlation factor>0.96. Furthermore, if peak component separation analysis was combined, low-resolution spectral data gave a similar S/G ratio. Either syringyl of guaiacyl marker bands can be assigned in the NIR-FTR spectra of wood blocks (saw-cut surface). This spectral technique may provide an easy-handling and non-destructive analytical method for lignin

  17. Mixture Design Approach on the Physical Properties of Lignin-Resorcinol-Formaldehyde Xerogels

    Directory of Open Access Journals (Sweden)

    Chris D. Castro

    2015-01-01

    Full Text Available Organic xerogels were functionalized by incorporating sugarcane bagasse lignin from soda pulping black liquor, not used so far in this materials, with the aim of introducing new functional groups on traditional gels that could improve its adsorptive capacity. Two mixing designs were applied to identify the reactive combinations that allow a well gel formation and to adjust models that predict physical properties. The designs study five components: resorcinol (R, 0.04–0.3, lignin (L, 0.004–0.14, formaldehyde (F, 0.08–0.17, water (W, 0.45–0.8, and NaOH (C, 0.0003–0.0035. The first experimental design was an extreme vertices design and its results showed shrinkage between 4.3 and 59.7 and a bulk density from 0.54 to 1.3; a mass ratio LR/F near 1.5 was required for gel formation. In the second design a D-Optimal was used to achieve better adjusted coefficients and incorporate the largest possible amount of lignin in the gels. Bulk density varies from 0.42 to 0.9, shrinkage varies from 3.42 to 25.35, and specific surface area reaches values of 451.86 m2/g with 13% lignin and 270 m2/g with 27% lignin. High catalyst content improves lignin dissolution and increase shrinkage and bulk density of xerogels and bulk density. Lignin contributes to reducing shrinkage and specific surface area due to his compact and rigid structure.

  18. Fate of Carbohydrates and Lignin during Composting and Mycelium Growth of Agaricus bisporus on Wheat Straw Based Compost.

    Directory of Open Access Journals (Sweden)

    Edita Jurak

    Full Text Available In wheat straw based composting, enabling growth of Agaricus bisporus mushrooms, it is unknown to which extent the carbohydrate-lignin matrix changes and how much is metabolized. In this paper we report yields and remaining structures of the major components. During the Phase II of composting 50% of both xylan and cellulose were metabolized by microbial activity, while lignin structures were unaltered. During A. bisporus' mycelium growth (Phase III carbohydrates were only slightly consumed and xylan was found to be partially degraded. At the same time, lignin was metabolized for 45% based on pyrolysis GC/MS. Remaining lignin was found to be modified by an increase in the ratio of syringyl (S to guaiacyl (G units from 0.5 to 0.7 during mycelium growth, while fewer decorations on the phenolic skeleton of both S and G units remained.

  19. Fate of Carbohydrates and Lignin during Composting and Mycelium Growth of Agaricus bisporus on Wheat Straw Based Compost.

    Science.gov (United States)

    Jurak, Edita; Punt, Arjen M; Arts, Wim; Kabel, Mirjam A; Gruppen, Harry

    2015-01-01

    In wheat straw based composting, enabling growth of Agaricus bisporus mushrooms, it is unknown to which extent the carbohydrate-lignin matrix changes and how much is metabolized. In this paper we report yields and remaining structures of the major components. During the Phase II of composting 50% of both xylan and cellulose were metabolized by microbial activity, while lignin structures were unaltered. During A. bisporus' mycelium growth (Phase III) carbohydrates were only slightly consumed and xylan was found to be partially degraded. At the same time, lignin was metabolized for 45% based on pyrolysis GC/MS. Remaining lignin was found to be modified by an increase in the ratio of syringyl (S) to guaiacyl (G) units from 0.5 to 0.7 during mycelium growth, while fewer decorations on the phenolic skeleton of both S and G units remained.

  20. Characterization of lignin-degrading enzymes (LDEs) from a dimorphic novel fungus and identification of products of enzymatic breakdown of lignin.

    Science.gov (United States)

    Sahadevan, Lipin Dev Mundur; Misra, Chandra Shekhar; Thankamani, V

    2016-06-01

    Lignin is a major component of all plants, the degradation of which remains a major challenge to date owing to its recalcitrant nature. Several classes of fungi have been studied to carry out this process to some extent, but overall the process remains inefficient. We have isolated a novel alkalophilic dimorphic lignin-degrading Deuteromycete from soil, identified as "uncultured" and coded as MVI.2011. Supernatant from 12-h culture of MVI.2011 in optimized mineral medium containing lignin pH 9.0 was analysed for Lignin Peroxidase, Manganese Peroxidase and Laccase. Enzyme purification was carried out by standard protocols using ammonium sulphate precipitation followed by further purification by Gel Permeation Chromatography. Analysis of total protein, specific enzyme activity and molecular weight of the GPC-purified LiP, MnP and Laccase showed 93.83 μg/ml, 5.27 U/mg, 42 kDa; 78.13 μg/ml, 13.18 U/mg, 45 kDa and 85.81 μg/ml, 4.77 U/mg, 62 kDa, respectively. The purified enzymes possessed high activity over a wide range of pH (4-11), and temperature (30-55 °C). The optimum substrate concentration was 20 μg/ml of lignin for all the three enzymes. CD spectra suggested that the predominant secondary structure was helix in LiP, and, turns in MnP and Laccase. The breakdown products of lignin degradation by MVI.2011 and the three purified enzymes were detected and identified by FTIR and GC-MS. They were oxalic acid, hentriacontane, derivatives of octadecane, nonane, etc. These vital compounds are certain to find application as biofuels, an alternate energy source in various industries.

  1. PYROLYSIS KINETICS OF WASHED PRECIPITATED LIGNIN

    Directory of Open Access Journals (Sweden)

    Christina Gustafsson

    2009-02-01

    Full Text Available This article describes the pyrolysis behavior of precipitated washed lignin in a Laminar Entrained Flow Reactor between 700 and 1000°C and at different residence times. Lignin was precipitated by acidification of softwood black liquor using CO2. After acid washing, the solid material was dried and sieved (80-100 μm. This material was then fed into the reactor at a rate of about 0.1 g/min. The formed gases were analyzed with respect to CO, CO2, and CH4, and char was collected and weighed. A traditional first order Arrhenius kinetic expression, based on the temperature of the particles with respect to residence time, was adapted to the experimental results. The activation energy was found to be 32.1 kJ/mol. The low ash content in the washed lignin gave a very low solid material residue after the reactor.

  2. Mechanochemical Lignin-Mediated Strecker Reaction

    Directory of Open Access Journals (Sweden)

    Saumya Dabral

    2017-01-01

    Full Text Available A mechanochemical Strecker reaction involving a wide range of aldehydes (aromatic, heteroaromatic and aliphatic, amines, and KCN afforded a library of α-aminonitriles upon mechanical activation. This multicomponent process was efficiently activated by lignocellulosic biomass as additives. Particularly, commercially available Kraft lignin was found to be the best activator for the addition of cyanide to the in situ formed imines. A comparative study of the 31P-NMR (Nuclear Magnetic Resonance along with IR (Infrared data analysis for the Kraft lignin and methylated Kraft lignin samples ascertained the importance of the free hydroxyl groups in the activation of the mechanochemical reaction. The solvent-free mechanochemical Strecker reaction was then coupled with a lactamization process leading to the formation of the N-benzylphthalimide (5a and the isoindolinone derivative 6a.

  3. The chemistry of subcritical water reactions of a hardwood derived lignin and lignin model compounds with nitrogen, hydrogen, carbon monoxide and carbon dioxide

    Science.gov (United States)

    Hill Bembenic, Meredith A.

    Biofuels, like cellulosic ethanol, may only be cost effective if the lignin byproduct is upgraded to value-added products. However, lignin's inherent aromatic structure and interunit crosslinkages hinder effective conversion. High temperature H2O is considered for lignin conversion, because H2O exhibits unusual properties at higher temperatures (particularly at its supercritical point of 374°C and 3205 psi) including a decreased ion product and a decreased static dielectric constant (similar to those of polar organic solvents at room temperature) such that there is a high solubility for organic compounds, like lignin. Much of the research concerning lignin and supercritical H2O has focused on further decomposition to gases (e.g., H2, CH4, and CO2) where nearly no char formation is expected in the presence of a catalyst. However, the conditions required for supercritical H2O are difficult to maintain, catalysts can be expensive, and gases are not favorable to the current liquid fuel infrastructure. Reactions using Organosolv lignin, subcritical H2O (365°C) and various industrial gases (N2, H2, CO, and CO2 at an initial pressure of 500 psi) for 30 min. were examined to determine both lignin's potential to generate value-added products (e.g., monomer compounds and methanol) and the role (if any) of the H2O and the gases during the reactions. The behavior of H2O at reaction temperature and pressure is expected to be similar to the behavior of supercritical H 2O without the need to maintain supercritical conditions. Different characterization techniques were used for the products collected including primarily GC/FID-TCD of the evolved gases, GC/MS analysis of the organic liquids, solid phase microextraction analysis of the water, and solid state 13C-NMR analysis of the residues. The reactor pressure at temperature was shown to influence the reactivity of the H2O and lignin, and the highest conversions (≈54--62%) were obtained when adding a gas. However, the

  4. Lignin as a renewable aromatic resource for the chemical industry

    OpenAIRE

    Gosselink, R.J.A.

    2011-01-01

    Valorization of lignin plays a key role in the further development of lignocellulosic biorefinery processes for biofuels and biobased materials production. Today’s increased demand for alternatives to fossil carbon-based products expands the interest and the need to create added value to the unconverted lignin fraction. The aim of the research was to study the potential of lignin to become a renewable aromatic resource for the chemical industry. Lignin can be considered as an abundantly...

  5. Lignin removal and benzene-alcohol extraction effects on lignin measurements of the hydrothermal pretreated bamboo substrate.

    Science.gov (United States)

    Ma, X J; Cao, S L; Yang, X F; Lin, L; Chen, L H; Huang, L L

    2014-01-01

    Lignin content of hydrothermal pretreated bamboo chips was determined by the two methods: TAPPI standard method (222om-06) and TAPPI standard method without benzene-alcohol extraction (BAE). The results showed that including BAE resulted in lower Klason lignin (KL) and acid soluble lignin (ASL) measurements in the prehydrolyzed substrate, that is to say, BAE removed parts of KL and ASL. Therefore, the TAPPI standard method should be modified by omitting the BAE for lignin measurements of pretreated substrate. The following lignin removal analysis suggested that lignin was removed from the bamboo substrate during pretreatment by a combination of degradation reaction and deconstruction; thereafter the pseudo lignin generated in the hydrothermal pretreatment and condensation reaction between the lignin fragments accounted for the later KL increase. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Pyrolysis of wheat straw-derived organosolv lignin

    NARCIS (Netherlands)

    Wild, P.J. de; Huijgen, W.J.J.; Heeres, H.J.

    2012-01-01

    The cost-effectiveness of a lignocellulose biorefinery may be improved by developing applications for lignin with a higher value than application as fuel. We have developed a pyrolysis based lignin biorefinery approach, called LIBRA, to transform lignin into phenolic bio-oil and biochar using bubbli

  7. Flocculation of high purity wheat straw soda lignin

    Science.gov (United States)

    Flocculant action on lignocellulose mixtures has been studied, but flocculant action on purified sulfur-free lignin has not been reported. In the last step of the industrial process, the purified lignin solution is acidified with sulfuric acid which causes the lignin to become insoluble. The feasi...

  8. Diesel-soluble lignin oils and methods of their production

    DEFF Research Database (Denmark)

    2016-01-01

    Solvent consumption in supercritical ethanol, propanol or butanol treatment of either refined pre-extracted lignin or comparatively impure lignin-rich solid residual from hydrothermally pretreated lignocellulosic biomass can be minimized by conducting the reaction at very high loading of lignin...

  9. Analytical methods for lignin characterization - Differential scanning calorimetry

    NARCIS (Netherlands)

    Koullas, D.P.; Koukios, E.G.; Avgerinos, E.; Abaecherli, A.; Gosselink, R.; Vasile, C.; Lehnen, R.; Saake, B.; Suren, J.

    2006-01-01

    Results of a round robin on lignin thermal analyses are reported. Six laboratories have conducted thermal analyses of four lignin types to determine their cp values and softening points, and to study the thermal behaviour, materials endo- and exotherms included. The lignin types examined were wood

  10. Genetic engineering of syringyl-enriched lignin in plants

    Science.gov (United States)

    Chiang, Vincent Lee; Li, Laigeng

    2004-11-02

    The present invention relates to a novel DNA sequence, which encodes a previously unidentified lignin biosynthetic pathway enzyme, sinapyl alcohol dehydrogenase (SAD) that regulates the biosynthesis of syringyl lignin in plants. Also provided are methods for incorporating this novel SAD gene sequence or substantially similar sequences into a plant genome for genetic engineering of syringyl-enriched lignin in plants.

  11. Lignin Hydrolysis and Phosphorylation Mechanism during Phosphoric Acid–Acetone Pretreatment: A DFT Study

    Directory of Open Access Journals (Sweden)

    Wu Qin

    2014-12-01

    Full Text Available The study focused on the structural sensitivity of lignin during the phosphoric acid–acetone pretreatment process and the resulting hydrolysis and phosphorylation reaction mechanisms using density functional theory calculations. The chemical stabilities of the seven most common linkages (β-O-4, β-β, 4-O-5, β-1, 5-5, α-O-4, and β-5 of lignin in H3PO4, CH3COCH3, and H2O solutions were detected, which shows that α-O-4 linkage and β-O-4 linkage tend to break during the phosphoric acid–acetone pretreatment process. Then α-O-4 phosphorylation and β-O-4 phosphorylation follow a two-step reaction mechanism in the acid treatment step, respectively. However, since phosphorylation of α-O-4 is more energetically accessible than phosphorylation of β-O-4 in phosphoric acid, the phosphorylation of α-O-4 could be controllably realized under certain operational conditions, which could tune the electron and hole transfer on the right side of β-O-4 in the H2PO4− functionalized lignin. The results provide a fundamental understanding for process-controlled modification of lignin and the potential novel applications in lignin-based imprinted polymers, sensors, and molecular devices.

  12. ''The control of lignin synthesis''

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, John E.

    2005-04-07

    In this project we tested the hypothesis that regulation of the synthesis of lignin in secondary xylem cells in conifer trees involves the transport of glucosylated lignin monomers to the wall of xylem cells, followed by de-glucosylation in the cell wall by monolignol-specific glucosidase enzymes, which activates the monomers for lignin polymerization. The information we gathered is relevant to the fundamental understanding of how trees make wood, and to the applied goal of more environmentally friendly pulp and paper production. We characterized the complete genomic structure of the Coniferin-specific Beta-glucosidase (CBG) gene family in the conifers loblolly pine (Pinus taeda) and lodgepole pine (Pinus contorta), and partial genomic sequences were obtained in several other tree species. Both pine species contain multiple CBG genes which raises the possibility of differential regulation, perhaps related to the multiple roles of lignin in development and defense. Subsequent projects will need to include detailed gene expression studies of each gene family member during tree growth and development, and testing the role of each monolignol-specific glucosidase gene in controlling lignin content.

  13. Lignin hydrolysis and phosphorylation mechanism during phosphoric acid-acetone pretreatment: a DFT study.

    Science.gov (United States)

    Qin, Wu; Wu, Lingnan; Zheng, Zongming; Dong, Changqing; Yang, Yongping

    2014-12-18

    The study focused on the structural sensitivity of lignin during the phosphoric acid-acetone pretreatment process and the resulting hydrolysis and phosphorylation reaction mechanisms using density functional theory calculations. The chemical stabilities of the seven most common linkages (β-O-4, β-β, 4-O-5, β-1, 5-5, α-O-4, and β-5) of lignin in H3PO4, CH3COCH3, and H2O solutions were detected, which shows that α-O-4 linkage and β-O-4 linkage tend to break during the phosphoric acid-acetone pretreatment process. Then α-O-4 phosphorylation and β-O-4 phosphorylation follow a two-step reaction mechanism in the acid treatment step, respectively. However, since phosphorylation of α-O-4 is more energetically accessible than phosphorylation of β-O-4 in phosphoric acid, the phosphorylation of α-O-4 could be controllably realized under certain operational conditions, which could tune the electron and hole transfer on the right side of β-O-4 in the H2PO4- functionalized lignin. The results provide a fundamental understanding for process-controlled modification of lignin and the potential novel applications in lignin-based imprinted polymers, sensors, and molecular devices.

  14. Influence of Alkaline Lignin and Degradation Products of Polyurethane Foam on Structure and Performance of Polyurethane Foam Composite%碱木质素和PUF的降解产物对聚氨酯材料结构和性能的影响

    Institute of Scientific and Technical Information of China (English)

    李长玉; 刘艳东; 王磊; 时金金; 吕晨曦

    2012-01-01

    以碱木质素和聚氨酯泡沫(PUF)的降解产物为添加剂制备复合聚氨酯泡沫材料,并表征了微观结构、表观密度、压缩性能、保温性能等.结果显示,碱木质素可提高与复合基体之间的相容性,原因是其存在强烈的氢键缔合作用.扫描电镜测试显示,碱木质素和PUF的降解产物对材料的微观结构有很大的影响,加入碱木质素有利于提高压缩模量,其压缩模量为146.44 MPa,加入PUF的降解产物会降低压缩模量,其压缩模量为101.59 MPa,而没有加碱木素也没有加PUF降解产物的其压缩模量108.53 MPa.PUF的降解产物的添加降低了样品的保温性能,加入PUF的降解产物的样品的导热系数为PUF降解产物的样品的导热系数为0.0325 W/(m·K)而不加PUF降解产物的样品的导热系数为0.0226 W/(m·K).%In order to study the influence of alkaline lignin and degradation products of polyurethane foam ( DPPUF) on structure and performance of polyurethane foam composites (PUF), the reticulated polyurethane foam composites were prepared by using alkaline lignin and DPPUF as raw materials. The FT-IR results showed that compatibility of alkaline lignin and reticulated polyurethane increased due to the existence of strong hydrogen bonding association. SEM analysis indicated that addition of the alkaline lignin and DPPUF could impact the microstructures of PUF. In addition, compression modulus of PUF and the DPPUF increased with the increase of alkaline lignin and reached 146.44 MPa. However, the compression modulus of PUFs would decrease after the introduction of DPPUF and reached 101. 59 MPa. Without the alkaline lignin and the DPPUF, the compression modulus of PUF was 108. 53MPa. The thermal conductivity of product with the renewable polyurethane foam is 0.0325 W/( m o K) while the thermal conductivity of product without the renewable polyurethane foam is 0.022 6 W/( mo K). This showed that the renewable polyurethane foam decreased the

  15. Research on renewable biomass resource-lignin%可再生生物质资源——木质素的研究

    Institute of Scientific and Technical Information of China (English)

    李忠正

    2012-01-01

    Lignin is an abundant natural aromatic renewable resource on earth. A 180-years long history has been past from the discovery of lignin to the determination of lignin aromatic compounds, and its basic types of functional groups and chemical structure. However, the speed of lignin research is slowed down due to the complexity and variability of lignin structure. The author describes the formation of lignin and their chemistry research system, reviews the development of lignin study, analyzes the characteristics and difficulties of lignin research, and highlights future research direction and hot topics.%木质素是天然芳香族可再生资源,从人类发现木质素到确定它是芳香族化合物,研究其基本官能团种类及化学结构,至今已有180年历史.但由于木质素结构的复杂性和多变性,其研究进展缓慢.笔者阐述了木质素及其化学研究体系的形成,综述了木质素研究的进展,分析了木质素研究的特点和难点,提出了今后木质素研究的方向和热点课题.

  16. Distribution of lignin and its coniferyl alcohol and coniferyl aldehyde groups in Picea abies and Pinus sylvestris as observed by Raman imaging.

    Science.gov (United States)

    Hänninen, Tuomas; Kontturi, Eero; Vuorinen, Tapani

    2011-10-01

    Wood cell wall consists of several structural components, such as cellulose, hemicelluloses and lignin, whose concentrations vary throughout the cell wall. It is a composite where semicrystalline cellulose fibrils, acting as reinforcement, are bound together by amorphous hemicelluloses and lignin matrix. Understanding the distribution of these components and their functions within the cell wall can provide useful information on the biosynthesis of trees. Raman imaging enables us to study chemistry of cell wall without altering the structure by staining the sample or fractionating it. Raman imaging has been used to analyze distributions of lignin and cellulose, as well as the functional groups of lignin in wood. In our study, we observed the distribution of cellulose and lignin, as well as the amount of coniferyl alcohol and aldehyde groups compared to the total amount of lignin in pine (Pinus sylvestris) and spruce (Picea abies) wood samples. No significant differences could be seen in lignin and cellulose distribution between these samples, while clear distinction was observed in the distribution of coniferyl alcohols and coniferyl aldehyde in them. These results could provide valuable insight on how two similar wood species control biosynthesis of lignin differently during the differentiation of cell wall.

  17. Decomposition of lignin from sugar cane bagasse during ozonation process monitored by optical and mass spectrometries.

    Science.gov (United States)

    Souza-Corrêa, J A; Ridenti, M A; Oliveira, C; Araújo, S R; Amorim, J

    2013-03-21

    Mass spectrometry was used to monitor neutral chemical species from sugar cane bagasse that could volatilize during the bagasse ozonation process. Lignin fragments and some radicals liberated by direct ozone reaction with the biomass structure were detected. Ozone density was monitored during the ozonation by optical absorption spectroscopy. The optical results indicated that the ozone interaction with the bagasse material was better for bagasse particle sizes less than or equal to 0.5 mm. Both techniques have shown that the best condition for the ozone diffusion in the bagasse was at 50% of its moisture content. In addition, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were employed to analyze the lignin bond disruptions and morphology changes of the bagasse surface that occurred due to the ozonolysis reactions as well. Appropriate chemical characterization of the lignin content in bagasse before and after its ozonation was also carried out.

  18. Synthesis and Characterization of Porous Hydrogel Based on Lignin and Polyacrylamide

    Directory of Open Access Journals (Sweden)

    Qinghua Feng

    2014-06-01

    Full Text Available A porous lignin-containing hydrogel was developed for dye removal via graft copolymerization of acetic acid lignin (AAL and acrylamide (AAm, in the presence of ethyleneglycol dimethacrylate (EGDMA as a crosslinker and H2O2 as an initiator. AAL was characterized by FT-IR and TGA. After being washed to remove impurities, the hydrogel was characterized by FT-IR, TGA, SEM, and swelling ratio. FT-IR spectra suggested that AAL was present in the hydrogel. The TGA curves revealed that the introduction of AAL had no significant impact on the thermal stability of PAAm. SEM images showed that the honeycomb-like structure of the hydrogel was improved with increasing AAL content. The swelling ratio data showed that the hydrogel with a high AAL/AAm ratio was sensitive to pH. Furthermore, increased lignin content of the hydrogel favors the dye adsorption.

  19. Polymer-grafted lignin surfactants prepared via reversible addition-fragmentation chain-transfer polymerization.

    Science.gov (United States)

    Gupta, Chetali; Washburn, Newell R

    2014-08-12

    Kraft lignin grafted with hydrophilic polymers has been prepared using reversible addition-fragmentation chain-transfer (RAFT) polymerization and investigated for use as a surfactant. In this preliminary study, polyacrylamide and poly(acrylic acid) were grafted from a lignin RAFT macroinitiator at average initiator site densities estimated to be 2 per particle and 17 per particle. The target degrees of polymerization were 50 and 100, but analysis of cleaved polyacrylamide was consistent with a higher average molecular weight, suggesting not all sites were able to participate in the polymerization. All materials were readily soluble in water, and dynamic light scattering data indicate polymer-grafted lignin coexisted in isolated and aggregated forms in aqueous media. The characteristic size was 15-20 nm at low concentrations, and aggregation appeared to be a stronger function of degree of polymerization than graft density. These species were surface active, reducing the surface tension to as low as 60 dyn/cm at 1 mg/mL, and a greater decrease was observed than for polymer-grafted silica nanoparticles, suggesting that the lignin core was also surface active. While these lignin surfactants were soluble in water, they were not soluble in hexanes. Thus, it was unexpected that water-in-oil emulsions formed in all surfactant compositions and solvent ratios tested, with average droplet sizes of 10-20 μm. However, although polymer-grafted lignin has structural features similar to nanoparticles used in Pickering emulsions, its interfacial behavior was qualitatively different. While at air-water interfaces, the hydrophilic grafts promote effective reductions in surface tension, we hypothesize that the low grafting density in these lignin surfactants favors partitioning into the hexanes side of the oil-water interface because collapsed conformations of the polymer grafts improve interfacial coverage and reduce water-hexanes interactions. We propose that polymer-grafted lignin

  20. Effect of biotic lignin decomposition on the fate of radiocesium-contaminated plant litter

    Energy Technology Data Exchange (ETDEWEB)

    Hashida, Shin-nosuke; Yoshihara, Toshihiro [Environmental Science Research Laboratory, Central Research Institute of Electric Power Industry, Abiko 1646, Abiko-shi, Chiba (Japan)

    2014-07-01

    Fungi are the most important components in the fate of radionuclides deposited in forests following the Fukushima nuclear accident. Pruned woody parts and litter contain a considerable amount of radiocesium. Studies that focused on the migration of radiocesium have demonstrated that its ecological half-life is lower in the humus layer than in the deeper soil zone, suggesting a substantial contribution of litter decomposition on the mobilization of radiocesium. Furthermore, white-rot fungi appear to play a key role in the mobilization of radiocesium because they are the primary source of enzymes necessary to degrade the litter organic matter. Cell walls are the primary component of plant litter; they are composed of cellulose, hemi-cellulose, and lignin. Although cellulose is the most abundant organic compound in litter, the strength of the cell wall is limited by rigid hemi-cellulose complexes that protect the surrounding cellulose microfibrils. In the cell wall, lignin fills the spaces between cellulose and hemi-cellulose; thus, the biotic degradation of lignin could be considered a primary step in litter decomposition. The contribution of the amount of lignin on the fate of radiocesium has not been identified, which limits the possibility of predicting the effect of the bacterial community structure that determines the biodegradation activity of lignin on the vertical migration of radiocesium. Here, we directly addressed the role of lignin as controller of the distribution of radiocesium in soil-ecosystems. Radiocesium-contaminated litter samples were collected with traps set under the target stands, i.e., Japanese flowering cherry trees (Prunus x yedoensis cv. Somei-Yoshino) and Japanese cedars (Cryptomeria japonica) at Abiko (Laboratory of Environmental Science, CRIEPI) located approximately 200 km SSW from the Fukushima Daiichi Nuclear Power Plant in 2011. The litter samples were inoculated with white-rot fungi having ligno-celluloses-degrading activity, i

  1. The use of natural abundance stable isotopic ratios to indicate the presence of oxygen-containing chemical linkages between cellulose and lignin in plant cell walls.

    Science.gov (United States)

    Zhou, Youping; Stuart-Williams, Hilary; Farquhar, Graham D; Hocart, Charles H

    2010-06-01

    Qualitative and quantitative understanding of the chemical linkages between the three major biochemical components (cellulose, hemicellulose and lignin) of plant cell walls is crucial to the understanding of cell wall structure. Although there is convincing evidence for chemical bonds between hemicellulose and lignin and the absence of chemical bonds between hemicellulose and cellulose, there is no conclusive evidence for the presence of covalent bonds between cellulose and lignin. This is caused by the lack of selectivity of current GC/MS-, NMR- and IR-based methods for lignin characterisation as none of these techniques directly targets the possible ester and ether linkages between lignin and cellulose. We modified the widely-accepted "standard" three-step extraction method for isolating cellulose from plants by changing the order of the steps for hemicellulose and lignin removal (solubilisation with concentrated NaOH and oxidation with acetic acid-containing NaClO(2), respectively) so that cellulose and lignin could be isolated with the possible chemical bonds between them intact. These linkages were then cleaved with NaClO(2) reagent in aqueous media of contrasting (18)O/(16)O ratios. We produced cellulose with higher purity (a lower level of residual hemicellulose and no detectable lignin) than that produced by the "standard" method. Oxidative artefacts may potentially be introduced at the lignin removal stage; but testing showed this to be minimal. Cellulose samples isolated from processing plant-derived cellulose-lignin mixtures in media of contrasting (18)O/(16)O ratios were compared to provide the first quantitative evidence for the presence of oxygen-containing ester and ether bonds between cellulose and lignin in Zea mays leaves. However, no conclusive evidence for the presence or lack of similar bonds in Araucaria cunninghamii wood was obtained. Copyright 2010 Elsevier Ltd. All rights reserved.

  2. Propensity of lignin to associate: light scattering photometry study with native lignins.

    Science.gov (United States)

    Contreras, Sofía; Gaspar, Armindo R; Guerra, Anderson; Lucia, Lucian A; Argyropoulos, Dimitris S

    2008-12-01

    Many studies of lignins in solution invoke association and aggregation phenomena to explain their solution behavior (e.g., reprecipitation onto pulp fibers, condensation, etc.). Following their colloidal (apparent) molecular weights in solution as a function of time allows us to explore observable dissociation phenomena. These measurements were carried out using multiple angle laser light scattering (MALLS) photometry in the static mode. The challenges and opportunities of measuring the specific refractive index increment (dn/dC) of lignin solutions and determining the kinetics of the dissociation process were thus investigated. Hardwood and softwood representative lignins were isolated, and method for their full dissolution in THF was further developed, which then lead to accurate dn/dC values being obtained as a function of time. When coupled to additional work using light scattering static measurements and Zimm plots for the same solutions, this effort offers insight into the aggregation and ensuing dissociative events that operate within the lignin macromolecules.

  3. Accelerated solvent extraction of lignin from Aleurites moluccana (Candlenut) nutshells.

    Science.gov (United States)

    Klein, Andrew P; Beach, Evan S; Emerson, John W; Zimmerman, Julie B

    2010-09-22

    Lignin from candlenut shells was isolated using an ethanol-water accelerated solvent extraction method. Yields (based on Klason lignin) increased from about 14 to 33% as temperature increased from 100 to 195 °C and were also influenced by the amount of aqueous acid used to precipitate lignin from the extraction liquor. These yields were higher than could be obtained using a conventional dioxane-water acidolysis method. The resulting lignin was characterized by IR, 31P NMR, and 1H-13C HMQC NMR spectroscopic techniques. The lignin contained predominantly guaiacyl units, and both the total hydroxyl group content and phenolic hydroxyl group content were high.

  4. Fractionation of bagasse into cellulose, hemicelluloses, and lignin with ionic liquid treatment followed by alkaline extraction.

    Science.gov (United States)

    Lan, Wu; Liu, Chuan-Fu; Sun, Run-Cang

    2011-08-24

    Lignocellulose materials are potentially valuable resources for transformation into biofuels and bioproducts. However, their complicated structures make it difficult to fractionate them into cellulose, hemicelluloses, and lignin, which limits their utilization and economical conversion into value-added products. This study proposes a novel and feasible fractionation method based on complete dissolution of bagasse in 1-butyl-3-methylimidazolium chloride ([C(4)mim]Cl) followed by precipitation in acetone/water (9:1, v/v) and extraction with 3% NaOH solution. The ionic liquid [C(4)mim]Cl was easily recycled after concentration and treatment with acetonitrile. (1)H NMR analysis confirmed that there was no obvious difference between the recycled [C(4)mim]Cl and fresh material. Bagasse was fractionated with this method to 36.78% cellulose, 26.04% hemicelluloses, and 10.51% lignin, accounting for 47.17 and 33.85% of the original polysaccharides and 54.62% of the original lignin, respectively. The physicochemical properties of the isolated fractions were characterized by chemical analysis, high-performance anion exchange chromatography (HPAEC), gel permeation chromatography (GPC), Fourier transform infrared (FT-IR), and (1)H and 2D (13)C-(1)H correlation (HSQC) nuclear magnetic resonance spectroscopy. The results showed that the acetone-soluble lignin and alkaline lignin fractions had structures similar to those of milled wood lignin (MWL). The easy extraction of the noncellulose components from homogeneous bagasse solution and amorphous regenerated materials resulted in the relatively high purity of cellulosic fraction (>92%). The hemicellulosic fraction was mainly 4-O-methyl-D-glucuronoxylans with some α-L-arabinofuranosyl units substituted at C-2 and C-3.

  5. POTENSI MELANOTUS SP. DALAM MENDEGRADASI LIGNIN

    Directory of Open Access Journals (Sweden)

    NUNIK SULISTINAH

    2008-06-01

    Full Text Available Ten isolates of fungus were isolated from oil palm stem at oil palm plantation in Medan All of them were tested its abilities to degrade lignin. The results showed that one of them was able to grow on ligninase media and the fungi has the ability to degrade ligin. The fungi is identified as Melanotus sp.

  6. Analytical methods for lignin characterization. I. Thermogravimetry

    NARCIS (Netherlands)

    Vasile, C.; Gosselink, R.J.A.; Quintus, P.; Koukios, E.G.; Koullas, D.P.; Avgerinos, E.; Abacherli, D.A.

    2006-01-01

    The paper discusses the results of a round robin experiment initiated by the participants to "EUROLIGNIN", an EC network, meant at standardizing thermogravimetry as an useful method for the thermal characterization of lignins obtained from different sources or by different extraction methods. Five

  7. Nylon biodegradation by lignin-degrading fungi.

    OpenAIRE

    Deguchi, T; Kakezawa, M; Nishida, T

    1997-01-01

    The biodegradation of nylon by lignin-degrading fungi was investigated. The fungus IZU-154 significantly degraded nylon-66 membrane under ligninolytic conditions. Nuclear magnetic resonance analysis showed that four end groups, CHO, NHCHO, CH3, and CONH2, were formed in the biodegraded nylon-66 membranes, suggesting that nylon-66 was degraded oxidatively.

  8. Analytical methods for lignin characterization. I. Thermogravimetry

    NARCIS (Netherlands)

    Vasile, C.; Gosselink, R.J.A.; Quintus, P.; Koukios, E.G.; Koullas, D.P.; Avgerinos, E.; Abacherli, D.A.

    2006-01-01

    The paper discusses the results of a round robin experiment initiated by the participants to "EUROLIGNIN", an EC network, meant at standardizing thermogravimetry as an useful method for the thermal characterization of lignins obtained from different sources or by different extraction methods. Five l

  9. Isolation and Irradiation-Modification of Lignin Specimens from Black Liquor and Evaluation of Their Effects on Wastewater Purification

    Directory of Open Access Journals (Sweden)

    Ke-Qin Wang

    2014-09-01

    Full Text Available In this study, crude lignin extracted from the black liquor generated by a pulp and paper mill was modified by different doses of irradiation. The crude and irradiation-modified lignins were used to treat wastewater that was generated during the production of starch glucoamylase. Changes to the physical and chemical properties and structure of the irradiation-modified lignins were determined using scanning electron microscopy, solubility analysis, elemental analysis, analysis of phenolic hydroxyl group, ultraviolet–visible spectroscopy, and Fourier transform infrared spectroscopy. Irradiation reduced the phenolic hydroxyl content in the lignin but increased its solubility by about 40%; analysis revealed that irradiation also destroyed the skeletal structure of the benzene ring in the lignin. After four minutes of settling, the total nitrogen (TN and chemical oxygen demand (COD in the wastewater reached 7.0 mg/L and 1573.1 mg/L, respectively. The settled solids content and protein recovery were 1.12 g/L and 98%, respectively. This study suggested that irradiation-modified lignin extracted from black liquor generated in the pulp and paper industry can be used to treat wastewater from the production of starch glucoamylase.

  10. Lignin isolation process from rice husk by alkaline hydrogen peroxide: Lignin and silica extracted

    Science.gov (United States)

    Ma'ruf, Anwar; Pramudono, Bambang; Aryanti, Nita

    2017-03-01

    Biomass is one of abundance resources in the world. Biomass consists of three main materials such as cellulose, hemicelluloses and lignin. Therefore, biomass can be referred to lignocellulosic material. Both the cellulose and hemicelluloses fractions are polymers of sugars, and thereby a potential source of fermentable sugars, or other processes that convert sugars into products. Lignin is a polymer compound which contains of phenolic compounds. Rice husk is one of biomass, which has high contain of lignin. Rice husk has special characteristics because of silica content. The aim of this paper is to analyze lignin and silica extracted during lignin isolation process of rice husk using alkaline hydrogen peroxide. Three main variables such as solvent/solid ratio, concentration of hydrogen peroxide and pH of the mixture are studied. The optimum conditions for lignin isolation are at solvent/solid ratio 9:1 ml/gr, hydrogen peroxide concentration of 1.5%v and pH of the mixture of 11.

  11. Molecular products and radicals from pyrolysis of lignin.

    Science.gov (United States)

    Kibet, J; Khachatryan, L; Dellinger, B

    2012-12-04

    Thermal degradation of lignin under two reaction regimes (pyrolysis in N(2) and oxidative pyrolysis in 4% O(2) in N(2)) has been investigated in a tubular, isothermal, flow-reactor over the temperature range 200-900 °C at a residence time of 0.2 s. Two experimental protocols were adopted: (1) Partial pyrolysis in which the same lignin sample was continuously pyrolyzed at each temperature and (2) conventional pyrolysis, in which new lignin samples were pyrolyzed at each pyrolysis temperature. The results identified common relationships between the two modes of experiments, as well as some differences. The majority of products from partial pyrolysis peaked between 300 and 500 °C, whereas for conventional pyrolysis reaction products peaked between 400 and 500 °C. The principal products were syringol (2,6-dimethoxy phenol), guaiacol (2-methoxy phenol), phenol, and catechol. Of the classes of compounds analyzed, the phenolic compounds were the most abundant, contributing over 40% of the total compounds detected. Benzene, styrene, and p-xylene were formed in significant amounts throughout the entire temperature range. Interestingly, six ringed polycyclic aromatic hydrocarbons were formed during partial pyrolysis. Oxidative pyrolysis did not result in large differences from pyrolysis; the main products still were syringol, guaiacol, phenol, the only significant difference being the product distribution peaked between 200 and 400 °C. For the first time, low temperature matrix isolation electron paramagnetic resonance was successfully interfaced with the pyrolysis reactor to elucidate the structures of the labile reaction intermediates. The EPR results suggested the presence of methoxyl, phenoxy, and substituted phenoxy radicals as precursors for formation of major products; syringol, guaiacol, phenols, and substituted phenols.

  12. Characteristics of Wheat Straw Lignins from Ethanol-based Organosolv Treatment

    NARCIS (Netherlands)

    Huijgen, W.J.J.; Telysheva, G.; Arshanitsa, A.; Gosselink, R.J.A.; Wild, de P.J.

    2014-01-01

    Non-purified lignins resulting from ethanol-based organosolv fractionation of wheat straw were characterized for the presence of impurities (carbohydrates and ash), functional groups (hydroxyl, carboxyl and methoxyl), phenyl-propanoid structural moieties, molar mass distribution and thermal behavior

  13. Efficient Cleavage of Lignin-Carbohydrate Complexes and Ultrafast Extraction of Lignin Oligomers from Wood Biomass by Microwave-Assisted Treatment with Deep Eutectic Solvent.

    Science.gov (United States)

    Liu, Yongzhuang; Chen, Wenshuai; Xia, Qinqin; Guo, Bingtuo; Wang, Qingwen; Liu, Shouxin; Liu, Yixing; Li, Jian; Yu, Haipeng

    2017-04-22

    Lignocellulosic biomass is an abundant and renewable resource for the production of biobased value-added fuels, chemicals, and materials, but its effective exploitation by an energy-efficient and environmentally friendly strategy remains a challenge. Herein, a facile approach for efficiently cleaving lignin-carbohydrate complexes and ultrafast fractionation of components from wood by microwave-assisted treatment with deep eutectic solvent is reported. The solvent was composed of sustainable choline chloride and oxalic acid dihydrate, and showed a hydrogen-bond acidity of 1.31. Efficient fractionation of lignocellulose with the solvent was realized by heating at 80 °C under 800 W microwave irradiation for 3 min. The extracted lignin showed a low molecular weight of 913, a low polydispersity of 1.25, and consisted of lignin oligomers with high purity (ca. 96 %), and thus shows potential in downstream production of aromatic chemicals. The other dissolved matter mainly comprised glucose, xylose, and hydroxymethylfurfural. The undissolved material was cellulose with crystal I structure and a crystallinity of approximately 75 %, which can be used for fabricating nanocellulose. Therefore, this work promotes an ultrafast lignin-first biorefinery approach while simultaneously keeping the undissolved cellulose available for further utilization. This work is expected to contribute to improving the economics of overall biorefining of lignocellulosic biomass. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  14. The Degradation and Condensation of Lignin Structure During Kraft Cooking of MWL from Jacaranda Copaid%蓝花楹磨木木素在硫酸盐法蒸煮过程中的反应

    Institute of Scientific and Technical Information of China (English)

    邵震宇; 谢益民; 周燕; 杨志勇

    2008-01-01

    在木糖存在的条件下,采用硫酸盐法蒸煮的方法对蓝花楹磨木木素(milled wood lignin,简称MWL)进行处理,然后对处理后的产物进行红外光谱和13C-NMR分析,研究蓝花楹MWL的结构变化,探讨在硫酸盐法蒸煮过程中木素-碳水化合物复合体(lignin-carbohydrate complexes,简称LCC)的形成情况.研究发现:蓝花楹MWL结构单元之间的α-烷基芳基醚键、β-O-4型连接键很容易发生断裂,而在这些连接键发生断裂的同时,形成的木素中间体与糖产生化学键的结合,蒸煮液中有新的LCC结构形成.

  15. STUDY ON LIGNIN COVERAGE OF MASSON PINE FIBER

    Directory of Open Access Journals (Sweden)

    Beihai He

    2010-06-01

    Full Text Available In order to obtain the adhesion force of fiber in a paper sheet easily, the relationships between internal bonding strength (IBS and surface lignin content of masson pine CTMP treated with peracetic acid (PAA have been investigated with XPS technique, and the surface morphology of fibers was also imaged by AFM. The results showed that the extent of lignin covered on the fiber surface was two times as high as that of whole pulp lignin, and the IBS was inversely proportional to surface lignin. The relationship between IBS and lignin coverage was formulated based on the experimental data. The mutual adhesion forces, cellulose-to-cellulose and lignin-to-lignin, were calculated using these equations, and the results were 28.69 mN/m and 2.487mN/m, respectively.

  16. Reactions of Lignin Model Compounds in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Holladay, John E.; Binder, Joseph B.; Gray, Michel J.; White, James F.; Zhang, Z. Conrad

    2009-09-15

    Lignin, a readily available form of biomass, awaits novel chemistry for converting it to valuable aromatic chemicals. Recent work has demonstrated that ionic liquids are excellent solvents for processing woody biomass and lignin. Seeking to exploit ionic liquids as media for depolymerization of lignin, we investigated reactions of lignin model compounds in these solvents. Using Brønsted acid catalysts in 1-ethyl-3-methylimidazolium triflate at moderate temperatures, we obtained up to 11.6% yield of the dealkylation product guaiacol from the model compound eugenol and cleaved phenethyl phenyl ether, a model for lignin ethers. Despite these successes, acid catalysis failed in dealkylation of the unsaturated model compound 4-ethylguaiacol and did not produce monomeric products from organosolv lignin, demonstrating that further work is required to understand the complex chemistry of lignin depolymerization.

  17. Comparative study of lignin characteristics from wheat straw obtained by soda-AQ and kraft pretreatment and effect on the following enzymatic hydrolysis process.

    Science.gov (United States)

    Yang, Haitao; Xie, Yimin; Zheng, Xing; Pu, Yunqiao; Huang, Fang; Meng, Xianzhi; Wu, Weibing; Ragauskas, Arthur; Yao, Lan

    2016-05-01

    To understand the structural changes of lignin after soda-AQ and kraft pretreatment, milled straw lignin, black liquor lignin and residual lignin extracted from wheat straw were characterized by FT-IR, UV, GPC and NMR. The results showed that the main lignin linkages were β-aryl ether substructures (β-O-4'), followed by phenylcoumaran (β-5') and resinol (β-β') substructures, while minor content of spirodienone (β-1'), dibenzodioxocin (5-5') and α,β-diaryl ether linkages were detected as well. After pretreatment, most lignin inter-units and lignin-carbohydrate complex (LCC) linkages were degraded and dissolved in black liquor, with minor amount left in residual pretreated biomass. In addition, through quantitative (13)C and 2D-HSQC NMR spectral analysis, lignin and LCC were found to be more degraded after kraft pretreatment than soda-AQ pretreatment. Furthermore, the subsequent enzymatic hydrolysis results showed that more cellulose in wheat straw was converted to glucose after kraft pretreatment, indicating that LCC linkages were important in the enzymatic hydrolysis process.

  18. Lignin depolymerization by fungal secretomes and a microbial sink

    Energy Technology Data Exchange (ETDEWEB)

    Salvachúa, Davinia; Katahira, Rui; Cleveland, Nicholas S.; Khanna, Payal; Resch, Michael G.; Black, Brenna A.; Purvine, Samuel O.; Zink, Erika M.; Prieto, Alicia; Martínez, María J.; Martínez, Angel T.; Simmons, Blake A.; Gladden, John M.; Beckham, Gregg T.

    2016-08-25

    In Nature, powerful oxidative enzymes secreted by white rot fungi and some bacteria catalyze lignin depolymerization and some microbes are able to catabolize the resulting aromatic compounds as carbon and energy sources. Taken together, these two processes offer a potential route for microbial valorization of lignin. However, many challenges remain in realizing this concept, including that oxidative enzymes responsible for lignin depolymerization also catalyze polymerization of low molecular weight (LMW) lignin. Here, multiple basidiomycete secretomes were screened for ligninolytic enzyme activities in the presence of a residual lignin solid stream from a corn stover biorefinery, dubbed DMR-EH (Deacetylation, Mechanical Refining, and Enzymatic Hydrolysis) lignin. Two selected fungal secretomes, with high levels of laccases and peroxidases, were utilized for DMR-EH lignin depolymerization assays. The secretome from Pleurotus eryngii, which exhibited the highest laccase activity, reduced the lignin average molecular weight by 63% and 75% at pH 7 compared to the Mw of the control treated at the same conditions and the initial DMR-EH lignin, respectively, and was applied in further depolymerization assays as a function of time. As repolymerization was observed after 3 days of incubation, an aromatic-catabolic microbe (Pseudomonas putida KT2440) was incubated with the fungal secretome and DMR-EH lignin. These experiments demonstrated that the presence of the bacterium enhances lignin depolymerization, likely due to bacterial catabolism of LMW lignin, which may partially prevent repolymerization. In addition, proteomics was also applied to the P. eryngii secretome to identify the enzymes present in the fungal cocktail utilized for the depolymerization assays, which highlighted a significant number of glucose/ methanol/choline (GMC) oxidoreductases and laccases. Overall, this study demonstrates that ligninolytic enzymes can be used to partially depolymerize a solid, high

  19. Lignin Depolymerization by Fungal Secretomes and a Microbial Sink

    Energy Technology Data Exchange (ETDEWEB)

    Salvachua, Davinia; Katahira, Rui; Cleveland, Nicholas S.; Khanna, Payal; Resch, Michael G.; Black, Brenna A.; Purvine, Samuel O.; Zink, Erika M.; Prieto, Alicia; Martinez, Maria J.; Martinez, Angel T.; Simmons, Blake A.; Gladden, John M.; Beckham, Gregg T.

    2016-11-21

    In Nature, powerful oxidative enzymes secreted by white rot fungi and some bacteria catalyze lignin depolymerization and some microbes are able to catabolize the resulting aromatic compounds as carbon and energy sources. Taken together, these two processes offer a potential route for microbial valorization of lignin. However, many challenges remain in realizing this concept, including that oxidative enzymes responsible for lignin depolymerization also catalyze polymerization of low molecular weight (LMW) lignin. Here, multiple basidiomycete secretomes were screened for ligninolytic enzyme activities in the presence of a residual lignin solid stream from a corn stover biorefinery, dubbed DMR-EH (Deacetylation, Mechanical Refining, and Enzymatic Hydrolysis) lignin. Two selected fungal secretomes, with high levels of laccases and peroxidases, were utilized for DMR-EH lignin depolymerization assays. The secretome from Pleurotus eryngii, which exhibited the highest laccase activity, reduced the lignin average molecular weight (Mw) by 63% and 75% at pH 7 compared to the Mw of the control treated at the same conditions and the initial DMR-EH lignin, respectively, and was applied in further depolymerization assays as a function of time. As repolymerization was observed after 3 days of incubation, an aromatic-catabolic microbe (Pseudomonas putida KT2440) was incubated with the fungal secretome and DMR-EH lignin. These experiments demonstrated that the presence of the bacterium enhances lignin depolymerization, likely due to bacterial catabolism of LMW lignin, which may partially prevent repolymerization. In addition, proteomics was also applied to the P. eryngii secretome to identify the enzymes present in the fungal cocktail utilized for the depolymerization assays, which highlighted a significant number of glucose/methanol/choline (GMC) oxidoreductases and laccases. Overall, this study demonstrates that ligninolytic enzymes can be used to partially depolymerize a solid

  20. Characterization of lignin and Mn peroxidases from Phanerochaete chrysosporium. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    1991-12-31

    Long-term objectives are to elucidate the role and mechanism of the various isozymes in lignin biodegradation. Work is described on electrochemical studies on lignin and Mn peroxidases. This study was performed to investigate the structural aspects which confer the lignin and Mn peroxidases with their high reactivity. The experimentally determined redox potential of the Fe{sup 3+}/Fe{sup 2+} couple for the lignin peroxidase isozymes H1, H2, H8 and H10 are very similar, near-130 mV. The redox potential for the Mn peroxidase isozymes H3 and H4 are similar to each other ({minus}88 mV and {minus}95 mV, respectively) and are more positive than the lignin peroxidases. The higher redox potential for the Fe{sup 3+}/Fe{sup 2+} couple is consistent with the heme active site of these fungal peroxidases being more electron deficient. To investigate the accessibility of the heme active site to the substrate which is oxidized [veratryl alcohol and Mn (II)], we investigated whether these substrates had any affect on the redox potential of the heme. The E{sub m7} value for lignin and Mn peroxidases are not affected by their respective substrates, veratryl alcohol and Mn (II). These results suggest that substrates do not directly interact with the ferric heme-iron as axial ligands. This is consistent with the present model for peroxidase catalysis. Suicide inhibitor (1) and nmr studies (2) indicate that the heme-iron of horseradish peroxidase (HRP) is not fully accessible to bulky substrates occur at the periphery of the heme.

  1. Top Value-Added Chemicals from Biomass - Volume II—Results of Screening for Potential Candidates from Biorefinery Lignin

    Energy Technology Data Exchange (ETDEWEB)

    Holladay, John E.; White, James F.; Bozell, Joseph J.; Johnson, David

    2007-10-01

    This report evaluates lignin’s role as a renewable raw material resource. Opportunities that arise from utilizing lignin fit into one of three categories: 1)power, fuel and syngas (generally near-term opportunities) 2) macromolecules (generally medium-term opportunities) 3) aromatics and miscellaneous monomers (long-term opportunities). Biorefineries will receive and process massive amounts of lignin. For this reason, how lignin can be best used to support the economic health of the biorefinery must be defined. An approach that only considers process heat would be shortsighted. Higher value products present economic opportunities and the potential to significantly increase the amount of liquid transportation fuel available from biomass. In this analysis a list of potential uses of lignin was compiled and sorted into “product types” which are broad classifications (listed above as power—fuel—syngas; macromolecules; and aromatics). In the first “product type” (power—fuel—gasification) lignin is used purely as a carbon source and aggressive means are employed to break down its polymeric structure. In the second “product type” (macromolecules) the opposite extreme is considered and advantage of the macromolecular structure imparted by nature is retained in high-molecular weight applications. The third “product type” (aromatics) lies somewhere between the two extremes and employs technologies that would break up lignin’s macromolecular structure but maintain the aromatic nature of the building block molecules. The individual opportunities were evaluated based on their technical difficulty, market, market risk, building block utility, and whether a pure material or a mixture would be produced. Unlike the “Sugars Top 10” report it was difficult to identify the ten best opportunities, however, the potential opportunities fell nicely into near-, medium- and long-term opportunities. Furthermore, the near-, medium- and long-term opportunities

  2. Deconstruction of lignin linked p-coumarates, ferulates and xylan by NaOH enhances the enzymatic conversion of glucan.

    Science.gov (United States)

    Murciano Martínez, Patricia; Punt, Arjen M; Kabel, Mirjam A; Gruppen, Harry

    2016-09-01

    Thermo-assisted NaOH pretreatment to deconstruct xylan and lignin in sugar cane bagasse (SCB) is poorly understood. Hence, in this research it is was aimed to study the effect of NaOH pretreatment on the insoluble remaining lignin structures. Hereto, SCB milled fibres were pretreated using different dosages of NaOH at different temperatures and residence times. Of untreated SCB about 63% of the lignin compounds were assigned as p-coumarates and ferulates, analysed by pyrolysis-GC/MS as 4-vinyl phenol and 4-vinyl guaiacol, and designated as non-core lignin (NCL) compounds. More severe NaOH pretreatments resulted in lower xylan and lower lignin recoveries in the insoluble residues. Especially, the relative abundance of NCL decreased and this decrease followed a linear trend with the decrease in xylan. Core lignin compounds, analysed as phenol, guaiacol and syringol, accumulated in the residues. The decrease in residual xylan and NCL correlated positively with the enzymatic hydrolysis of the residual glucan.

  3. Preparation and characterization of Kraft lignin-based moisture-responsive films with reversible shape-change capability.

    Science.gov (United States)

    Dallmeyer, Ian; Chowdhury, Sudip; Kadla, John F

    2013-07-08

    Preparation of moisture-responsive Kraft lignin-based materials by electrospinning blends of Kraft lignin fractions with different physical properties is presented. The differences in thermal mobility between lignin fractions are shown to influence the degree of interfiber fusion occurring during oxidative thermostabilization of electrospun nonwoven fabrics, resulting in different material morphologies including submicrometer fibers, bonded nonwovens, porous films, and smooth films. The relative amount of different lignin fractions and degree of fiber flow and fiber fusion is shown to influence the tendency for the electrospun materials to be transformed into moisture-responsive materials capable of reversible changes in shape. Material characterization by scanning electron microscopy and atomic force microscopy as well characterization of the chemical and physical properties of Kraft lignin fractions by dynamic rheology, 1H and 13C NMR, and gel permeation chromatography combined with multiangle laser light scattering are presented. A proposed mechanism underlying moisture-responsiveness, shape change, and shape recovery is discussed based on the differences in chemical structure and physical properties of Kraft lignin fractions.

  4. Uv Photofragmentation Spectroscopy of Model Lignin-Alkali Ion Complexes: Extending Lignomics Into the Spectroscopic Regime

    Science.gov (United States)

    Dean, Jacob C.; Burke, Nicole L.; Hopkins, John R.; Redwine, James; Biswas, Bidyut; Ramachandran, P. V.; McLuckey, Scott A.; Zwier, Timothy S.

    2014-06-01

    Lignin is a heteroaromatic biopolymer that is an essential component in the cell wall of plants. The structural and chemical properties of lignin provide plants with macroscopic structural rigidity, and protection against microbial invasion leading to subsequent cell wall degradation. For this reason, lignin presents a major inhibition to the efficient harvesting of biomass. Given the variability of lignin composition and structure among species, environment, etc., the field of "lignomics" seeks to "sequence" lignin oligomers into constituent unit types (H, G, S) and linkages. This is predominantly done by means of tandem mass-spectrometry, by first generating a library of characteristic fragmentation pathways built from collision-induced dissociation of model dilignol ions, and applying them to the interpretation of fragmentation in larger ions. While these methods have proven powerful, UV photofragmentation spectroscopy of lignin ions cooled in a 22-pole cold ion trap provides an alternative approach to lignomics based on fragmentation following resonant UV excitation. This approach serves as a complimentary method to pure MSn-based methods with the potential for unveiling dissociation pathways only accessed by UV excitation. Further, the multichromophoric nature of lignin enables site-selectivity for the energy imparted into the molecule/ion when differentiation of the site absorptions may be possible. IR spectroscopy of the cold ions can be used for detailed analysis of the preferred conformations and binding sites of metal cations. UV spectroscopy and photofragmentation mass spectrometry has been carried out on the model (G-type) β-O-4 and β-β dilignol linkages complexed with Li+ and Na+. The UV spectral signatures were found to vary between dilignols and metal complexes, and unique photofragmentation pathways were observed among the four complexes. IR spectroscopy in the OH stretch region was used as a probe of the conformation and binding preferences. In

  5. Oxidative depolymerization of lignin in ionic liquids.

    Science.gov (United States)

    Stärk, Kerstin; Taccardi, Nicola; Bösmann, Andreas; Wasserscheid, Peter

    2010-06-21

    Beech lignin was oxidatively cleaved in ionic liquids to give phenols, unsaturated propylaromatics, and aromatic aldehydes. A multiparallel batch reactor system was used to screen different ionic liquids and metal catalysts. Mn(NO(3))(2) in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [EMIM][CF(3)SO(3)] proved to be the most effective reaction system. A larger scale batch reaction with this system in a 300 mL autoclave (11 g lignin starting material) resulted in a maximum conversion of 66.3 % (24 h at 100 degrees C, 84x10(5) Pa air). By adjusting the reaction conditions and catalyst loading, the selectivity of the process could be shifted from syringaldehyde as the predominant product to 2,6-dimethoxy-1,4-benzoquinone (DMBQ). Surprisingly, the latter could be isolated as a pure substance in 11.5 wt % overall yield by a simple extraction/crystallization process.

  6. Incorporation of hydroxy-cinnamaldehydes into lignins

    Science.gov (United States)

    John. Ralph; Hoon. Kim; Fachuang. Lu; Sally A. Ralph; Larry L. Landucci; Takashi. Ito; Shingo. Kawai

    1999-01-01

    Peroxidase/H2O2-mediated radical coupling of hydroxycinnamaldehydes produced 81O14-, 8-5-, 818-, and 5-5dimers as had been documented earlier (although we found that the 815-dimer is produced in its cyclic phenylcoumaran form at neutral pH). Spectral data from dimers and oligomers has allowed a more substantive assignment of aldehyde components in lignins isolated from...

  7. PREPARATION AND PROPERTIES OF CHITOSAN/LIGNIN COMPOSITE FILMS

    Institute of Scientific and Technical Information of China (English)

    Long Chen; Chang-yu Tang; Nan-ying Ning; Chao-yu Wang; Qiang Fu; Qin Zhang

    2009-01-01

    Biodegradable composite films based on chitosan and lignin with various composition were prepared via the solution-casting technique.FT-IR results indicate the existence of hydrogen bonding between chitosan and lignin,and SEM images show that lignin could be well dispersed in chitosan when the content of lignin is below 20 wt% due to the strong interfacial interaction.As a result of strong interaction and good dispersion,the tensile strength,storage modulus,thermal degradation temperature and glass transition temperature of chitosan have been largely improved by adding lignin.Our work provides a simple and cheap way to prepare fully biodegradable chitosan/lignin composites,which could be used as packaging films or wound dressings.

  8. Comparison of lignin extraction processes: Economic and environmental assessment.

    Science.gov (United States)

    Carvajal, Juan C; Gómez, Álvaro; Cardona, Carlos A

    2016-08-01

    This paper presents the technical-economic and environmental assessment of four lignin extraction processes from two different raw materials (sugarcane bagasse and rice husks). The processes are divided into two categories, the first processes evaluates lignin extraction with prior acid hydrolysis step, while in the second case the extraction processes are evaluated standalone for a total analysis of 16 scenarios. Profitability indicators as the net present value (NPV) and environmental indicators as the potential environmental impact (PEI) are used through a process engineering approach to understand and select the best lignin extraction process. The results show that both economically and environmentally process with sulfites and soda from rice husk presents the best results; however the quality of lignin obtained with sulfites is not suitable for high value-added products. Then, the soda is an interesting option for the extraction of lignin if high quality lignin is required for high value-added products at low costs.

  9. Lignin profiling in extracted xylans by size-exclusion chromatography.

    Science.gov (United States)

    Hutterer, Christian; Schild, Gabriele; Kliba, Gerhard; Potthast, Antje

    2016-10-20

    Utilization of the polymeric parts of lignocellulose is expected to gain increasing importance in future biorefinery scenarios. In that respect, a particular focus is placed on hemicelluloses from different wood species gained from an industrially feasible upgrading step in the production of dissolving pulps from paper pulps. During alkaline post-extractions for hemicellulose removal, residual lignins are extracted as well. They are either covalently linked to the extracted hardwood xylans or simply co-dissolved in the alkaline lye. In order to better describe the lignin in xylan containing lyes, a method for lignin profiling was set up by hyphenating size-exclusion chromatography of xylans with UV detection which facilitates visualization of the residual lignin distribution. Simultaneous lignin quantification was achieved with lignin standards prepared from Kraft cooking liquors. The setup presented may serve as advanced characterization for novel xylan products. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Biobased Epoxy Resins from Deconstructed Native Softwood Lignin.

    Science.gov (United States)

    van de Pas, Daniel J; Torr, Kirk M

    2017-08-14

    The synthesis of novel epoxy resins from lignin hydrogenolysis products is reported. Native lignin in pine wood was depolymerized by mild hydrogenolysis to give an oil product that was reacted with epichlorohydrin to give epoxy prepolymers. These were blended with bisphenol A diglycidyl ether or glycerol diglycidyl ether and cured with diethylenetriamine or isophorone diamine. The key novelty of this work lies in using the inherent properties of the native lignin in preparing new biobased epoxy resins. The lignin-derived epoxy prepolymers could be used to replace 25-75% of the bisphenol A diglycidyl ether equivalent, leading to increases of up to 52% in the flexural modulus and up to 38% in the flexural strength. Improvements in the flexural strength were attributed to the oligomeric products present in the lignin hydrogenolysis oil. These results indicate lignin hydrogenolysis products have potential as sustainable biobased polyols in the synthesis of high performance epoxy resins.

  11. Evidence for lignin oxidation by the giant panda fecal microbiome.

    Directory of Open Access Journals (Sweden)

    Wei Fang

    Full Text Available The digestion of lignin and lignin-related phenolic compounds from bamboo by giant pandas has puzzled scientists because of the lack of lignin-degrading genes in the genome of the bamboo-feeding animals. We constructed a 16S rRNA gene library from the microorganisms derived from the giant panda feces to identify the possibility for the presence of potential lignin-degrading bacteria. Phylogenetic analysis showed that the phylotypes of the intestinal bacteria were affiliated with the phyla Proteobacteria (53% and Firmicutes (47%. Two phylotypes were affiliated with the known lignin-degrading bacterium Pseudomonas putida and the mangrove forest bacteria. To test the hypothesis that microbes in the giant panda gut help degrade lignin, a metagenomic library of the intestinal bacteria was constructed and screened for clones that contained genes encoding laccase, a lignin-degrading related enzyme. A multicopper oxidase gene, designated as lac51, was identified from a metagenomic clone. Sequence analysis and copper content determination indicated that Lac51 is a laccase rather than a metallo-oxidase and may work outside its original host cell because it has a TAT-type signal peptide and a transmembrane segment at its N-terminus. Lac51 oxidizes a variety of lignin-related phenolic compounds, including syringaldazine, 2,6-dimethoxyphenol, ferulic acid, veratryl alcohol, guaiacol, and sinapinic acid at conditions that simulate the physiologic environment in giant panda intestines. Furthermore, in the presence of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS, syringic acid, or ferulic acid as mediators, the oxidative ability of Lac51 on lignin was promoted. The absorbance of lignin at 445 nm decreased to 36% for ABTS, 51% for syringic acid, and 51% for ferulic acid after incubation for 10 h. Our findings demonstrate that the intestinal bacteria of giant pandas may facilitate the oxidation of lignin moieties, thereby clarifying the digestion

  12. Solubilization and Mineralization of Lignin by White Rot Fungi

    OpenAIRE

    Boyle, C. David; Bradley R. Kropp; Reid, Ian D.

    1992-01-01

    The white rot fungi Lentinula edodes, Phanerochaete chrysosporium, Pleurotus sajor-caju, Flammulina velutipes, and Schizophyllum commune were grown in liquid media containing 14C-lignin-labelled wood, and the formation of water-soluble 14C-labelled products and 14CO2, the growth of the fungi, and the activities of extracellular lignin peroxidase, manganese peroxidase, and laccase were measured. Conditions that affect the rate of lignin degradation were imposed, and both long-term (0- to 16-da...

  13. Biodegradation of alkaline lignin by Bacillus ligniniphilus L1

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Daochen; Zhang, Peipei; Xie, Changxiao; Zhang, Weimin; Sun, Jianzhong; Qian, Wei-Jun; Yang, Bin

    2017-02-21

    Background: Lignin is the most abundant aromatic biopolymer in the biosphere and it comprises up to 30% of plant biomass. Although lignin is the most recalcitrant component of the plant cell wall, still there are microorganisms able to decompose it or degrade it. Fungi are recognized as the most widely used microbes for lignin degradation. However, bacteria have also been known to be able to utilize lignin as a carbon or energy source. Bacillus ligniniphilus L1 was selected in this study due to its capability to utilize alkaline lignin as a single carbon or energy source and its excellent ability to survive in extreme environments. Results: To investigate the aromatic metabolites of strain L1 decomposing alkaline lignin, GC-MS analyze was performed and fifteen single phenol ring aromatic compounds were identified. The dominant absorption peak included phenylacetic acid, 4-hydroxy-benzoicacid, and vanillic acid with the highest proportion of metabolites resulting in 42%. Comparison proteomic analysis were carried out for further study showed that approximately 1447 kinds of proteins were produced, 141 of which were at least 2-fold up-regulated with alkaline lignin as the single carbon source. The up-regulated proteins contents different categories in the biological functions of protein including lignin degradation, ABC transport system, environmental response factors, protein synthesis and assembly, etc. Conclusions: GC-MS analysis showed that alkaline lignin degradation of strain L1 produced 15 kinds of aromatic compounds. Comparison proteomic data and metabolic analysis showed that to ensure the degradation of lignin and growth of strain L1, multiple aspects of cells metabolism including transporter, environmental response factors, and protein synthesis were enhanced. Based on genome and proteomic analysis, at least four kinds of lignin degradation pathway might be present in strain L1, including a Gentisate pathway, the benzoic acid pathway and the

  14. Selective conversion of biorefinery lignin into dicarboxylic acids.

    Science.gov (United States)

    Ma, Ruoshui; Guo, Mond; Zhang, Xiao

    2014-02-01

    The emerging biomass-to-biofuel conversion industry has created an urgent need for identifying new applications for biorefinery lignin. This paper demonstrates a new route to producing dicarboxylic acids from biorefinery lignin through chalcopyrite-catalyzed oxidation in a highly selective process. Up to 95 % selectivity towards stable dicarboxylic acids was obtained for several types of biorefinery lignin and model compounds under mild, environmentally friendly reaction conditions. The findings from this study paved a new avenue to biorefinery lignin conversions and applications. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Experimental Study of Mechanistic Acid Deconstruction of Lignin

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, M.; Kim, S.; Chmely, S. C.; Katahira, R.; Foust, T. D.; Beckham, G. T.

    2012-01-01

    Lignin is a major component of biomass, which remains highly underutilized in selective biomass conversion strategies to renewable fuels and chemicals. Here we are interested in studying the mechanisms related to the acid deconstruction of lignin with a combined theoretical and experimental approach. Quantum mechanical calculations were employed to elucidate possible deconstruction mechanisms with transition state theory. Model dimers, imitating H, S, and G lignins, were synthesized with the most abundant {beta} - O - 4 linkage in lignin. These compounds were then depolymerized using various acids and at different operating conditions. The deconstruction products were analyzed to complement the QM studies and investigate proposed mechanisms.

  16. Effective Release of Lignin Fragments from Lignocellulose by Lewis Acid Metal Triflates in the Lignin-First Approach.

    Science.gov (United States)

    Huang, Xiaoming; Zhu, Jiadong; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

    2016-12-08

    Adding value to lignin, the most complex and recalcitrant fraction in lignocellulosic biomass, is highly relevant to costefficient operation of biorefineries. We report the use of homogeneous metal triflates to rapidly release lignin from biomass. Combined with metal-catalyzed hydrogenolysis, the process separates woody biomass into few lignin-derived alkylmethoxyphenols and cellulose under mild conditions. Model compound studies show the unique catalytic properties of metal triflates in cleaving lignin-carbohydrate interlinkages. The lignin fragments can then be disassembled by hydrogenolysis. The tandem process is flexible and allows obtaining good aromatic monomer yields from different woods (36-48 wt %, lignin base). The cellulose-rich residue is an ideal feedstock for established biorefining processes. The highly productive strategy is characterized by short reaction times, low metal triflate catalyst requirement, and leaving cellulose largely untouched. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Diverse bacteria with lignin degrading potentials isolated from two ranks of coal

    Directory of Open Access Journals (Sweden)

    Lu Wang

    2016-09-01

    Full Text Available Taking natural coal as a seed bank of bacterial strains able to degrade lignin that is with molecular structure similar to coal components, we isolated 393 and 483 bacterial strains from a meager lean coal sample from Hancheng coalbed and a brown coal sample from Bayannaoer coalbed, respectively by using different media. Statistical analysis showed that isolates were significantly more site-specific than medium-specific. Of the 876 strains belonging to 27 genera in Actinobacteria, Firmicutes, and Proteobacteria, 612 were positive for lignin degradation function, including 218 strains belonging to 35 species in Hancheng and 394 strains belonging to 19 species in Zhongqi. Among them, the dominant lignin-degrading strains were Thauera (Hancheng, Arthrobacter (Zhongqi and Rhizobium (both. The genes encoding the laccases- or laccase-like multicopper oxidases, key enzymes in lignin production and degradation, were detected in three genera including Massilia for the first time, which was in high expression by real time PCR (qRT-PCR detection, confirming coal as a good seed bank.

  18. Adsorption of mercury on lignin: combined surface complexation modeling and X-ray absorption spectroscopy studies.

    Science.gov (United States)

    Lv, Jitao; Luo, Lei; Zhang, Jing; Christie, Peter; Zhang, Shuzhen

    2012-03-01

    Adsorption of mercury (Hg) on lignin was studied at a range of pH values using a combination of batch adsorption experiments, a surface complexation model (SCM) and synchrotron X-ray absorption spectroscopy (XAS). Surface complexation modeling indicates that three types of acid sites on lignin surfaces, namely aliphatic carboxylic-, aromatic carboxylic- and phenolic-type surface groups, contributed to Hg(II) adsorption. The bond distance and coordination number of Hg(II) adsorption samples at pH 3.0, 4.0 and 5.5 were obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy analysis. The results of SCM and XAS combined reveal that the predominant adsorption species of Hg(II) on lignin changes from HgCl(2)(0) to monodentate complex -C-O-HgCl and then bidentate complex -C-O-Hg-O-C- with increasing pH value from 2.0 to 6.0. The good agreement between SCM and XAS results provides new insight into understanding the mechanisms of Hg(II) adsorption on lignin.

  19. Experimental Researches on Milled Wood Lignin Pyrolysis Based on Analysis of Bio-oil

    Institute of Scientific and Technical Information of China (English)

    GUO Xiu-juan; WANG Shu-rong; WANG Kai-ge; LUO Zhong-yang

    2011-01-01

    The structure of milled wood lignin(MWL), isolated via the Bj(6)rkman procedure, was studied by means of 1H NMR spectroscopy and Fourier transform infrared spectroscopy, and then its pyrolytic product distribution was investigated on a pyrolysis device. MWL obtained from Manchurian Ash(MA) contained more methoxyl and free phenolic hydroxyl groups per C9 unit than MWL from Mongolian Pine(MP) due to the existence of both guaiacyl and syringyl units, which have a major influence on the pyrolysis behavior of lignin. The results of pyrolysis show that MWL from MA generated a higher yield of bio-oil, mainly composed of phenols, guaiacols, syringols and catechols,and a less yield of char, in addition to the gaseous products CO, CO2, methane and methanol, compared with MWL from MP. Guaiacol and syringol were the typical products from G-lignin and S-lignin, probably attributed to the easier cleavage of the aryl-alkyl linkage in the side chain compared with the C-OCH3 bond in the benzene ring. The degradation of MWL from MP was dominated by the demethylation reaction and the cleavage of aliphatic -CH2OH at the γ-position, followed by the cracking of the Cα-Cβ and C4-Cα bonds.

  20. Template-mediated synthesis and bio-functionalization of flexible lignin-based nanotubes and nanowires

    Science.gov (United States)

    Caicedo, Hector M.; Dempere, Luisa A.; Vermerris, Wilfred

    2012-03-01

    Limitations of cylindrical carbon nanotubes based on the buckminsterfullerene structure as delivery vehicles for therapeutic agents include their chemical inertness, sharp edges and toxicological concerns. As an alternative, we have developed lignin-based nanotubes synthesized in a sacrificial template of commercially available alumina membranes. Lignin is a complex phenolic plant cell wall polymer that is generated as a waste product from paper mills and biorefineries that process lignocellulosic biomass into fuels and chemicals. We covalently linked isolated lignin to the inner walls of activated alumina membranes and then added layers of dehydrogenation polymer onto this base layer via a peroxidase-catalyzed reaction. By using phenolic monomers displaying different reactivities, we were able to change the thickness of the polymer layer deposited within the pores, resulting in the synthesis of nanotubes with a wall thickness of approximately 15 nm or nanowires with a nominal diameter of 200 nm. These novel nanotubes are flexible and can be bio-functionalized easily and specifically, as shown by in vitro assays with biotin and Concanavalin A. Together with their intrinsic optical properties, which can also be varied as a function of their chemical composition, these lignin-based nanotubes are expected to enable a variety of new applications including as delivery systems that can be easily localized and imaged after uptake by living cells.

  1. Low-Energy Catalytic Electrolysis for Simultaneous Hydrogen Evolution and Lignin Depolymerization.

    Science.gov (United States)

    Du, Xu; Liu, Wei; Zhang, Zhe; Mulyadi, Arie; Brittain, Alex; Gong, Jian; Deng, Yulin

    2017-03-09

    Here, a new proton-exchange-membrane electrolysis is presented, in which lignin was used as the hydrogen source at the anode for hydrogen production. Either polyoxometalate (POM) or FeCl3 was used as the catalyst and charge-transfer agent at the anode. Over 90 % Faraday efficiency was achieved. In a thermal-insulation reactor, the heat energy could be maintained at a very low level for continuous operation. Compared to the best alkaline-water electrolysis reported in literature, the electrical-energy consumption could be 40 % lower with lignin electrolysis. At the anode, the Kraft lignin (KL) was oxidized to aromatic chemicals by POM or FeCl3 , and reduced POM or Fe ions were regenerated during the electrolysis. Structure analysis of the residual KL indicated a reduction of the amount of hydroxyl groups and the cleavage of ether bonds. The results suggest that POM- or FeCl3 -mediated electrolysis can significantly reduce the electrolysis energy consumption in hydrogen production and, simultaneously, depolymerize lignin to low-molecular-weight value-added aromatic chemicals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Simulation of Syngas Production from Lignin Using Guaiacol as a Model Compound

    Directory of Open Access Journals (Sweden)

    Nancy Eloísa Rodríguez-Olalde

    2015-06-01

    Full Text Available Lignin is an abundant component in biomass that can be used a feedstock for producing several value-added products, including biofuels. However, lignin is a complex molecule (involving in its structure three types of phenylpropane units: coumaryl, coniferyl and sinapyl, which is difficult to implement in any process simulation task. The lignin from softwood is formed mainly by coniferyl units; therefore, in this work the use of the guaiacol molecule to model softwood lignin in the simulation of the syngas process (H2 + CO is proposed. A Gibbs reactor in ASPEN PLUS® was feed with ratios of water and guaiacol from 0.5 to 20. The pressure was varied from 0.05 to 1.01 MPa and the temperature in the range of 200–3200 °C. H2, CO, CO2, CH4, O2 and C as graphite were considered in the output stream. The pressure, temperature and ratio water/guaiacol conditions for syngas production for different H2/CO ratio are discussed. The obtained results allow to determine the operating conditions to improve the syngas production and show that C as graphite and water decomposition can be avoided.

  3. Lignin recovery. A resource to value; La lignina: una risorsa da valorizzare

    Energy Technology Data Exchange (ETDEWEB)

    Zimbardi, P.; Cardinale, G.; Demichele, M.; Nanna, F.; Viggiano, D. [ENEA, Centro Ricerche Trisaia, Rotondella, MT (Italy). Dipt. Energia; Bonini, C.; D' Alessio, L.; D' Auria, M.; Teghil, R.; Tofani, D. [Basilicata Univ., Potenza (Italy). Dipt. di Chimica

    1999-07-01

    In the present paper, the effects of the steam explosion (ES) pretreatment conditions on recovery and chemical structure of wheat straw lignin are reported. The experimental data of lignin recovery by caustic extraction, followed by acid precipitation, have been interpolated to obtain the dependence on the time and temperature of SE. The lignin has been characterised by using several methods. Preliminary results on the synthesis of copolymers lignin-styrene are also reported. [Italian] Si ripotano i risultati piu' rilevanti di un'attivita' di ricerca condotta dall'ENEA e dall'universita' della Basilicata, finalizzata alla valorizzazione della lignina. Sono stati indagati gli effetti del trattamento con vapore d'acqua ad alta pressione (processo steam explosion) sulla struttura chimica della lignina e la possibilita' di isolarla con alte rese di estrazione dalla paglia di grano. La lignina, estratta dalla biomassa trattata con una soluzione acquosa di idrossido di sodio ed isolata acidificando la soluzione con acido solforico, e' stata analizzata con diverse tecniche microscopiche, spettroscopiche e cromatografiche. Sono riportati i dati sperimentali interpolati ottenendo la relazione empirica che lega la resa di recupero alla temperatura e alla durata del trattamento di steam explosion.

  4. Biosynthesis and incorporation of side-chain-truncated lignin monomers to reduce lignin polymerization and enhance saccharification.

    Science.gov (United States)

    Eudes, Aymerick; George, Anthe; Mukerjee, Purba; Kim, Jin S; Pollet, Brigitte; Benke, Peter I; Yang, Fan; Mitra, Prajakta; Sun, Lan; Cetinkol, Ozgül P; Chabout, Salem; Mouille, Grégory; Soubigou-Taconnat, Ludivine; Balzergue, Sandrine; Singh, Seema; Holmes, Bradley M; Mukhopadhyay, Aindrila; Keasling, Jay D; Simmons, Blake A; Lapierre, Catherine; Ralph, John; Loqué, Dominique

    2012-06-01

    Lignocellulosic biomass is utilized as a renewable feedstock in various agro-industrial activities. Lignin is an aromatic, hydrophobic and mildly branched polymer integrally associated with polysaccharides within the biomass, which negatively affects their extraction and hydrolysis during industrial processing. Engineering the monomer composition of lignins offers an attractive option towards new lignins with reduced recalcitrance. The presented work describes a new strategy developed in Arabidopsis for the overproduction of rare lignin monomers to reduce lignin polymerization degree (DP). Biosynthesis of these 'DP reducers' is achieved by expressing a bacterial hydroxycinnamoyl-CoA hydratase-lyase (HCHL) in lignifying tissues of Arabidopsis inflorescence stems. HCHL cleaves the propanoid side-chain of hydroxycinnamoyl-CoA lignin precursors to produce the corresponding hydroxybenzaldehydes so that plant stems expressing HCHL accumulate in their cell wall higher amounts of hydroxybenzaldehyde and hydroxybenzoate derivatives. Engineered plants with intermediate HCHL activity levels show no reduction in total lignin, sugar content or biomass yield compared with wild-type plants. However, cell wall characterization of extract-free stems by thioacidolysis and by 2D-NMR revealed an increased amount of unusual C₆C₁ lignin monomers most likely linked with lignin as end-groups. Moreover the analysis of lignin isolated from these plants using size-exclusion chromatography revealed a reduced molecular weight. Furthermore, these engineered lines show saccharification improvement of pretreated stem cell walls. Therefore, we conclude that enhancing the biosynthesis and incorporation of C₆C₁ monomers ('DP reducers') into lignin polymers represents a promising strategy to reduce lignin DP and to decrease cell wall recalcitrance to enzymatic hydrolysis. © 2012 The Authors. Plant Biotechnology Journal © 2012 Society for Experimental Biology, Association of Applied

  5. Characterization and enzymatic hydrolysis of wood from transgenic Pinus taeda engineered with syringyl lignin or reduced lignin content

    Energy Technology Data Exchange (ETDEWEB)

    Edmunds, Charles W.; Peralta, Perry; Kelley, Stephen S.; Chiang, Vincent L.; Sharma-Shivappa, Ratna R.; Davis, Mark F.; Harman-Ware, Anne E.; Sykes, Robert W.; Gjersing, Erica; Cunningham, Michael W.; Rottmann, William; Miller, Zachary D.; Peszlen, Ilona

    2017-02-22

    Softwood is an abundant resource; however, currently its utilization for bioconversion to obtain platform sugars is limited. Pinus taeda trees which were genetically modified to either produce S lignin or to decrease lignin content were characterized with a suite of analytic techniques. Syringyl lignin was visualized in the secondary xylem of one genetic line with Maule staining. Solid-state nuclear magnetic resonance identified the S lignin units were coupled into the lignin through ..beta..-O-4 linkages, and thioacidolysis measured approximately 13% S lignin content in the same sample. Reductions of the lignin of as much as 33% were observed in the transgenics. To better understand how these modifications affect bioconversion, their amenability to hot water and dilute acid pretreatments and enzymatic hydrolysis was evaluated. Lignin reductions resulted in 1.9-3.2-fold increases in glucose release compared to the control. However, no apparent benefit was observed by S lignin incorporation at the concentrations reported in this study. These results highlight the potential for softwood cell wall properties to be improved for bioenergy/biochemical applications.

  6. Thioacidolysis Marker Compound for Ferulic Acid Incorporation into Angiosperm Lignins (and an Indicator for Cinnamoyl-coenzyme-A Reductase Deficiency

    Science.gov (United States)

    A molecular marker compound, derived from lignin by the thioacidolysis degradative method, for structures produced when ferulic acid is incorporated into lignification in angiosperms (poplar, Arabidopsis, tobacco) has been structurally identified as 1,2,2-trithioethyl ethylguaiacol [1-(4-hydroxy-3-m...

  7. Development and evaluation of an automatically adjusting coarse-grained force field for a β-O-4 type lignin from atomistic simulations

    Science.gov (United States)

    Li, Wenzhuo; Zhao, Yingying; Huang, Shuaiyu; Zhang, Song; Zhang, Lin

    2017-01-01

    This goal of this work was to develop a coarse-grained (CG) model of a β-O-4 type lignin polymer, because of the time consuming process required to achieve equilibrium for its atomistic model. The automatic adjustment method was used to develop the lignin CG model, which enables easy discrimination between chemically-varied polymers. In the process of building the lignin CG model, a sum of n Gaussian functions was obtained by an approximation of the corresponding atomistic potentials derived from a simple Boltzmann inversion of the distributions of the structural parameters. This allowed the establishment of the potential functions of the CG bond stretching and angular bending. To obtain the potential function of the CG dihedral angle, an algorithm similar to a Fourier progression form was employed together with a nonlinear curve-fitting method. The numerical potentials of the nonbonded portion of the lignin CG model were obtained using a potential inversion iterative method derived from the corresponding atomistic nonbonded distributions. The study results showed that the proposed CG model of lignin agreed well with its atomistic model in terms of the distributions of bond lengths, bending angles, dihedral angles and nonbonded distances between the CG beads. The lignin CG model also reproduced the static and dynamic properties of the atomistic model. The results of the comparative evaluation of the two models suggested that the designed lignin CG model was efficient and reliable.

  8. Degradation of /sup 14/C-labeled lignins and /sup 14/C-labeled aromatic acids by fusarium solani

    Energy Technology Data Exchange (ETDEWEB)

    Norris, D.M.

    1980-08-01

    Abilities of isolate AF-W1 of Fusarium solani to degrade the side chain and the ring structure of synthetic dehydrogenative polymerizates, aromatic acids, or lignin in sound wood were investigated under several conditions of growth substrate or basal medium and pH. Significant transformations of lignins occurred in 50 days in both unextracted and extracted sound wood substrances with 3% malt as the growth substrate and the pH buffered initially at 4.0 with 2,2-dimethylsuccinate. Degradation of lignin in such woods also occurred under unbuffered pH conditions when a basal medium of either 3% malt or powdered cellulose in deionized water was present. Decomposition of the lignin in these woods did not occur in cultures where D-glucose was present as a growth substrate. F. solani significantly transformed, as measured as evolved /sup 14/CO/sub 2/, both synthetic side chain (beta, gamma)-/sup 14/C- and U-ring-/sup 14/C-labeled lignins in 30 days under liquid culture conditions of only distilled deionized water and no pH adjustment. Degradation of dehydrogenative polymerizates by F. solani was reduced drastically when D2 was the liquid medium. AF-W1 also cleaved the alpha-/sup 14/C from p- hydroxybenzoic acid and evolved /sup 14/CO/sub 2/ from the substrace, (3-/sup 14/C) cinnamic acid. Thus, the fungus cleaved side chain carbon from substrate that originally lacked hydroxyl substitution on the aromatic nucleus. Surprisingly, small amounts of /sup 14/C cleaved from aromatic acids by F. solani were incorporated into cell mass. Initial buffering of the culture medium to pH 4.0 or 5.0 with 0.1 M2,2-dimethylsuccinate significantly increased F. solani degradation of all lignins or aromatic acids. Results indicated that AF-W1 used lignin as a sole carbon source.

  9. Quantitative proteomic analysis of the influence of lignin on biofuel production by Clostridium acetobutylicum ATCC 824

    National Research Council Canada - National Science Library

    Raut, Mahendra P; Couto, Narciso; Pham, Trong K; Evans, Caroline; Noirel, Josselin; Wright, Phillip C

    2016-01-01

    ... cellobiose, prior to bioproduction of acetone-butanol-ethanol (ABE) and hydrogen. Fermentation capability is limited by lignin and thus process optimization requires knowledge of lignin inhibition...

  10. Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Stahl, Shannon S; Rahimi, Alireza

    2015-03-03

    Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

  11. Wheat straw lignin degradation induction to aromatics by por Aspergillus spp. and Penicillium chrysogenum

    Directory of Open Access Journals (Sweden)

    Baltierra-Trejo Eduardo

    2016-02-01

    Full Text Available Wheat straw is a recalcitrant agricultural waste; incineration of this material represents an important environmental impact. Different reports have been made regarding the use of the structural components of wheat straw, i.e. cellulose, hemicellulose and lignin; however, lignin has been less exploited because it is largely considered the recalcitrant part. Residual wheat straw lignin (REWSLI has a potential biotech-nological value if depolymerization is attained to produce aromatics. Ligninolytic mitosporic fungus represent an alternative where very little research has been done, even though they are capable of depol-ymerize REWSLI in simple nutritional conditions in relatively short periods, when compared to basidio-mycetes. The aim of this research was to study the depolymerization activity of Aspergillus spp and Penicillium spp on semipurified REWSLI as the sole carbon source to produce aromatics. The depoly-merization capacity was determined by the activity of the laccase, lignin peroxidase and manganese peroxidase enzymes. The generated aromatics derived from the REWSLI depolymerization were identi-fied by gas chromatography. Obtained results revealed that Penicillium chrysogenum depolymerized the lignin material by 34.8% during the 28-day experimentation period. Laccase activity showed the largest activity with 111 U L-1 in a seven-day period, this enzyme induction was detected in a smaller period than that required by basidiomycetes to induce it. Moreover, the enzymatic activity was produced with-out the addition of an extra carbon source as metabolic inductor. Aspergillus spp and Penicillium spp generated guaiacol, vanillin, and hydroxybenzoic, vanillinic, syringic and ferulic acid with a maximum weekly production of 3.5, 3.3, 3.2, 3.3, 10.1 and 21.9 mg mL-1, respectively.

  12. Near-Ir surface-enhanced Raman spectrum of lignin

    Science.gov (United States)

    Umesh P. Agarwal; Richard S. Reiner

    2009-01-01

    Compacted 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...

  13. Noncatalytic Direct Liquefaction of Biorefinery Lignin by Ethanol

    DEFF Research Database (Denmark)

    Nielsen, Joachim Bachmann; Jensen, Anders; Madsen, Line Riis

    2017-01-01

    There is a growing interest in lignin valorization to biofuels and chemicals. Here, we propose a novel and simple noncatalytic process to directly liquefy lignin rich solid residual from second generation bioethanol production by solvolysis with ethanol. Through an extensive parameter study...

  14. Metal Triflates for the Production of Aromatics from Lignin

    NARCIS (Netherlands)

    Deuss, Peter J.; Lahive, Ciaran W.; Lancefield, Christopher S.; Westwood, Nicholas J.; Kamer, Paul C. J.; Barta, Katalin; de Vries, Johannes G.

    2016-01-01

    The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields under mild reaction conditions. The methodology

  15. Activated effect of lignin on α-amylase.

    Science.gov (United States)

    Zhang, Juan; Cui, Jun-Hui; Yin, Tingting; Sun, Lizhou; Li, Genxi

    2013-12-01

    This paper reports a new kind of activator of α-amylase, lignin, which can greatly increase α-amylase activity. The promoted ratio of lignin is even much higher than that of chloride ion, the traditional activator of α-amylase. Further experimental results reveal that lignin may interact with α-amylase to form a 1:1 complex with a binding constant of 4.47×10(5) M(-1). The binding is spontaneous and lignin/α-amylase complex formation is an exothermal reaction. Hydrogen bonding plays a key role and non-radiation energy transfers from α-amylase to lignin in the binding process. Lignin, combining with α-amylase, conforms to a first-order exponential decay function. The formation of the lignin/α-amylase complex results in the reduction of α-helical content from 57.7% to 53.9%, the increase of the polarity around tryptophan residues, the decrease of the hydrophobicity, and the enlargement of protein granule volume. This work will give a deeper insight into lignin as a kind of dietary fibre, known as an important food functional factor. Furthermore, it also contributes to the exploration of an activator of α-amylase, used in the food industry.

  16. [Characterization of lignin and Mn peroxidases from Phanerochaete chrysosporium

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

    Lignin peroxidases were investigated with respect to enzyme kinetics and NMR spectroscopy of the heme domain. MN peroxidases were studied with respect to the role of oxalate in enzyme activity, the NMR spectroscopy of the heme domain. Gene expression of both lignin and MN peroxidases were examined as well as expression of site-directed mutants aimed at scale up production of these enzymes.

  17. Lignin-degrading enzyme from the hymenomycete Phanerochaete chrysosporium Burds

    Energy Technology Data Exchange (ETDEWEB)

    Tien, M.; Kirk, T.K.

    1983-08-12

    The extracellular fluid of ligninolytic cultures of the wood-decomposing basidiomycete Phanerochaete chrysosporium Burds contains an enzyme that degrades lignin substructure model compounds as well as spruce and birch lignins. It has a molecular size of 42,000 daltons and requires hydrogen peroxide for activity. (Refs. 24).

  18. Anatomy and lignin distribution in reaction phloem fibres of several Japanese hardwoods.

    Science.gov (United States)

    Nakagawa, Kaori; Yoshinaga, Arata; Takabe, Keiji

    2012-09-01

    Although tension wood formation and the structure of gelatinous fibres (G-fibres) have been widely investigated, studies of the influence of the reaction phenomenon on phloem fibres have been few and incomplete in comparison with those of xylem wood fibres. This study was undertaken to clarify the influence of stem inclination on phloem fibres using several Japanese hardwood species that produce different G-fibre types in tension wood. Eight hardwood species were inclined at 30-45° at the beginning of April. Specimens were collected in July and December. The cell-wall structure and lignin distribution of phloem fibres on both the tension and opposite sides were compared by light microscopy, ultraviolet microscopy, confocal laser scanning microscopy after staining with acriflavine, and transmission electron microscopy after staining with potassium permanganate. Three types of changes were found in tension-side phloem fibres: (1) increases in the proportion of the syringyl unit in lignin in the S(1) and S(2) layers and compound middle lamella (Cercidiphyllum japonicum), (2) formation of unlignified gelatinous layers (Melia azedarach and Acer rufinerve) and (3) increases in the number of layers (n) in the multi-layered structure of S(1) + S(2) + n (G + L) (Mallotus japonicus). Other species showed no obvious change in cell-wall structure or lignin distribution. Phloem fibres of the tree species examined in our study showed three types of changes in lignin distribution and cell-wall structure. The reaction phenomenon may vary with tree species and may not be closely related to G-fibre type in tension wood.

  19. Lignin-based cement fluid loss control additive

    Energy Technology Data Exchange (ETDEWEB)

    Schilling, P.

    1990-05-22

    This patent describes a hydraulic cement slurry composition. It comprises: a hydraulic cement, and the following expressed as parts by weight per 100 parts of the hydraulic cement, water from about 25 to 105 parts, and from abut 0.5 to 2.5 parts of a compound selected from the group consisting of a sulfonated lignin and a sulfomethylated lignin, wherein the lignin has been sequentially crosslinked by reacting the lignin with a member of the group consisting of formaldehyde and epichlorohydrin and alkoxylated with between about 2 to about 6 moles of a compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and a combination thereof per 1000 g of the lignin.

  20. Selective production of 4-ethylphenolics from lignin via mild hydrogenolysis.

    Science.gov (United States)

    Ye, Yueyuan; Zhang, Yu; Fan, Juan; Chang, Jie

    2012-08-01

    Selective production of 4-ethylphenolics from lignin via mild hydrogenolysis was reported in this short communication. The hydrogenolysis of lignin was carried out in an autoclave with 65 vol.% ethanol/water as solvent, with 5% Ru/C, Pd/C and Pt/C as catalysts. The influences of catalysts, lignin species, and reaction conditions including reaction temperature, reaction time, and initial H(2) pressure on yield of target compounds were investigated. 3.1% 4-Ethylphenol and 1.3% 4-ethylguaiacol based on lignin could be obtained simultaneously from hydrogenolysis of corn stalk lignin, which is approximate to the yield obtained from petrochemical route. The results of this work showed that this novel method is a quite promising technique for the substitution of petrochemical route. Copyright © 2012 Elsevier Ltd. All rights reserved.

  1. INFLUENCE OF REACTION CONDITIONS ON LIGNIN HYDROTHERMAL TREATMENT

    Directory of Open Access Journals (Sweden)

    Xabier eErdocia

    2014-04-01

    Full Text Available Organosolv lignin, obtained from olive tree pruning under optimised conditions, was subjected to a hydrothermal depolymerisation process catalysed by sodium hydroxide. The depolymerisation of lignin was carried out at 300 ºC using different reaction times (20, 40, 60, 70, 80, 90 and 100 min in order to study the influence of this parameter on lignin depolymerisation. The resulting products (oil and residual lignin were measured and analysed by different techniques (GC/MS, HPSEC and pyrolysis-GC/MS in order to determine their nature and composition. Coke was also formed, at a lower quantity, incompetitive repolymerisation reactions during the lignin hydrothermal treatment. The maximum oil yield and concentration of monomeric phenolic compounds was obtained after80 min of reaction time. The highest reaction time studied (100 min had the worst results with the lowest oil yield and highest coke production.

  2. POLYETHER POLYURETHANE FROM MODIFIED WHEAT STRAW OXYGEN-ALKALINE LIGNIN

    Institute of Scientific and Technical Information of China (English)

    QuanxiaoLiu; HuaiyuZhan; BeihaiHe; ShuhuiYang; JianhuaLiu; JianluLiu(1); ZhenxingPang

    2004-01-01

    Polyether polyurethane was synthesized from modified wheat straw oxygen-alkaline lignin, polyethylene glycol and two different diisocyanates (diphenylemethane-4, 4'-diisocyanate, tolulene diisocyanate) by solution casting method, its properties were investigated. The results show that modified wheat straw oxygen-alkaline lignin can substitute part of polyethylene glycol to react with diisocyanate to synthesize polyurethane. The molar ratio of NCO to OH and modified wheat straw oxygen-alkaline lignin content affect the properties of lignin-based polyether polyurethane respectively. The addition of plasticizer in the polyurethane synthesis process improves the properties of synthesized polyurethane, especially the elasticity of polyurethane. The synthesized polyurethane from modified wheat straw oxygen-alkali lignin can be used as both engineering plastic and hard foam plastic in future.

  3. POLYETHER POLYURETHANE FROM MODIFIED WHEAT STRAW OXYGEN-ALKALINE LIGNIN

    Institute of Scientific and Technical Information of China (English)

    Quanxiao Liu; Huaiyu Zhan; Beihai He; Shuhui Yang; Jianhua Liu; Jianlu Liu; Zhenxing Pang

    2004-01-01

    Polyether polyurethane was synthesized from modified wheat straw oxygen-alkaline lignin,polyethylene glycol and two different diisocyanates (diphenylemethane-4, 4′-diisocyanate, tolulene diisocyanate) by solution casting method, its properties were investigated. The results show that modified wheat straw oxygen-alkaline lignin can substitute part of polyethylene glycol to react with diisocyanate to synthesize polyurethane. The molar ratio of NCO to OH and modified wheat straw oxygen-alkaline lignin content affect the properties of lignin-based polyether polyurethane respectively. The addition of plasticizer in the polyurethane synthesis process improves the properties of synthesized polyurethane, especially the elasticity of polyurethane. The synthesized polyurethane from modified wheat straw oxygen-alkali lignin can be used as both engineering plastic and hard foam plastic in future.

  4. Dissolution of wood flour and lignin in 1-butyl-3-methyl-1-imidazolium chloride

    Directory of Open Access Journals (Sweden)

    Yasmin Nasiri Khonsari

    2013-10-01

    Full Text Available The ionic solvent, 1-butyl-3-methyl imidazolium chloride was used to dissolve the samples. Two lignocellulosic material including bagasse soda lignin and Populus deltoides wood flour were used. One gram of samples were dissolved in 10 ml ionic solvent, 1-butyl-3-methyl- imidazolium chloride at 70 ºC for 72 h while stirring with a magnetic stirrer. The wood flour and lignin samples were acetylated with addition of acetic anhydride to each container with a ratio of 0.25 ml/ 0.25 ml. The samples were heated for 3 days at 110 ° C. Two control samples (without acetylation and two treatments (acetylation were used. The functional groups were determined using FT-IR Spectrometer. The number and type of carbon and their structure were examined using 13CNMR Spectrometer. The guaiacyl, syringyl, coniferyl alcohol and biphenyls structures were identified.

  5. Modification of chemical reactivity of enzymatic hydrolysis lignin by ultrasound treatment in dilute alkaline solutions.

    Science.gov (United States)

    Ma, Zhuoming; Li, Shujun; Fang, Guizhen; Patil, Nikhil; Yan, Ning

    2016-12-01

    In this study, we have explored various ultrasound treatment conditions for structural modification of enzymatic hydrolysis lignin (EHL) for enhanced chemical reactivity. The key structural modifications were characterized by using a combination of analytical methods, including, Fourier Transform-Infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance ((1)H NMR), Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and Folin-Ciocalteu (F-C) method. Chemical reactivity of the modified EHL samples was determined by both 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity and their reactivity towards formaldehyde. It was observed that the modified EHL had a higher phenolic hydroxyl group content, a lower molecular weight, a higher reactivity towards formaldehyde, and a greater antioxidant property. The higher reactivity demonstrated by the samples after treatment suggesting that ultrasound is a promising method for modifying enzymatic hydrolysis lignin for value-added applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Extraction and characterization of lignin from different biomass resources

    Directory of Open Access Journals (Sweden)

    Dereca Watkins

    2015-01-01

    Full Text Available Lignocellulosic biomass has been acknowledged for potential use to produce chemicals and biomaterials. Lignin is the second most abundant natural polymer with cellulose being number one, making up to 10–25% of lignocellulosic biomass. Lignin is a three-dimensional, highly cross-linked macromolecule composed of three types of substituted phenols, which include: coniferyl, sinapyl, and p-coumaryl alcohols by enzymatic polymerization, yielding a vast number of functional groups and linkages. There is a wide range of lignin sources available, including: jute, hemp, cotton, and wood pulp. Hence, the lignin's physical and chemical behavior will be different with respect to the original source and extraction method used. The objective of this research is to extract lignin from nonwood cellulosic biomass (Wheat straw, Pine straw, Alfalfa, Kenaf, and Flax fiber by formic acid treatment followed by peroxyformic acid treatment for the potential use as a partial replacement for the phenol precursor in resole phenolic systems. Isolated lignins were purified to remove impurities and characterized by Fourier transform infrared spectroscopy (FTIR, Thermogravimetric analysis (TGA and Differential scanning calorimetry (DSC analysis to compare thermal properties and chemical composition. It was found that lignin obtained from alfalfa provided the greatest yield of the various sources. Enthalpy measurements were higher for lignin from flax fiber and alfalfa at 190.57 and 160.90 J/g, respectively. The source of lignin samples was seen to affect the thermal properties. Overall, lignin extracted from wheat straw had the greatest thermal stability followed very closely by that obtained from flax fiber.

  7. Effects of UV weathering on surface properties of polypropylene composites reinforced with wood flour, lignin, and cellulose

    Science.gov (United States)

    Peng, Yao; Liu, Ru; Cao, Jinzhen; Chen, Yu

    2014-10-01

    In this study, the influence of accelerated weathering on polypropylene composites reinforced with wood flour (WF), lignin, and cellulose at different loading levels were evaluated. Six groups of samples were exposed in a QUV accelerated weathering tester for a total of 960 h. The surface color, surface gloss, contact angle and flexural properties of the samples were tested. Besides, the weathered surface was characterized by SEM and ATR-FTIR. The results revealed that (1) the discoloration of composites was accelerated by the presence of lignin, especially at high content; (2) composites containing lignin showed less loss of flexural strength and modulus, less cracks, and better hydrophobicity on weathered surface than other groups, confirming its functions of stabilization and antioxidation; (3) cellulose-based composites exhibited better color stability but more significant deterioration in flexural properties after weathering compared to other composites, suggesting that such kind of composites could not be used as load-bearing structure in outdoor applications.

  8. Effect of Lignin Derivatives in the Bio-Polyols from Microwave Liquefied Bamboo on the Properties of Polyurethane Foams

    Directory of Open Access Journals (Sweden)

    Jiulong Xie

    2013-12-01

    Full Text Available Bamboo residues were subjected to a microwave-assisted liquefaction process for the production of crude bio-polyols (CBP. The fractionated bio-polyols (FBP were obtained by the removal of lignin derivatives from the crude bio-polyols (CBP using a simple method. Polyurethane (PU foams were successfully prepared from both CBP and FBP. The object of this study was to evaluate the effect of lignin derivatives in bio-polyols on the physical properties, thermal stability, and microstructure of PU foams. The results revealed that the PU foam made from CBP had a higher density and superior thermal stability compared to that made from FBP; however, they were also much more fragile. Scanning electron microscope (SEM images indicated that the lignin compounds in the CBP had impact on the structure of the PU foam.

  9. Expression profile of small RNAs in Acacia mangium secondary xylem tissue with contrasting lignin content - potential regulatory sequences in monolignol biosynthetic pathway.

    Science.gov (United States)

    Ong, Seong Siang; Wickneswari, Ratnam

    2011-11-30

    Lignin, after cellulose, is the second most abundant biopolymer accounting for approximately 15-35% of the dry weight of wood. As an important component during wood formation, lignin is indispensable for plant structure and defense. However, it is an undesirable component in the pulp and paper industry. Removal of lignin from cellulose is costly and environmentally hazardous process. Tremendous efforts have been devoted to understand the role of enzymes and genes in controlling the amount and composition of lignin to be deposited in the cell wall. However, studies on the impact of downregulation and overexpression of monolignol biosynthesis genes in model species on lignin content, plant fitness and viability have been inconsistent. Recently, non-coding RNAs have been discovered to play an important role in regulating the entire monolignol biosynthesis pathway. As small RNAs have critical functions in various biological process during wood formation, small RNA profiling is an important tool for the identification of complete set of differentially expressed small RNAs between low lignin and high lignin secondary xylem. In line with this, we have generated two small RNAs libraries from samples with contrasting lignin content using Illumina GAII sequencer. About 10 million sequence reads were obtained in secondary xylem of Am48 with high lignin content (41%) and a corresponding 14 million sequence reads were obtained in secondary xylem of Am54 with low lignin content (21%). Our results suggested that A. mangium small RNAs are composed of a set of 12 highly conserved miRNAs families found in plant miRNAs database, 82 novel miRNAs and a large proportion of non-conserved small RNAs with low expression levels. The predicted target genes of those differentially expressed conserved and non-conserved miRNAs include transcription factors associated with regulation of the lignin biosynthetic pathway genes. Some of these small RNAs play an important role in epigenetic silencing

  10. Lignocellulose Biomass: Constitutive Polymers. Biological Processes of Lignin Degradation; Biomasa lignocelulosica, polimeros constitutivos. Procesos biologicos de degradacion de la lignina

    Energy Technology Data Exchange (ETDEWEB)

    Martin, C.; Manzanares, P.

    1994-07-01

    The structure of the lignocellulosic materials and the chemical composition of their main constitutive polymers, cellulose, hemicelluloses and lignin are described. The most promising transformation processes according to the type of biomass considered: hardwood, softwood an herbaceous and the perspectives of biotechnological processes for bio pulping, bio bleaching and effluents decolorisation in the paper pulp industry are also discussed. (Author) 7 refs.

  11. Abundance and characteristics of lignin liquid intermediates in wood (Pinus ponderosa Dougl. ex Laws.) during hot water extraction

    Science.gov (United States)

    Manuel Raul Pelaez-Samaniego; Vikram Yadama; Manuel Garcia-Perez; Eini Lowell

    2015-01-01

    The objective of this research was to investigate the effects of the conditions of hot water extraction (HWE) on abundance, properties, and structure of lignin depolymerization products. HWE of extracted softwood (ponderosa pine) was conducted using temperatures from 140 to 320°C for 90 min. HWE materials were then subjected to a soxhlet...

  12. Producing a True Lignin Depolymerase for Biobleaching Softwood Kraft Pulp

    Energy Technology Data Exchange (ETDEWEB)

    Simo Sarkanen

    2002-02-04

    This project constituted an intensive effort devoted to producing, from the white-rot fungus Tramets Cingulata, a lignin degrading enzyme (lignin depolymerase) that is directly able to biobleach or delignify softwood kraft pulp brownstock. To this end, the solutions in which T. cingulata was grown contained dissolved kraft lignin which fulfilled two functions; it behaved as a lignin deploymerase substrate and it also appeared to act as an inducer of enzyme expression. However, the lignin depolymerase isoenzymes (and other extracellular T. cingulata enzymes) interacted very strongly with both the kraft lignin components and the fungal hypae, so the isolating these proteins from the culture solutions proved to be unexpectedly difficult. Even after extensive experimentation with a variety of protein purification techniques, only one approach appeared to be capable of purifying lignin depolymerases to homogeneity. Unfortunately the procedure was extremely laborious; it involved the iso electric focusing of concentrated buffer-exchanged culture solutions followed by electro-elution of the desired protein bands from the appropriate polyacrylamide gel segments

  13. Dissolving Lignin in Water through Enzymatic Sulfation with Aryl Sulfotransferase.

    Science.gov (United States)

    Prinsen, Pepijn; Narani, Anand; Hartog, Aloysius F; Wever, Ron; Rothenberg, Gadi

    2017-05-22

    We introduce the concept of using site-specific sulfation of various lignins for increasing their aqueous solubility and thereby their processability. Using p-nitrophenylsulfate as a sulfate source and an aryl sulfotransferase enzyme as catalyst, lignins are easily sulfated at ambient conditions. We demonstrate the specific sulfation of phenolic hydroxyl groups on five different lignins: Indulin AT (Kraft softwood), Protobind 1000 (mixed wheat straw/Sarkanda grass soda) and three organosolv lignins. The reaction proceeds smoothly and the increase in solubility is visible to the naked eye. We then examine the reaction kinetics, and show that these are easily monitored qualitatively and quantitatively using UV/Vis spectroscopy. The UV/Vis results are validated with (31) P NMR spectroscopy of the lignin phenol groups after derivatization with phosphorylation reagent II. In general, the results are more significant with organosolv lignins, as Kraft and soda lignins are produced from aqueous lignocellulose extraction processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Tunable Pickering emulsions with polymer-grafted lignin nanoparticles (PGLNs).

    Science.gov (United States)

    Silmore, Kevin S; Gupta, Chetali; Washburn, Newell R

    2016-03-15

    Lignin is an abundant biopolymer that has native interfacial functions but aggregates strongly in aqueous media. Polyacrylamide was grafted onto kraft lignin nanoparticles using reversible addition-fragmentation chain transfer (RAFT) chemistry to form polymer-grafted lignin nanoparticles (PGLNs) that tune aggregation strength while retaining interfacial activities in forming Pickering emulsions. Polymer graft density on the particle surface, ionic strength, and initial water and cyclohexane volume fractions were varied and found to have profound effects on emulsion characteristics, including emulsion volume fraction, droplet size, and particle interfacial concentration that were attributed to changes in lignin aggregation and hydrophobic interactions. In particular, salt concentration was found to have a significant effect on aggregation, zeta potential, and interfacial tension, which was attributed to changes in solubility of both the kraft lignin and the polyacrylamide grafts. Dynamic light scattering, UV-vis spectroscopy, optical microscopy, and tensiometry were used to quantify emulsion properties and nanoparticle behavior. Under all conditions, the emulsions exhibited relatively fast creaming but were stable against coalescence and Ostwald ripening for a period of months. All emulsions were also oil-in-water (o/w) emulsions, as predicted by the Bancroft rule, and no catastrophic phase inversions were observed for any nanoparticle compositions. We conclude that lower grafting density of polyacrylamide on a lignin core resulted in high levels of interfacial activity, as characterized by higher concentration at the water-cyclohexane interface with a corresponding decrease in interfacial tension. These results indicate that the interfacial properties of polymer-grafted lignin nanoparticles are primarily due to the native hydrophobic interactions of the lignin core. These results suggest that the forces that drive aggregation are also correlated with interfacial

  15. Organic amine catalytic organosolv pretreatment of corn stover for enzymatic saccharification and high-quality lignin.

    Science.gov (United States)

    Tang, Chenglun; Shan, Junqiang; Chen, Yanjun; Zhong, Lingxia; Shen, Tao; Zhu, Chenjie; Ying, Hanjie

    2017-05-01

    A novel and efficient organic amine and organosolv synergetic pretreatment method was developed to overcome the recalcitrance of lignocellulose to produce fermentable sugars and high-quality salt-free lignin. After optimization of the process parameters, a delignification of 81.7% and total sugar yield of 83.2% (87.1% glucose, 75.4% xylose) could be obtained using n-propylamine (10mmol/g, biomass) as a catalyst and aqueous ethanol (60%, v/v) as a solvent. The susceptibility of the substrates to enzymatic digestibility was explained by their physical and chemical characteristics. The physical structure of extracted lignin showed higher β-aryl ether bonds content and functionalities, offering the potential for further downstream upgrading. The role of organic amine catalyst and a synergistic mechanism is proposed for the present system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Synthesis of novel ionic liquids from lignin-derived compounds

    Energy Technology Data Exchange (ETDEWEB)

    Socha, Aaron; Singh, Seema; Simmons, Blake A.; Bergeron, Maxime

    2017-09-19

    Methods and compositions are provided for synthesizing ionic liquids from lignin derived compounds comprising: contacting a starting material comprising lignin with a depolymerization agent to depolymerize the lignin and form a mixture of aldehyde containing compounds; contacting the mixture of aldehyde containing compounds with an amine under conditions suitable to convert the mixture of aldehyde containing compounds to a mixture of amine containing compounds; and contacting the mixture of amine containing compounds with an acid under conditions suitable to form an ammonium salt, thereby preparing the ionic liquid.

  17. Stimulation of two step degradation of sodium ascorbate by lignins.

    Science.gov (United States)

    Sakagami, H; Satoh, K

    1996-01-01

    Alkali-lignin stimulated the degradation of sodium ascorbate in phosphate-buffered saline, fetal bovine serum and culture medium, but not in distilled water. ESR spectroscopy revealed that alkali-lignin stimulated ascorbyl radical production even in distilled water. Similar stimulation activity was found in several other plant extracts, commercial and natural lignified materials. These data suggest that the lignin-stimulated degradation process of ascorbate might be separated into two processes, the first being the ascorbyl radical production process and the second the degradation process.

  18. Quantification of lignin-carbohydrate linkages with high-resolution NMR spectroscopy.

    Science.gov (United States)

    Balakshin, Mikhail; Capanema, Ewellyn; Gracz, Hanna; Chang, Hou-min; Jameel, Hasan

    2011-06-01

    A quantitative approach to characterize lignin-carbohydrate complex (LCC) linkages using a combination of quantitative ¹³C NMR and HSQC 2D NMR techniques has been developed. Crude milled wood lignin (MWLc), LCC extracted from MWLc with acetic acid (LCC-AcOH) and cellulolytic enzyme lignin (CEL) preparations were isolated from loblolly pine (Pinus taeda) and white birch (Betula pendula) woods and characterized using this methodology on a routine 300 MHz NMR spectrometer and on a 950 MHz spectrometer equipped with a cryogenic probe. Structural variations in the pine and birch LCC preparations of different types (MWL, CEL and LCC-AcOH) were elucidated. The use of the high field NMR spectrometer equipped with the cryogenic probe resulted in a remarkable improvement in the resolution of the LCC signals and, therefore, is of primary importance for an accurate quantification of LCC linkages. The preparations investigated showed the presence of different amounts of benzyl ether, γ-ester and phenyl glycoside LCC bonds. Benzyl ester moieties were not detected. Pine LCC-AcOH and birch MWLc preparations were preferable for the analysis of phenyl glycoside and ester LCC linkages in pine and birch, correspondingly, whereas CEL preparations were the best to study benzyl ether LCC structures. The data obtained indicate that pinewood contains higher amounts of benzyl ether LCC linkages, but lower amounts of phenyl glycoside and γ-ester LCC moieties as compared to birch wood.

  19. Lignin engineering in field-grown poplar trees affects the endosphere bacterial microbiome.

    Science.gov (United States)

    Beckers, Bram; Op De Beeck, Michiel; Weyens, Nele; Van Acker, Rebecca; Van Montagu, Marc; Boerjan, Wout; Vangronsveld, Jaco

    2016-02-23

    Cinnamoyl-CoA reductase (CCR), an enzyme central to the lignin biosynthetic pathway, represents a promising biotechnological target to reduce lignin levels and to improve the commercial viability of lignocellulosic biomass. However, silencing of the CCR gene results in considerable flux changes of the general and monolignol-specific lignin pathways, ultimately leading to the accumulation of various extractable phenolic compounds in the xylem. Here, we evaluated host genotype-dependent effects of field-grown, CCR-down-regulated poplar trees (Populus tremula × Populus alba) on the bacterial rhizosphere microbiome and the endosphere microbiome, namely the microbiota present in roots, stems, and leaves. Plant-associated bacteria were isolated from all plant compartments by selective isolation and enrichment techniques with specific phenolic carbon sources (such as ferulic acid) that are up-regulated in CCR-deficient poplar trees. The bacterial microbiomes present in the endosphere were highly responsive to the CCR-deficient poplar genotype with remarkably different metabolic capacities and associated community structures compared with the WT trees. In contrast, the rhizosphere microbiome of CCR-deficient and WT poplar trees featured highly overlapping bacterial community structures and metabolic capacities. We demonstrate the host genotype modulation of the plant microbiome by minute genetic variations in the plant genome. Hence, these interactions need to be taken into consideration to understand the full consequences of plant metabolic pathway engineering and its relation with the environment and the intended genetic improvement.

  20. Lignin peroxidase-negative mutant of the white-rot basidiomycete Phanerochaete chrysosporium.

    OpenAIRE

    Boominathan, K; Dass, S B; Randall, T A; Kelley, R.L.; Reddy, C A

    1990-01-01

    Phanerochaete chrysosporium produces two classes of extracellular heme proteins, designated lignin peroxidases and manganese peroxidases, that play a key role in lignin degradation. In this study we isolated and characterized a lignin peroxidase-negative mutant (lip mutant) that showed 16% of the ligninolytic activity (14C-labeled synthetic lignin----14CO2) exhibited by the wild type. The lip mutant did not produce detectable levels of lignin peroxidase, whereas the wild type, under identical...

  1. Synthesis of Pd(0) nanocatalyst using lignin in water for the Mizoroki-Heck reaction under solvent-free conditions.

    Science.gov (United States)

    Marulasiddeshwara, M B; Kumar, P Raghavendra

    2016-02-01

    Palladium(0) nanospheres with an average size of 1-5 nm were synthesized and stabilized by lignin in water without any reducing agent. The lignin supported palladium(0) nanoparticles (lignin@Pd-NPs) were characterized by UV-vis., FT-IR, SEM, TEM, HRICP-AES, EDX and PXRD. Absence of the peak at 430 nm in UV-vis., spectrum confirmed the reduction of Pd(II) to Pd(0). The five characteristic peaks at (111), (200), (220), (311) and (222) corresponding to the 2θ values 40°, 46.7°, 67.9°, 81.9° and 86.9°, respectively, appeared in PXRD spectrum indicated the crystallographic planes of Pd(0) with fcc structure. The Pd(0) loaded on lignin was 0.0467 mmol/g determined by HRICP-AES and 0.89% (w/w) by EDX. The performance of lignin@Pd-NPs catalyst have been investigated for the Mizoroki-Heck CC bond formation reactions between n-butyl propene-2-enoate and halobenzenes and substituted halobenzenes in polar to highly polar solvents as well as under solvent-free conditions in the presence of organic or inorganic bases. The lignin@Pd-NPs was found to be a highly efficient catalyst to yield the desired products of up to 94% under solvent-free conditions in short reaction times. The catalyst was heterogeneous and hence recovered by filtration and reused several times in the subsequent batches of the same reaction.

  2. Water-Soluble Lignins from Different Bioenergy Crops Stimulate the Early Development of Maize (Zea mays, L.).

    Science.gov (United States)

    Savy, Davide; Cozzolino, Vincenza; Vinci, Giovanni; Nebbioso, Antonio; Piccolo, Alessandro

    2015-11-05

    The molecular composition of water-soluble lignins isolated from four non-food bioenergy crops (cardoon CAR, eucalyptus EUC, and two black poplars RIP and LIM) was characterized in detail, and their potential bioactivity towards maize germination and early growth evaluated. Lignins were found to not affect seed germination rates, but stimulated the maize seedling development, though to a different extent. RIP promoted root elongation, while CAR only stimulated the length of lateral seminal roots and coleoptile, and LIM improved only the coleoptile development. The most significant bioactivity of CAR was related to its large content of aliphatic OH groups, C-O carbons and lowest hydrophobicity, as assessed by (31)P-NMR and (13)C-CPMAS-NMR spectroscopies. Less bioactive RIP and LIM lignins were similar in composition, but their stimulation of maize seedling was different. This was accounted to their diverse content of aliphatic OH groups and S- and G-type molecules. The poorest bioactivity of the EUC lignin was attributed to its smallest content of aliphatic OH groups and largest hydrophobicity. Both these features may be conducive of a EUC conformational structure tight enough to prevent its alteration by organic acids exuded from vegetal tissues. Conversely the more labile conformational arrangements of the other more hydrophilic lignin extracts promoted their bioactivity by releasing biologically active molecules upon the action of exuded organic acids. Our findings indicate that water-soluble lignins from non-food crops may be effectively used as plant biostimulants, thus contributing to increase the economic and ecological liability of bio-based industries.

  3. Combination of six enzymes of a marine Novosphingobium converts the stereoisomers of β-O-4 lignin model dimers into the respective monomers.

    Science.gov (United States)

    Ohta, Yukari; Nishi, Shinro; Hasegawa, Ryoichi; Hatada, Yuji

    2015-10-19

    Lignin, an aromatic polymer of phenylpropane units joined predominantly by β-O-4 linkages, is the second most abundant biomass component on Earth. Despite the continuous discharge of terrestrially produced lignin into marine environments, few studies have examined lignin degradation by marine microorganisms. Here, we screened marine isolates for β-O-4 cleavage activity and determined the genes responsible for this enzymatic activity in one positive isolate. Novosphingobium sp. strain MBES04 converted all four stereoisomers of guaiacylglycerol-β-guaiacyl ether (GGGE), a structural mimic of lignin, to guaiacylhydroxypropanone as an end metabolite in three steps involving six enzymes, including a newly identified Nu-class glutathione-S-transferase (GST). In silico searches of the strain MBES04 genome revealed that four GGGE-metabolizing GST genes were arranged in a cluster. Transcriptome analysis demonstrated that the lignin model compounds GGGE and (2-methoxyphenoxy)hydroxypropiovanillone (MPHPV) enhanced the expression of genes in involved in energy metabolism, including aromatic-monomer assimilation, and evoked defense responses typically expressed upon exposure to toxic compounds. The findings from this study provide insight into previously unidentified bacterial enzymatic systems and the physiological acclimation of microbes associated with the biological transformation of lignin-containing materials in marine environments.

  4. Potential of lignin from Canna edulis ker residue in the inhibition of α-d-glucosidase: Kinetics and interaction mechanism merging with docking simulation.

    Science.gov (United States)

    Xie, Fan; Gong, Shengxiang; Zhang, Wei; Wu, Jinhong; Wang, Zhengwu

    2017-02-01

    In this study, we extracted lignin from Canna edulis ker residue. Its chemical structure, inhibitory activity on α-d-glucosidase, and kinetics as well as interaction mechanism were investigated by using spectrum analysis and docking simulation. The isolated lignin was composed by guaiacyl and syringal units, and exhibited stronger inhibition on α-d-glucosidase than acarbose with the half maximal inhibitory concentration at 5.3±0.3μM. It was a non-competitive inhibitior with Km and Ki values of 0.53±0.02mM and 0.92±0.12μM, respectively. It could quench the intrinsic fluorescence of α-d-glucosidase through a static quenching mode. The calculated values of enthalpy and entropy change were 20.8±2.5kJmol(-1) and 172.7±0.8Jmol(-1)K(-1), respectively. There was a single binding site on α-d-glucosidase for lignin, and the binding distance was 3.2nm. The molecular docking analysis exhibited that the hydrogen bonds, hydropholic interaction, and van der Waals forces were the main forces for lignin bind to α-d-glucosidase. This work provides a new insight into the interaction between the lignin and α-d-glucosidase, which might be beneficial to type 2 diabetes with the application of lignin in functional food and pharmacy fields.

  5. Chemical Composition of Hypodermal and Endodermal Cell Walls and Xylem Vessels Isolated from Clivia miniata (Identification of the Biopolymers Lignin and Suberin).

    Science.gov (United States)

    Zeier, J.; Schreiber, L.

    1997-01-01

    The occurrence of the biopolymers lignin and suberin was investigated with hypodermal (HCW) and endodermal cell walls (ECW) and xylem vessels (XV) isolated from Clivia miniata Reg. roots. Both biopolymers were detected in HCW and ECW, whereas in XV, typical aliphatic suberin monomers were missing and only representative lignin monomers such as guaiacyl (G) and syringyl (S) units could be detected. The absolute amounts of lignin were about one order of magnitude higher compared with suberin in both HCW and ECW. The ratios of the two aromatic lignin units (G/S) decreased from 39 in XV and 10 in HCW to about 1 in ECW, indicating significant differences in lignin structure and function between the three investigated samples. Additionally, compared with the detectable lignin-derived aromatic units G and S, significantly higher amounts of esterified p-coumaric acid-derived aromatic monomers were obtained with HCW, but not with ECW. This is interpreted as a functional adaption of HCW toward pathogen defense at the root/soil interface. The final aim of this study was to provide a thorough chemical characterization of the composition of HCW, ECW, and XV, which in turn will form the basis for a better understanding of the relevant barriers toward the passive, radial, and apoplastic diffusion of solutes from the soil across the root cortex into the root cylinder. PMID:12223670

  6. Membrane Technology for the Recovery of Lignin: A Review

    Directory of Open Access Journals (Sweden)

    Daniel Humpert

    2016-09-01

    Full Text Available Utilization of renewable resources is becoming increasingly important, and only sustainable processes that convert such resources into useful products can achieve environmentally beneficial economic growth. Wastewater from the pulp and paper industry is an unutilized resource offering the potential to recover valuable products such as lignin, pigments, and water [1]. The recovery of lignin is particularly important because it has many applications, and membrane technology has been investigated as the basis of innovative recovery solutions. The concentration of lignin can be increased from 62 to 285 g∙L−1 using membranes and the recovered lignin is extremely pure. Membrane technology is also scalable and adaptable to different waste liquors from the pulp and paper industry.

  7. Hydrothermal fractionation of woody biomass: Lignin effect on sugars recovery.

    Science.gov (United States)

    Yedro, Florencia M; Cantero, Danilo A; Pascual, Marcos; García-Serna, Juan; Cocero, M José

    2015-09-01

    Subcritical water was employed to fractionate woody biomass into carbohydrates and lignin. Nine urban trees species (hardwood and softwood) from Spain were studied. The experiments were carried out in a semi-continuous reactor at 250 °C for 64 min. The hemicellulose and cellulose recovery yields were between 30%wt. and 80%wt. while the lignin content in the solid product ranged between 32%wt. and 92%wt. It was observed that an increment of solubilized lignin disfavored the hydrolysis of hemicelluloses. It was determined that the maximum extraction of hemicellulose was achieved at 20 min of solid reaction time while the extraction of celluloses not exhibited a maximum value. The hydrolysis of hemicellulose and cellulose would be governed by the hydrolysis kinetic and the polymers accessibility. In addition, the extraction of hemicellulose was negatively affected by the lignin content in the raw material while cellulose hydrolysis was not affected by this parameter.

  8. Valorization of lignin from biorefineries for fuels and chemicals

    DEFF Research Database (Denmark)

    Nielsen, Joachim Bachmann

    to deoxygenation as the majority of CO2 comes from the lignin. Solvent reaction routes were investigated in a separate study where different primaryalcohols (methanol, ethanol, 1-propanol and 1-butanol) were used. Primary reactions responsible for solvent loss were direct decomposition to gas through...... without theneed for exhaustive deoxygenation. Batch autoclave experiments on lignin supercritical solvolysis in ethanol revealed the effects of different reaction temperatures, reaction times and degrees of ligninloading on product yields and bio-oil quality. The highest oil yield of 50 wt......Direct lignin liquefaction is a promising process for lignin valorization in which ligninis treated in a solvent at elevated temperature and pressure. Liquefaction of sulfur freelignin obtained as a waste product from 2nd generation bio-ethanol production canprovide a sulfur free bio-oil which may...

  9. Treatment of Lignin and Waste residues by Flash Pyrolysis

    DEFF Research Database (Denmark)

    Jensen, Peter Arendt; Trinh, Ngoc Trung; Dam-Johansen, Kim

    Lignin, sewage sludge and macroalg ae (nonconventional biomasses) fast pyrolysis properties has been studied through experimental investigations on a la boratory Pyrolysis Centrifugal Reactor (PCR) and a model on lignin pyrolysis have been developed. Fu rthermore the nonconventional biomass...... ethanol plant a bio-oil can be produced with oil yields of 36% (daf) and an oil en ergy recovery of 45%. This is a relatively low bio-oil yield compared to other feedstock’s, however, it may increase the value of the lignin residual product, such that the lignin char is used for combustion on the ethanol...... plant, and the bio-oil is sold for use on heavy oil burners. The macroalgae is a promising feedstock w ith a high bio-oil yield of 54 wt% daf and an energy recovery of 76 % in the liquid oil. Detailed characteriza tion of the pyrolysis products in the form of bio-oil, gas and char has been performed...

  10. LIGNIN ADSORPTION AND KAPPA NUMBER IN ETHANOL PULPING

    Institute of Scientific and Technical Information of China (English)

    Yongjian Xu; Xinping Li; Meiyun Zhang

    2004-01-01

    The effect of washing temperature, washing stages and the cooking operation on the ethanol pulp had been investigated, and the reason for higher kappa number of the ethanol pulp was discussed. The results preliminarily showed that the dissolved lignin could re-adsorb to fiber surface by means of fiber classification technology and explained the questions found during the study. Some measures were taken to reduce the kappa number, the results had shown that there was obvious absorption in the ethanol pulping;lignin remained in the pulp could easily be dissolved and the pulp with lower kappa number could be obtained at a higher temperature; the kappa number could reduce by increasing washing time; it could enable dissolved lignin to separate out from the ethanol pulp and restrain the lignin absorption by blowing cooking liquid at high temperature.

  11. Lignin in Marine Environment and Its Analysis-A Review

    Institute of Scientific and Technical Information of China (English)

    LI Xianguo; ZHANG Ting; SUN Shuwen; LAN Haiqing; YU Tao

    2012-01-01

    Lignin is a group of phenolic polymers which is abundant in the woody tissues of vascular plants,and is essentially absent from all other living organisms.It has therefore been accepted as a tracer for terrestrial organic carbon (TOC) in marine environment since the 1970s.Lignin polymers are not amenable to direct chemical analysis without prior isolation.This review focused on the methods of chemical decomposition,extraction,derivatization and detection of lignin in marine environment.We described and compared several chemical decomposition methods,including nitrobenzene oxidation,alkaline cupric oxide (CuO) oxidation and thermochemolysis,and detection methods such as gas chromatography (GC),gas chromatography-mass spectrometry (GC-MS),high performance liquid chromatography (HPLC) and so on.Possible improvement of lignin analysis and the application prospects of this tracer were also discussed.

  12. Membrane Technology for the Recovery of Lignin: A Review

    Science.gov (United States)

    Humpert, Daniel; Ebrahimi, Mehrdad; Czermak, Peter

    2016-01-01

    Utilization of renewable resources is becoming increasingly important, and only sustainable processes that convert such resources into useful products can achieve environmentally beneficial economic growth. Wastewater from the pulp and paper industry is an unutilized resource offering the potential to recover valuable products such as lignin, pigments, and water [1]. The recovery of lignin is particularly important because it has many applications, and membrane technology has been investigated as the basis of innovative recovery solutions. The concentration of lignin can be increased from 62 to 285 g∙L−1 using membranes and the recovered lignin is extremely pure. Membrane technology is also scalable and adaptable to different waste liquors from the pulp and paper industry. PMID:27608047

  13. Transcription factors for modification of lignin content in plants

    Science.gov (United States)

    Wang, Huanzhong; Chen, Fang; Dixon, Richard A.

    2015-06-02

    The invention provides methods for modifying lignin, cellulose, xylan, and hemicellulose content in plants, and for achieving ectopic lignification and, for instance, secondary cell wall synthesis in pith cells, by altered regulation of a WRKY transcription factor. Nucleic acid constructs for altered WRKY-TF expression are described. Transgenic plants are provided that comprise modified pith cell walls, and lignin, cellulose, and hemicellulose content. Plants described herein may be used, for example, as improved biofuel feedstock and as highly digestible forage crops.

  14. Plants with modified lignin content and methods for production thereof

    Science.gov (United States)

    Zhao, Qiao; Chen, Fang; Dixon, Richard A.

    2014-08-05

    The invention provides methods for decreasing lignin content and for increasing the level of fermentable carbohydrates in plants by down-regulation of the NST transcription factor. Nucleic acid constructs for down-regulation of NST are described. Transgenic plants are provided that comprise reduced lignin content. Plants described herein may be used, for example, as improved biofuel feedstock and as highly digestible forage crops. Methods for processing plant tissue and for producing ethanol by utilizing such plants are also provided.

  15. Transcription factors for modification of lignin content in plants

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Huanzhong; Chen, Fang; Dixon, Richard A.

    2015-06-02

    The invention provides methods for modifying lignin, cellulose, xylan, and hemicellulose content in plants, and for achieving ectopic lignification and, for instance, secondary cell wall synthesis in pith cells, by altered regulation of a WRKY transcription factor. Nucleic acid constructs for altered WRKY-TF expression are described. Transgenic plants are provided that comprise modified pith cell walls, and lignin, cellulose, and hemicellulose content. Plants described herein may be used, for example, as improved biofuel feedstock and as highly digestible forage crops.

  16. Pinoresinol reductase 1 impacts lignin distribution during secondary cell wall biosynthesis in Arabidopsis.

    Science.gov (United States)

    Zhao, Qiao; Zeng, Yining; Yin, Yanbin; Pu, Yunqiao; Jackson, Lisa A; Engle, Nancy L; Martin, Madhavi Z; Tschaplinski, Timothy J; Ding, Shi-You; Ragauskas, Arthur J; Dixon, Richard A

    2015-04-01

    Pinoresinol reductase (PrR) catalyzes the conversion of the lignan (-)-pinoresinol to (-)-lariciresinol in Arabidopsis thaliana, where it is encoded by two genes, PrR1 and PrR2, that appear to act redundantly. PrR1 is highly expressed in lignified inflorescence stem tissue, whereas PrR2 expression is barely detectable in stems. Co-expression analysis has indicated that PrR1 is co-expressed with many characterized genes involved in secondary cell wall biosynthesis, whereas PrR2 expression clusters with a different set of genes. The promoter of the PrR1 gene is regulated by the secondary cell wall related transcription factors SND1 and MYB46. The loss-of-function mutant of PrR1 shows, in addition to elevated levels of pinoresinol, significantly decreased lignin content and a slightly altered lignin structure with lower abundance of cinnamyl alcohol end groups. Stimulated Raman scattering (SRS) microscopy analysis indicated that the lignin content of the prr1-1 loss-of-function mutant is similar to that of wild-type plants in xylem cells, which exhibit a normal phenotype, but is reduced in the fiber cells. Together, these data suggest an association of the lignan biosynthetic enzyme encoded by PrR1 with secondary cell wall biosynthesis in fiber cells.

  17. Function of the iron-binding chelator produced by Coriolus versicolor in lignin biodegradation

    Institute of Scientific and Technical Information of China (English)

    WANG Lu; YAN WenChao; CHEN JiaChuan; HUANG Feng; GAO PeiJi

    2008-01-01

    An ultrafiltered low-molecular-weight preparation of chelating compounds was isolated from a wood-containing culture of the white-rot basidiomycete Coriolus versicolor. This preparation could chelate Fe3+ and reduce Fe3+ to Fe2+, demonstrating that the substance may serve as a ferric chelator,oxygen-reducing agent, and redox-cycling molecule, which would include functioning as the electron transport carrier in Fenton reaction. Lignin was treated with the iron-binding chelator and the changes in structure were investigated by 1H-NMR, 13C-NMR, difference spectrum caused by ionization under alkaline conditions and nitrobenzene oxidation. The results indicated that the iron-binding chelator could destroy the β-O-4 bonds in etherified lignin units and insert phenolic hydroxyl groups. The low-molecular-weight chelator secreted by C. versicolor resulted in new phenolic substructures in the lignin polymer, making it susceptible to attack by laccase or manganese peroxidase. Thus, the synergic action of the iron-binding chelator and the lignocellulolytic enzymes made the substrate more accessible to degradation.

  18. Cu(II Ion Adsorption onto Hydroxymethylated Lignin-Chitosan Crosslinked Membrane

    Directory of Open Access Journals (Sweden)

    Han Shiyan

    2014-07-01

    Full Text Available A crosslinked chitosan membrane (I and a hydroxymethylated lignin-chitosan crosslinked membrane (II were prepared using glutaraldehyde as the crosslinking agent. Fourier transform infrared spectroscopy (FTIR was used to identify the chemical structures of the crosslinked membranes and the presence of an absorption peak at 1515 cm-1 indicated the presence of lignin. Scanning electron microscope (SEM images revealed that membrane (I possessed a smooth surface, while membrane (II exhibited a homogeneous embossed surface without any agglomeration. The Cu(II ion adsorption properties of both membranes were analyzed. The results indicated that the static adsorption capacities of membranes (I and (II were 195 g Cu(II/cm2 and 275 g Cu(II/cm2, respectively, and their dynamic chelation capacities were 2.89 g Cu(II/cm2 and 4.59 g Cu(II/cm2, respectively. Membrane (I was suitable only for use in aqueous solutions with pH values of 3.5 to 9.0, while membrane (II maintained its shape even in concentrated hydrochloric acid or 1 M NaOH solution. The Cu(II ion absorption properties and resistance to acid and alkali of membrane (II were superior to those of membrane (I, indicating that hydroxymethylation of the lignin-chitosan crosslinked membrane is worthy of further investigation.

  19. Function of the iron-binding chelator produced by Coriolus versicolor in lignin biodegradation.

    Science.gov (United States)

    Wang, Lu; Yan, WenChao; Chen, JiaChuan; Huang, Feng; Gao, PeiJi

    2008-03-01

    An ultrafiltered low-molecular-weight preparation of chelating compounds was isolated from a wood-containing culture of the white-rot basidiomycete Coriolus versicolor. This preparation could chelate Fe3+ and reduce Fe3+ to Fe2+, demonstrating that the substance may serve as a ferric chelator, oxygen-reducing agent, and redox-cycling molecule, which would include functioning as the electron transport carrier in Fenton reaction. Lignin was treated with the iron-binding chelator and the changes in structure were investigated by 1H-NMR, 13C-NMR, difference spectrum caused by ionization under alkaline conditions and nitrobenzene oxidation. The results indicated that the iron-binding chelator could destroy the beta-O-4 bonds in etherified lignin units and insert phenolic hydroxyl groups. The low-molecular-weight chelator secreted by C. versicolor resulted in new phenolic substructures in the lignin polymer, making it susceptible to attack by laccase or manganese peroxidase. Thus, the synergic action of the iron-binding chelator and the lignocellulolytic enzymes made the substrate more accessible to degradation.

  20. Synthesis of rare earth doped TiO2 nanorods as photocatalysts for lignin degradation.

    Science.gov (United States)

    Song, Liang; Zhao, Xueyuan; Cao, Lixin; Moon, Ji-Won; Gu, Baohua; Wang, Wei

    2015-10-28

    A two-step process is developed to synthesize rare earth doped titania nanorods (RE-TiO2 NRs) as photocatalysts for efficient degradation of lignin under simulated sunlight irradiation. In this approach, protonated titanate nanotubes with layered structures were first prepared by a hydrothermal approach, and rare earth metal ions were subsequently bound to the negatively charged surface of the synthesized titanate via electrostatic incorporation. The as-synthesized RE-TiO2 NRs after calcination generally showed much higher photocatalytic efficiencies than those of undoped TiO2 NRs or the commercial P25 TiO2 photocatalyst. Using methyl orange (MO) as a probing molecule, we demonstrate that Eu-TiO2 NRs are among the best for degrading MO, with an observed rate constant of 4.2 × 10(-3) s(-1). The La(3+), Sm(3+), Eu(3+) and Er(3+) doped TiO2 NRs also showed higher photocatalytic efficiencies in degrading MO than the commercial P25 TiO2. We further demonstrate that lignin can be photodegraded effectively and rapidly at room temperature under simulated sunlight through two reaction routes, which could be important in controlling ways of lignin depolymerization or the formation of reaction products.

  1. Function of the iron-binding chelator produced by Coriolus versicolor in lignin biodegradation

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    An ultrafiltered low-molecular-weight preparation of chelating compounds was isolated from a wood-containing culture of the white-rot basidiomycete Coriolus versicolor. This preparation could chelate Fe3+ and reduce Fe3+ to Fe2+, demonstrating that the substance may serve as a ferric chelator, oxygen-reducing agent, and redox-cycling molecule, which would include functioning as the electron transport carrier in Fenton reaction. Lignin was treated with the iron-binding chelator and the changes in structure were investigated by 1H-NMR, 13C-NMR, difference spectrum caused by ionization under alkaline conditions and nitrobenzene oxidation. The results indicated that the iron-binding chelator could destroy the β-O-4 bonds in etherified lignin units and insert phenolic hydroxyl groups. The low-molecular-weight chelator secreted by C. versicolor resulted in new phenolic substructures in the lignin polymer, making it susceptible to attack by laccase or manganese peroxidase. Thus, the synergic action of the iron-binding chelator and the lignocellulolytic enzymes made the substrate more acces- sible to degradation.

  2. Preparation and properties of lignin-epoxy resin composite

    Directory of Open Access Journals (Sweden)

    Quanfu Yin

    2012-11-01

    Full Text Available A cross-linked biomass-polymer composite with a lignin content of up to 60% was prepared by blending lignin with an epoxy resin and polyamine using a hot press molding process. The characteristics of the curing reaction of lignin with epoxy resin were studied using DSC and FTIR analysis. The effect of molding temperature and molding pressure on the mechanical properties and microstructure of the lignin/epoxy resin composite was also studied by SEM, DMA, and TG analyses. The results showed that the epoxy resin can be cured by lignin, and the curing temperature for the blends can be reduced by the introduction of a polyamine cure agent. The properties of the composite, such as bending strength, impact strength, glass-transition temperature, and thermal stability, were evidently influenced by the molding process. A good interfacial combination was formed between lignin and epoxy resin. Increasing the molding temperature and pressure proved beneficial to achieve a better interfacial combination for the composite, and the degree of ductile fracture was increased in the fracture surface of the composite.

  3. TREATMENT OF SWEET GUM LIGNIN BY LACCASE AND LMS

    Institute of Scientific and Technical Information of China (English)

    Huali Wei; Shulan Shi; Jicheng Pei

    2004-01-01

    Cellulolytic enzyme lignin (CEL) from sweet gum is treated by laccase and laccase/mediator system (LMS). Phenolic hydroxyl content of lignin is measured, and IR, GPC, 13C-NMR spectrograms are analyzed. Compared with control sample, phenolic hydroxyl content of lignin is a little higher after laccase treatment, whereas they are lower after LMS treatment. In LMS, lignin modification by laccase/ABTS is greater than by laccase/VA. It is found from IR that in lignin treated by laccase and LMS, relative content of siringyl hydroxyl group is higher, and α- conjugated carbonyl group content is a little higher. From GPC analysis, compared with control sample, molecular weight decrease after the treatment by laccase and LMS. And the decrement is greater by laccase alone than by LMS. According to 13C-NMR, relative content of carbonyl group and methoxyl group increase during the treatment by laccase alone, but the amount of them are lower after LMS treatment.And the amount of Cαand C β in β-O-4 has a little decrement after LMS treatment. It indicates that the oxidation of lignin by laccase and LMS proceed through different reaction pathways.

  4. TREATMENT OF SWEET GUM LIGNIN BY LACCASE AND LMS

    Institute of Scientific and Technical Information of China (English)

    HualiWei; ShulanShi; JichengPei

    2004-01-01

    Cellulolytic enzyme lignin (CEL) from sweet gum is treated by laccase and laccase/mediator system (LMS). Phenoli hydroxyl content of lignin is measured, and IR, GPC, 13C-NMR spectrograms are analyzed. Compar. I with control sample, phenolic hydroxyl content of lignin is a little higher after laccase treatment, whereas they are lower after LMStreatment. In LMS, lignin modification by laccase/ABTS is greater than by laccase/VA. It is found from IR that in lignin treated by laccase and LMS, relative content of siringyl hydroxyl group is higher, and α- conjugated carbonyl group content is a little higher. From GPC analysis, compared with control sample, molecular weight decrease after the treatment by laccase and LMS. And the decrement is greater bv laccase alone than by LMS. According to 13C-NMR, relative content of carbonyl group and methoxvl group increase during the treatment by laccase alone, but theamount of them are lower after LMS treatment. And the amount of Cα and Cβ in β-Ο-4 has a little decrement after LMS treatment. It indicates that the oxidation of lignin by laccase and LMS proceed through different reaction pathways.

  5. Study on biodegradation process of lignin by FTIR and DSC.

    Science.gov (United States)

    Liu, Yang; Hu, Tianjue; Wu, Zhengping; Zeng, Guangming; Huang, Danlian; Shen, Ying; He, Xiaoxiao; Lai, Mingyong; He, Yibin

    2014-12-01

    The biodegradation process of lignin by Penicillium simplicissimum was studied to reveal the lignin biodegradation mechanisms. The biodegradation products of lignin were detected using Fourier transform infrared spectroscopy (FTIR), UV-Vis spectrophotometer, different scanning calorimeter (DSC), and stereoscopic microscope. The analysis of FTIR spectrum showed the cleavage of various ether linkages (1,365 and 1,110 cm(-1)), oxidation, and demethylation (2,847 cm(-1)) by comparing the different peak values in the corresponding curve of each sample. Moreover, the differences (Tm and ΔHm values) between the DSC curves indirectly verified the FTIR analysis of biodegradation process. In addition, the effects of adding hydrogen peroxide (H2O2) to lignin biodegradation process were analyzed, which indicated that H2O2 could accelerate the secretion of the MnP and LiP and improve the enzymes activity. What is more, lignin peroxidase and manganese peroxidase catalyzed the lignin degradation effectively only when H2O2 was presented.

  6. Biobleaching of flax by degradation of lignin with laccase

    Directory of Open Access Journals (Sweden)

    Yotova, L. K.

    2007-02-01

    Full Text Available Research on lignin biodegradation has become of great interest, due to the fact that lignin is one of the most abundant renewable materials, next to cellulose. Lignin is also the substance that gives color to raw flax fibers. In order to bleach the flax and to keep its tenacity high enough for textile applications, it is necessary to remove the lignin and partially to preserve the pectin. Lignin and pectin are the main constituents of the layer which sticks the flax cells together within the multicellular technical fiber. White-rot fungi and their oxidative enzymes, laccases and peroxid-ases (lignin peroxidases and manganese peroxidases, are being applied for the biobleaching of papermaking pulp, thereby reducing the need for environmentally harmful chemicals. Some data also suggest that it is possible to use other phenolytic enzymes, such as pure laccase, for this purpose. The objective of the present work was to study the possibility of bleaching flax fibers by pure laccase and combined laccase peroxide treatment, aimed at obtaining fibers with high whiteness and well-preserved tenacity.

  7. Experiences of Kraft Lignin Functionalization by Enzymatic and Chemical Oxidation

    Directory of Open Access Journals (Sweden)

    Anna Kalliola

    2014-10-01

    Full Text Available Linear hydrophilic derivatives are expected to soften lignin and improve its utilization in composite applications. Oxidation by means of laccase in the presence of oxygen was employed in an attempt to functionalize commercial kraft lignin by vanillic acid-PEG ester and ether derivatives. Thielavia arenaria and Melanocarpus albomyces laccases at pH 6 and 8 were used. According to O2 consumption and the increase in molar mass, the tested laccases were active toward the lignin and the vanillic acid derivatives and also formed corresponding phenoxyl radicals. However, homogenous polymerization instead of cross-coupling and functionalization took place. As an alternative, lignin functionalization by the ester derivative by chemical oxidation under alkali-O2 conditions was also tested. Efficient lignin polymerization was observed. However, functionalization was not detected. Interestingly, a clear decrease in lignin glass transition temperature was obtained by an isolation procedure that included freeze-drying. This suggests that functionalization may not be necessary to induce the desired softening effect.

  8. A radioimmunoassay for lignin in plant cell walls

    Energy Technology Data Exchange (ETDEWEB)

    Dawley, R.M.

    1989-01-01

    Lignin detection and determination in herbaceous tissue requires selective, specific assays which are not currently available. A radioimmunoassay (RIA) was developed to study lignin metabolism in these tissues. A {beta}-aryl ether lignin model compound was synthesized, linked to keyhole limpet hemocyanin using a water-soluble carbodiimide, and injected into rabbits. The highest titer of the antiserum obtained was 34 {eta}g/mL of model derivatized BSA. An in vitro system was developed to characterize the RIA. The model compound was linked to amino activated polyacrylamide beads to mimic lignin in the cell walls. {sup 125}I Radiolabelled protein A was used to detect IgG antibody binding. The RIA was shown in the in vitro system to exhibit saturable binding. The amount of antibody bound decreased when the serum was diluted. Immunoelectrophoresis and competitive binding experiments confirmed that both aromatic rings of the lignin model compound had been antigenic. Chlorogenic acid, a phenolic known to be present in plant cells, did not compete for antibody binding. The RIA was used to measure lignin in milled plant samples and barley seedlings. Antiserum binding to wheat cell walls and stressed barley segments was higher than preimmune serum binding. Antibody binding to stressed barley tissue decreased following NaClO{sub 2} delignification. The RIA was found to be less sensitive than expected, so several avenues for improving the method are discussed.

  9. Characterization of anaerobic consortia coupled lignin depolymerization with biomethane generation.

    Science.gov (United States)

    Wu, Yi-Rui; He, Jianzhong

    2013-07-01

    Two sediment-free microbial consortia (LI3 and LP3) were established to depolymerize lignin under anaerobic conditions. During depolymerizing high molecular weight lignin to low molecular weight molecules, the two cultures produced biomethane up to 151.7 and 113.0 mL g(-1) total lignin. Furthermore, LI3 and LP3 could also utilize the biomass - oil palm empty fruit bunch fiber (OPEFB) to produce 190.6 and 195.6 mL methaneg(-1) total lignin in OPEFB, and at the same time improve the bioavailability of lignocellulosic matters for further enzymatic hydrolysis. The microbial community analysis by denature gradient gel electrophoresis (DGGE) and the high-density 16S rDNA gene microarray (PhyloChip) exhibited that Methanomethylovorans sp. (LI3) and Methanoculleus sp. (LP3) were the main methanogens present, and phylum Firmicutes and Bacteroidetes were mainly involved in the lignin depolymerization. The established microbial consortia with both lignin depolymerization and biomethane production provide profound application on the environmental friendly pretreatment of lignocellulosic materials.

  10. Bioconversion of lignin model compounds with oleaginous Rhodococci

    Energy Technology Data Exchange (ETDEWEB)

    Kosa, Matyas; Ragauskas, Arthur J. [Georgia Institute of Technology, Atlanta, GA (United States). Dept. of Chemistry and Biochemistry

    2012-01-15

    Although economically efficient biomass conversion depends on the utilization of the complete cell wall (biorefinery concept), including polysaccharides and lignin, current biofuels research concentrate mostly on cellulose conversion, while lignin is viewed as a side-product that is used primarily as a thermal resource. Microbiological conversion of lignin is almost exclusive to fungi, usually resulting in increased cell mass and lignolytic enzymes. Some bacteria can also degrade lignin-related compounds using the {beta}-ketoadipate pathway; for example, Rhodococcus opacus DSM 1069 can degrade coniferyl alcohol and grow on it as sole carbon source. Moreover, this strain belongs to the actinomycetes group that is also known for oleaginous species with lipid accumulation over 20%. Present work shows that R. opacus DSM 1069 and PD630 strains under nitrogen limiting conditions can convert lignin model compounds into triacylglycerols, also known as neutral lipids. 4-Hydroxybenzoic and vanillic acid lignin model compounds were used as sole carbon sources, and after brief adaptation periods, the cells not only began growing but accumulated lipids to the level of oleaginicity. These lipids were extracted for transesterification and analysis of fatty acid methyl esters showed good composition for biodiesel applications with no aromatics. Furthermore, the two strains showed distinct substrate metabolism and product profiles. (orig.)

  11. Lignin-modifying enzymes of the white rot basidiomycete Ganoderma lucidum

    Energy Technology Data Exchange (ETDEWEB)

    D/Souza, T.M.; Merritt, C.S.; Reddy, C.A.

    1999-12-01

    Ganoderma lucidum, a white rot basidiomycete widely distributed worldwide, was studied for the production of the lignin-modifying enzymes laccase, manganese-dependent peroxidase (MnP), and lignin peroxidase (LiP). Laccase levels observed in high-nitrogen shaken cultures were much greater than those seen in low-nitrogen, malt extract, or wool-grown cultures and those reported for most other white rot fungi to date. Laccase production was readily seen in cultures grown with pine or poplar as the sole carbon and energy source. Cultures containing both pine and poplar showed 5- to 10-fold-higher levels of laccase than cultures containing pine or poplar alone. Since syringyl units are structural components important in poplar lignin and other hardwoods but much less so in pine lignin and other softwoods, pine cultures were supplemented with syringic acid, and this resulted in laccase levels comparable to those seen in pine-plus-poplar cultures. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis of concentrated extracellular culture fluid from HM cultures showed two laccase activity bands, where as isoelectric focusing revealed five major laccase activity bands with estimated pIs of 3.0, 4.25, 4.5, and 5.1. Low levels of MnP activity were detected in poplar-grown cultures but not in cultures grown with pine, with pine plus syringic acid, or in HN medium. No LiP activity was seen in any of the media tested; however, probing the genomic DNA with the LiP cDNA (CLG4) from the white rot fungus Phanerochaete chrysosporium showed distinct hybridization bands suggesting the presence of lip-like sequences in G. lucidum.

  12. System analyse cellulose ethanol in combines - Combustion characterisation of lignin from cellulose based ethanol production; Systemanalys foer cellulosabaserad etanol i kombinat - Foerbraenningskarakterisering av lignin fraan cellulosabaserad etanolproduktion

    Energy Technology Data Exchange (ETDEWEB)

    Lindstedt, Jan; Wingren, Anders; Magnusson, Staffan; Wiinikka, Henrik; Westbom, Urban; Lidman, Marcus; Groenberg, Carola

    2012-02-15

    In this work 3 different hydrolysed lignin fractions produced from Sugarcane Bagasse, Spruce and Wheat Straw were burned in a 150 kW horizontal furnace equipped with a powder burner to assess the combustion behaviour of hydrolysed lignin fuels. The combustion experiments showed that the feeding properties of all three lignin fractions were better compared to ordinary wood powder

  13. Improving the pH-stability of Versatile Peroxidase by Comparative Structural Analysis with a Naturally-Stable Manganese Peroxidase.

    Science.gov (United States)

    Sáez-Jiménez, Verónica; Fernández-Fueyo, Elena; Medrano, Francisco Javier; Romero, Antonio; Martínez, Angel T; Ruiz-Dueñas, Francisco J

    2015-01-01

    Versatile peroxidase (VP) from the white-rot fungus Pleurotus eryngii is a high redox potential peroxidase of biotechnological interest able to oxidize a wide range of recalcitrant substrates including lignin, phenolic and non-phenolic aromatic compounds and dyes. However, the relatively low stability towards pH of this and other fungal peroxidases is a drawback for their industrial application. A strategy based on the comparative analysis of the crystal structures of VP and the highly pH-stable manganese peroxidase (MnP4) from Pleurotus ostreatus was followed to improve the VP pH stability. Several interactions, including hydrogen bonds and salt bridges, and charged residues exposed to the solvent were identified as putatively contributing to the pH stability of MnP4. The eight amino acid residues responsible for these interactions and seven surface basic residues were introduced into VP by directed mutagenesis. Furthermore, two cysteines were also included to explore the effect of an extra disulfide bond stabilizing the distal Ca2+ region. Three of the four designed variants were crystallized and new interactions were confirmed, being correlated with the observed improvement in pH stability. The extra hydrogen bonds and salt bridges stabilized the heme pocket at acidic and neutral pH as revealed by UV-visible spectroscopy. They led to a VP variant that retained a significant percentage of the initial activity at both pH 3.5 (61% after 24 h) and pH 7 (55% after 120 h) compared with the native enzyme, which was almost completely inactivated. The introduction of extra solvent-exposed basic residues and an additional disulfide bond into the above variant further improved the stability at acidic pH (85% residual activity at pH 3.5 after 24 h when introduced separately, and 64% at pH 3 when introduced together). The analysis of the results provides a rational explanation to the pH stability improvement achieved.

  14. Improving the pH-stability of Versatile Peroxidase by Comparative Structural Analysis with a Naturally-Stable Manganese Peroxidase.

    Directory of Open Access Journals (Sweden)

    Verónica Sáez-Jiménez

    Full Text Available Versatile peroxidase (VP from the white-rot fungus Pleurotus eryngii is a high redox potential peroxidase of biotechnological interest able to oxidize a wide range of recalcitrant substrates including lignin, phenolic and non-phenolic aromatic compounds and dyes. However, the relatively low stability towards pH of this and other fungal peroxidases is a drawback for their industrial application. A strategy based on the comparative analysis of the crystal structures of VP and the highly pH-stable manganese peroxidase (MnP4 from Pleurotus ostreatus was followed to improve the VP pH stability. Several interactions, including hydrogen bonds and salt bridges, and charged residues exposed to the solvent were identified as putatively contributing to the pH stability of MnP4. The eight amino acid residues responsible for these interactions and seven surface basic residues were introduced into VP by directed mutagenesis. Furthermore, two cysteines were also included to explore the effect of an extra disulfide bond stabilizing the distal Ca2+ region. Three of the four designed variants were crystallized and new interactions were confirmed, being correlated with the observed improvement in pH stability. The extra hydrogen bonds and salt bridges stabilized the heme pocket at acidic and neutral pH as revealed by UV-visible spectroscopy. They led to a VP variant that retained a significant percentage of the initial activity at both pH 3.5 (61% after 24 h and pH 7 (55% after 120 h compared with the native enzyme, which was almost completely inactivated. The introduction of extra solvent-exposed basic residues and an additional disulfide bond into the above variant further improved the stability at acidic pH (85% residual activity at pH 3.5 after 24 h when introduced separately, and 64% at pH 3 when introduced together. The analysis of the results provides a rational explanation to the pH stability improvement achieved.

  15. Lignin as a molecular marker of land management impacts on soil C storage and turnover

    Science.gov (United States)

    Panettieri, Marco; Rumpel, Cornelia; Dignac, Marie-France; Billiou, Daniel; Chabbi, Abad

    2017-04-01

    Implementation of temporary grassland on cropped lands may be a sustainable option to enhance the carbon storage via the accumulation of soil organic matter (SOM). However, carbon storage is not only a matter of quantity, since higher inputs of labile carbon may stimulate soil microbial and fungal communities and induce the degradation of the formerly stabilized SOM, through the so-called priming effect. Therefore, targeted strategies for carbon storage need to consider the stability of newly added SOM at long term. Recently, soil ecologist emphasized the huge spatial variability of soil structure and properties, and the fact that many ecosystem functions of SOM are only achieved if it decomposes. Thus, more attention must be paid to fluxes of carbon rather than to the quantities accumulated. The present study aims to cope with the listed problems. The aim of the study was to use lignin as a molecular marker of plant C turnover, to assess carbon storage provided by a temporary (ley) grassland system situated at the long term experimental observatory in Lusignan (http://www.soere-acbb.com/). Our conceptual approach included plots under permanent grassland, permanent cropland and bare fallow as controls. A soil fractionation into water stable aggregates has been chosen as a strategy to overcome spatial complexity, and compound specific analyses were focused on lignin phenols within the aggregates. The hypothesis of this work is that lignin turnovers may be influenced by land uses, lignin localisation within soil compartments, the nature of litter input (above vs. belowground biomass), aggregate distribution, and plant cover characteristics (crop vs. grass). To test the hypothesis, cycles of storage and degradation of lignin were studied using compound specific stable isotope probing, taking advantage of in situ labelling provided by the switches from C3 to C4 plants (i.e. grassland to continuous maize) in the experimental area. Lignin monophenols were extracted and

  16. Base-Catalyzed Depolymerization of Solid Lignin-Rich Streams Enables Microbial Conversion

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Salvachua Rodriguez, Davinia [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Katahira, Rui [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pleitner, Brenna P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Cleveland, Nicholas S [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Nolker, Michelle L [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Smith, Holly K [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Rodriguez, Alberto [Sandia National Laboratories; Baidoo, Edward E. K. [Lawrence Berkeley National Laboratory; DOE Joint BioEnergy Institute; Keasling, Jay D. [Lawrence Berkeley National Laboratory; DOE Joint BioEnergy InstituteUniversity of California, Berkeley; Technical University of Denmark; Simmons, Blake A. [Sandia National Laboratories; Lawrence Berkeley National Laboratory; DOE Joint BioEnergy Institute; Technical University of Denmark; Gladden, John M. [Sandia National Laboratories; DOE Joint BioEnergy Institute

    2017-08-01

    Lignin valorization offers significant potential to enhance the economic viability of lignocellulosic biorefineries. However, because of its heterogeneous and recalcitrant nature, conversion of lignin to value-added coproducts remains a considerable technical challenge. In this study, we employ base-catalyzed depolymerization (BCD) using a process-relevant solid lignin stream produced via deacetylation, mechanical refining, and enzymatic hydrolysis to enable biological lignin conversion. BCD was conducted with the solid lignin substrate over a range of temperatures at two NaOH concentrations, and the results demonstrate that the lignin can be partially extracted and saponified at temperatures as low as 60 degrees C. At 120 degrees C and 2% NaOH, the high extent of lignin solubility was accompanied by a considerable decrease in the lignin average molecular weight and the release of lignin-derived monomers including hydroxycinnamic acids. BCD liquors were tested for microbial growth using seven aromatic-catabolizing bacteria and two yeasts. Three organisms (Pseudomonas putida KT2440, Rhodotorula mucilaginosa, and Corynebacterium glutamicum) tolerate high BCD liquor concentrations (up to 90% v/v) and rapidly consume the main lignin-derived monomers, resulting in lignin conversion of up to 15%. Furthermore, as a proof of concept, muconic acid production from a representative lignin BCD liquor was demonstrated with an engineered P. putida KT2440 strain. These results highlight the potential for a mild lignin depolymerization process to enhance the microbial conversion of solid lignin-rich biorefinery streams.

  17. IMAGING WOOD PULP FIBRE SURFACE LIGNIN BY FLUORESCENCE CONFOCAL LASER SCANNING MICROSCOPY

    Institute of Scientific and Technical Information of China (English)

    Kecheng Li; Douglas W. Reeve

    2004-01-01

    A novel methodology for imaging wood pulp fibre surface lignin by fluorescence confocal laser scanning microscopy was developed. Various imaging modes and imaging conditions were explored for quantitative analysis. Acridine Orange was used for labelling lignin and the orthochromatic labelling condition was developed. Withthe thusly established methodology, the distribution of lignin across the fibre wall was clearly imaged. It was found that surface lignin concentration is about 2-4 times higher than bulk lignin concentration, and that high concentration of lignin was also found on the fibre lumen surfaces and pit borders.

  18. IMAGING WOOD PULP FIBRE SURFACE LIGNIN BY FLUORESCENCE CONFOCAL LASER SCANNING MICROSCOPY

    Institute of Scientific and Technical Information of China (English)

    KechengLi; DouglasW.Reeve

    2004-01-01

    A novel methodology for imaging wood pulp fibre surface lignin by fluorescence confocal laser scanning microscopy was developed. Various imaging modes and imaging conditions were explored for quantitative analysis. Acridine Orange was used for labelling lignin and the orthochromatic labelling condition was developed. With the thusly established methodology, the distribution of lignin across the fibre wall was clearly imaged. It was found that surface lignin concentration is about 2-4 times higher than bulk lignin concentration and that high concentration of lignin was also found on the fibre lumen surfaces and pit borders.

  19. Molecular architecture requirements for polymer-grafted lignin superplasticizers.

    Science.gov (United States)

    Gupta, Chetali; Sverdlove, Madeline J; Washburn, Newell R

    2015-04-07

    Superplasticizers are a class of anionic polymer dispersants used to inhibit aggregation in hydraulic cement, lowering the yield stress of cement pastes to improve workability and reduce water requirements. The plant-derived biopolymer lignin is commonly used as a low-cost/low-performance plasticizer, but attempts to improve its effects on cement rheology through copolymerization with synthetic monomers have not led to significant improvements. Here we demonstrate that kraft lignin can form the basis for high-performance superplasticizers in hydraulic cement, but the molecular architecture must be based on a lignin core with a synthetic-polymer corona that can be produced via controlled radical polymerization. Using slump tests of ordinary Portland cement pastes, we show that polyacrylamide-grafted lignin prepared via reversible addition-fragmentation chain transfer polymerization can reduce the yield stress of cement paste to similar levels as a leading commercial polycarboxylate ether superplasticizer at concentrations ten-fold lower, although the lignin material produced via controlled radical polymerization does not appear to reduce the dynamic viscosity of cement paste as effectively as the polycarboxylate superplasticizer, despite having a similar affinity for the individual mineral components of ordinary Portland cement. In contrast, polyacrylamide copolymerized with a methacrylated kraft lignin via conventional free radical polymerization having a similar overall composition did not reduce the yield stress or the viscosity of cement pastes. While further work is required to elucidate the mechanism of this effect, these results indicate that controlling the architecture of polymer-grafted lignin can significantly enhance its performance as a superplasticizer for cement.

  20. Coproduction of lignin and glucose from vine shoots by eco-friendly strategies: Toward the development of an integrated biorefinery.

    Science.gov (United States)

    Dávila, Izaskun; Gullón, Patricia; Andrés, María A; Labidi, Jalel

    2017-11-01

    The objective of this work was to study the suitability of the pretreated vine shoots as a source of lignin and to determine its structural features. The best conditions to achieve the aim of this work were 12% NaOH, 124°C and 105min, as they permitted a removal of 67.7% of the lignin present in the pretreated vine shoots and the obtaining of a solid with a 69.4% of glucan. This delignified solid was subjected to an enzymatic hydrolysis achieving a conversion of glucan to glucose close to 100%. The characterization of lignins extracted from pretreated vine shoots was carried out for the first time and the following techniques were employed: a quantitative acid hydrolysis, HPSEC, TGA, FTIR and Pyrolysis-GC/MS. With this proposal, products from the main fractions of the vine shoots (hemicellulosic oligosaccharides, lignin fragments and cellulosic substrates) could be obtained separately, being potentially suitable for further applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Ultrasound-enhanced extraction of lignin from bamboo (Neosinocalamus affinis): characterization of the ethanol-soluble fractions.

    Science.gov (United States)

    Li, Ming-Fei; Sun, Shao-Ni; Xu, Feng; Sun, Run-Cang

    2012-03-01

    Bamboo was submitted to ultrasound-assisted extraction in aqueous ethanol to evaluate the effect of ultrasonic irradiation on the dissolution of lignin. In this case, the dewaxed bamboo culms were subjected to ball milling for 48 h, and then were suspended in 95% ethanol followed by ultrasonic irradiations for varied times at 20 °C to obtain ethanol-soluble fractions. The structural and thermal properties of the ethanol-soluble fractions were comparatively investigated by chemical analysis including alkaline nitrobenzene oxidation, bound carbohydrate determination, FT-IR spectra, HSQC spectra, TG, and DTA. The results showed that the yields of the ethanol-soluble fractions were between 4.29% and 4.76% for the fractions prepared with ultrasonic irradiation time ranging from 5 to 55 min, as compared to 4.02% for the fraction prepared without ultrasonic irradiation. It was found that the lignin content of the fraction increased with the increase of the ultrasonic irradiation time. There was a slight increase of the molecular weight of the lignin with the increase of the ultrasonic irradiation time. Alkaline nitrobenzene oxidation coupled with HSQC analysis indicated that the lignin in the fractions was mainly composed of GSH type units as well as minor amounts of ferulic acids. In addition, the fraction prepared with ultrasonic irradiation exhibited a slightly higher thermal stability as compared to the fraction prepared without ultrasonic irradiation. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Degradation of lignin β-aryl ether units in Arabidopsis thaliana expressing LigD, LigF and LigG from Sphingomonas paucimobilis SYK-6

    DEFF Research Database (Denmark)

    Mnich, Ewelina; Vanholme, Ruben; Oyarce, Paula;

    2017-01-01

    -lignification modifications into the lignin structure. The three enzymes were targeted to the secretory pathway. Phenolic metabolite profiling and 2D HSQC NMR of the transgenic lines showed an increase in oxidized guaiacyl and syringyl units without concomitant increase in oxidized β-aryl-ether units, showing lignin bond...

  3. New cellulose-lignin hydrogels and their application in controlled release of polyphenols

    Energy Technology Data Exchange (ETDEWEB)

    Ciolacu, Diana, E-mail: dciolacu@icmpp.ro; Oprea, Ana Maria; Anghel, Narcis; Cazacu, Georgeta; Cazacu, Maria

    2012-04-01

    Novel superabsorbant cellulose-lignin hydrogels (CL) were prepared by a new two-step procedure consisting in dissolving cellulose in an alkaline solution with further mixing with lignin, followed by the chemical crosslinking with epichlorohydrin. The crosslinking occurrence was verified by Fourier Transform Infrared spectroscopy (FT-IR). The effect of the structure features of cellulose-lignin hydrogels on their dehydration heat was evaluated by Differential Scanning Calorimetry (DSC). The Scanning Electron Microscopy (SEM) images reveal some morphological aspects of the hydrogels. The degree as well as the rate of swelling in a mixture of water:ethanol = 19:1 were estimated. The possible application of these hydrogels as controlled release systems was tested. Polyphenols known as having a wide range of biological effects were selected to be incorporated in such hydrogels by an optimal procedure. The extract of grapes seeds from the Chambourcin type was used as a source of polyphenols (PF). The amount of the incorporated polyphenols was estimated by UV-VIS measurements. Characterization of the hydrogels containing polyphenols was performed by FTIR spectroscopy. Some parameters were estimated based on the registered spectra, as H-bond energy (E{sub H}), the asymmetric index (a/b) and the enthalpy of H-bond formation ({Delta}H). The modifications of the thermal behavior and morphology induced by the presence of the polyphenols in hydrogels were highlighted by DSC and SEM, respectively. The release of polyphenols from CL hydrogels depended on the lignin content from matrices, as assessed by spectral studies. Both loading with polyphenols and their release can be controlled by the composition of the hydrogels. The kinetic of polyphenols release was studied. - Highlights: Black-Right-Pointing-Pointer A unique method to obtain cellulose-lignin hydrogels. Black-Right-Pointing-Pointer The application of these hydrogels as controlled release systems was tested. Black

  4. Cinnamic acid increases lignin production and inhibits soybean root growth.

    Directory of Open Access Journals (Sweden)

    Victor Hugo Salvador

    Full Text Available Cinnamic acid is a known allelochemical that affects seed germination and plant root growth and therefore influences several metabolic processes. In the present work, we evaluated its effects on growth, indole-3-acetic acid (IAA oxidase and cinnamate 4-hydroxylase (C4H activities and lignin monomer composition in soybean (Glycine max roots. The results revealed that exogenously applied cinnamic acid inhibited root growth and increased IAA oxidase and C4H activities. The allelochemical increased the total lignin content, thus altering the sum and ratios of the p-hydroxyphenyl (H, guaiacyl (G, and syringyl (S lignin monomers. When applied alone or with cinnamic acid, piperonylic acid (PIP, a quasi-irreversible inhibitor of C4H reduced C4H activity, lignin and the H, G, S monomer content compared to the cinnamic acid treatment. Taken together, these results indicate that exogenously applied cinnamic acid can be channeled into the phenylpropanoid pathway via the C4H reaction, resulting in an increase in H lignin. In conjunction with enhanced IAA oxidase activity, these metabolic responses lead to the stiffening of the cell wall and are followed by a reduction in soybean root growth.

  5. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

    Energy Technology Data Exchange (ETDEWEB)

    Elder, Thomas; Berstis, Laura; Beckham, Gregg T.; Crowley, Michael F.

    2016-06-15

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the ..alpha..-O cleavage reaction is lower than that of the ..beta..-O reaction. The catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.

  6. Rapid room temperature solubilization and depolymerization of polymeric lignin at high loadings

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Jian; Dutta, Tanmoy; Parthasarathi, Ramakrishnan; Kim, Kwang Ho; Tolic, Nikola; Chu, Rosalie K.; Isern, Nancy G.; Cort, John R.; Simmons, Blake A.; Singh, Seema

    2016-10-03

    The relatively poor solubility of lignin in most pretreatment solvents remains one of the biggest challegnes in lignin valorization to improve overall biorefinery economics. In this work, rapid room temperature solubilization of lignin at high solid loadings (>30 wt%) can be easily achieved in a single step using ethylene glycol (EG). The solubilized lignin can be rapidly and quantitively recovered with the addtion of ethanol. The computational and nuclear magnetic resonance (NMR) spectroscopic studies confirm that strong hydrogen bond interactions between EG and the free hydroxyl groups present in lignin contribute to the lignin dissolution. In addition, hydrogen peroxide mediated depolymerization of dissolved lignin at low temperature (80 oC) was tested and the effect of EG molecules on depolymerization of ligin was also theoritically studied. The findings of this work provide mechanistic insights of hydrogen bond interactions in high lignin solubilization and valorization.

  7. Comparative study of organosolv lignin extracted from prairie cordgrass, switchgrass and corn stover.

    Science.gov (United States)

    Cybulska, Iwona; Brudecki, Grzegorz; Rosentrater, Kurt; Julson, James L; Lei, Hanwu

    2012-08-01

    Lignin extracted from prairie cordgrass, switchgrass, and corn stover (using ethyl acetate-ethanol-water organosolv pretreatment) was analyzed and characterized using several methods. These methods included analysis of purity (by determination of Klason lignin, carbohydrate, and ash contents), solubility (with several organic solvents), phenolic group analysis (ultraviolet ionization difference spectra, and nitrobenzene oxidation), and general functional group analysis (by (1)H NMR). Results showed that all the examined lignin samples were relatively pure (contained over 50% Klason lignin, less than 5% carbohydrate contamination, and less than 3% ash), but switchgrass-derived lignin was observed to be the purest. All the lignins were found to contain high amounts of phenolic groups, while switchgrass-derived lignin was the most phenolic, according to the ionization difference spectra. Nitrobenzene oxidation revealed that all the lignin samples contained available guaiacyl units in high amounts. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Lignin Modification for Biopolymer/Conjugated Polymer Hybrids as Renewable Energy Storage Materials.

    Science.gov (United States)

    Nilsson, Ting Yang; Wagner, Michal; Inganäs, Olle

    2015-12-07

    Lignin derivatives, which arise as waste products from the pulp and paper industry and are mainly used for heating, can be used as charge storage materials. The charge storage function is a result of the quinone groups formed in the lignin derivative. Herein, we modified lignins to enhance the density of such quinone groups by covalently linking monolignols and quinones through phenolation. The extra guaiacyl, syringyl, and hydroquinone groups introduced by phenolation of kraft lignin derivatives were monitored by (31) P nuclear magnetic resonance and size exclusion chromatography. Electropolymerization in ethylene glycol/tetraethylammonium tosylate electrolyte was used to synthesize the kraft lignin/polypyrrole hybrid films. These modifications changed the phenolic content of the kraft lignin with attachment of hydroquinone units yielding the highest specific capacity (around 70 mA h g(-1) ). The modification of softwood and hardwood lignin derivatives yielded 50 % and 23 % higher charge capacity than the original lignin, respectively.

  9. Enzymatic polymerisation and effect of fractionation of dissolved lignin from Eucalyptus globulus Kraft liquor.

    Science.gov (United States)

    Gouveia, S; Fernández-Costas, C; Sanromán, M A; Moldes, D

    2012-10-01

    The potential ability of the laccase from Myceliophthora thermophila, either alone or with low molecular weight (LMW) additives, to polymerise a dissolved lignin from Kraft liquor of eucalypt cooking was investigated. A previous study of enzymatic performance (activity and stability) was carried out using a design experiment methodology. In addition, Kraft dissolved lignin (KDL) was fractionated according to two different protocols (solvent extraction and acidic fractionation) in order to identify possible lignin fractions with noticeable polymerisation ability. KDL and its corresponding lignin fractions were treated with laccase and analysed by size exclusion chromatography and Fourier transform infrared spectroscopy. The results provide conclusive evidence of notable lignin modifications after incubation with laccase. Moreover, lignin fractionation allows to obtain lignin fractions with different chemical characteristics and polymerisation capability. Depending on the type of raw lignin, molecular weight can increase from 4- to 21-fold by means of laccase polymerisation. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. LIGNIN ADSORPTION AND KAPPA NUMBER IN ETHANOL PULPING

    Institute of Scientific and Technical Information of China (English)

    YongjianXu; XinpingLi; MeiyunZhang

    2004-01-01

    The effect of washing temperature, washing stagesand the cooking operation on the ethanol pulp hadbeen investigated, and the reason for higher kappanumber of the ethanol pulp was discussed. Theresults preliminarily showed that the dissolved lignincould re-adsorb to fiber surface by means of fiberclassification technology and explained the questionsfound during the study. Some measures were taken toreduce the kappa number, the results had shown thatthere was obvious absorption in the ethanol pulping;lignin remained in the pulp could easily be dissolvedand the pulp with lower kappa number could beobtained at a higher temperature; the kappa numbercould reduce by increasing washing time; it couldenable dissolved lignin to separate out fi'om theethanol pulp and restrain the lignin absorption byblowing cooking liquid at high temperature.

  11. Monolignol ferulate conjugates are naturally incorporated into plant lignins.

    Science.gov (United States)

    Karlen, Steven D; Zhang, Chengcheng; Peck, Matthew L; Smith, Rebecca A; Padmakshan, Dharshana; Helmich, Kate E; Free, Heather C A; Lee, Seonghee; Smith, Bronwen G; Lu, Fachuang; Sedbrook, John C; Sibout, Richard; Grabber, John H; Runge, Troy M; Mysore, Kirankumar S; Harris, Philip J; Bartley, Laura E; Ralph, John

    2016-10-01

    Angiosperms represent most of the terrestrial plants and are the primary research focus for the conversion of biomass to liquid fuels and coproducts. Lignin limits our access to fibers and represents a large fraction of the chemical energy stored in plant cell walls. Recently, the incorporation of monolignol ferulates into lignin polymers was accomplished via the engineering of an exotic transferase into commercially relevant poplar. We report that various angiosperm species might have convergently evolved to natively produce lignins that incorporate monolignol ferulate conjugates. We show that this activity may be accomplished by a BAHD feruloyl-coenzyme A monolignol transferase, OsFMT1 (AT5), in rice and its orthologs in other monocots.

  12. Monolignol ferulate conjugates are naturally incorporated into plant lignins

    Science.gov (United States)

    Karlen, Steven D.; Zhang, Chengcheng; Peck, Matthew L.; Smith, Rebecca A.; Padmakshan, Dharshana; Helmich, Kate E.; Free, Heather C. A.; Lee, Seonghee; Smith, Bronwen G.; Lu, Fachuang; Sedbrook, John C.; Sibout, Richard; Grabber, John H.; Runge, Troy M.; Mysore, Kirankumar S.; Harris, Philip J.; Bartley, Laura E.; Ralph, John

    2016-01-01

    Angiosperms represent most of the terrestrial plants and are the primary research focus for the conversion of biomass to liquid fuels and coproducts. Lignin limits our access to fibers and represents a large fraction of the chemical energy stored in plant cell walls. Recently, the incorporation of monolignol ferulates into lignin polymers was accomplished via the engineering of an exotic transferase into commercially relevant poplar. We report that various angiosperm species might have convergently evolved to natively produce lignins that incorporate monolignol ferulate conjugates. We show that this activity may be accomplished by a BAHD feruloyl–coenzyme A monolignol transferase, OsFMT1 (AT5), in rice and its orthologs in other monocots. PMID:27757415

  13. Pemanfaatan Lignin Isolat Lindi Hitam Dari Toba Pulp Lestari

    OpenAIRE

    Sah, Nasir

    2015-01-01

    Utilization of black liquor lignin isolates natural binder of Toba Pulp Lestari as asphalt reinforcement has been done. Asphalt modifier made in 9 different types of formulations with a variation ratio of lignin isolates with asphalt at 40:60 ; 35:65 ; 30:70 ; 25:75 ; 20:80 ; 15:85 ; 10:90 ; 5:95 and 0:100 (b/b) in 100 grams, the addition of 300 grams of fine sand aggregate, and processed in an extruder at a temperature of 150oC. Mechanical properties and thermal properties of tested asphalt ...

  14. Catalytic hydrotreatment of Alcell lignin fractions using a Ru/C catalyst

    NARCIS (Netherlands)

    Kloekhorst, Arjan; Heeres, Hero Jan

    2016-01-01

    We here report the catalytic hydrotreatment of three different Alcell lignin fractions using a Ru/C catalyst in a batch reactor set-up (400 °C, 4 h, 100 bar H2 intake, 5 wt% catalyst on lignin). The fractions, obtained by a solvent fractionation scheme from Alcell lignin, differ in composition and m

  15. Paving the Way for Lignin Valorisation : Recent Advances in Bioengineering, Biorefining and Catalysis

    NARCIS (Netherlands)

    Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T; Ralph, John; Kennema, Marco; Bruijnincx, Pieter C A; Weckhuysen, Bert M

    2016-01-01

    Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of

  16. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen

    NARCIS (Netherlands)

    Zakzeski, J.; Weckhuysen, B.M.

    2011-01-01

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compo

  17. Synthesis and characterization of biodegradable lignin nanoparticles with tunable surface properties

    NARCIS (Netherlands)

    Richter, Alexander P.; Bharti, Bhuvnesh; Armstrong, Hinton B.; Brown, Joseph S.; Plemmons, Dayne; Paunov, Vesselin N.; Stoyanov, Simeon D.; Velev, Orlin D.

    2016-01-01

    Lignin nanoparticles can serve as biodegradable carriers of biocidal actives with minimal environmental footprint. Here we describe the colloidal synthesis and interfacial design of nanoparticles with tunable surface properties using two different lignin precursors, Kraft (Indulin AT) lignin and

  18. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen

    NARCIS (Netherlands)

    Zakzeski, J.; Weckhuysen, B.M.

    2011-01-01

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model

  19. The Paleozoic Origin of Enzymatic Lignin Decomposition Reconstructed from 31 Fungal Genomes

    Science.gov (United States)

    Dimitrios Floudas; Manfred Binder; Robert Riely; Kerrie Barry; Robert A. Blanchette; Bernard Henrissat; Angel T. Martínez; Robert Otillar; Joseph W. Spatafora; Jagjit S. Yadav; Andrea Aerts; Isabelle Benoit; Alex Boyd; Alexis Carlson; Alex Copeland; Pedro M. Coutinho; Ronald P. deVries; Patricia Ferreira; Keisha Findley; Brian Foster; Jill Gaskell; Dylan Glotzer; Pawe³ Górecki; Joseph Heitman; Cedar Hesse; Chiaki Hori; Kiyohiko Igarashi; Joel A. Jurgens; Nathan Kallen; Phil Kersten; Annegret Kohler; Ursula Kües; T. K. ArunKumar; Alan Kuo; Kurt LaButti; Luis F. Larrondo; Erika Lindquist; Albee Ling; Vincent Lombard; Susan Lucas; Taina Lundell; Rachael Martin; David J. McLaughlin; Ingo Morgenstern; Emanuelle Morin; Claude Murat; Laszlo G. Nagy; Matt Nolan; Robin A. Ohm; Aleksandrina Patyshakuliyeva; Antonis Rokas; Francisco J. Ruiz-Dueñas; Grzegorz Sabat; Asaf Salamov; Masahiro Samejima; Jeremy Schmutz; Jason C. Slot; Franz St. John; Jan Stenlid; Hui Sun; Sheng Sun; Khajamohiddin Syed; Adrian Tsang; Ad Wiebenga; Darcy Young; Antonio Pisabarro; Daniel C. Eastwood; Francis Martin; Dan Cullen; Igor V. Grigoriev; David S. Hibbett

    2012-01-01

    Wood is a major pool of organic carbon that is highly resistant to decay, owing largely to the presence of lignin. The only organisms capable of substantial lignin decay are white rot fungi in the Agaricomycetes, which also contains non–lignin-degrading brown rot and ectomycorrhizal species. Comparative analyses of 31 fungal genomes (12 generated for this study)...

  20. Coupling and reactions of 5- hydroxyconiferyl alcohol in lignin formation

    Science.gov (United States)

    Thomas Elder; Laura Berstis; Gregg T. Beckham; Michael F. Crowley

    2016-01-01

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-...

  1. Synthesis and characterization of biodegradable lignin nanoparticles with tunable surface properties

    NARCIS (Netherlands)

    Richter, Alexander P.; Bharti, Bhuvnesh; Armstrong, Hinton B.; Brown, Joseph S.; Plemmons, Dayne; Paunov, Vesselin N.; Stoyanov, Simeon D.; Velev, Orlin D.

    2016-01-01

    Lignin nanoparticles can serve as biodegradable carriers of biocidal actives with minimal environmental footprint. Here we describe the colloidal synthesis and interfacial design of nanoparticles with tunable surface properties using two different lignin precursors, Kraft (Indulin AT) lignin and

  2. Precipitation and valorisation of lignin obtained from South African Kraft mill black liquor

    CSIR Research Space (South Africa)

    Namane, Mpho

    2016-04-01

    Full Text Available was established. Lignin was precipitated from kraft mill black liquor by utilising sulphuric acid and three organic acids (acetic, citric, and formic acids). During recovery of the lignin, it was noticed that recovery of the precipitated lignin was a long...

  3. 木质素/热塑性塑料复合材料界面增容的研究进展%Progress of interfacial compatibilization methods of lignin/thermoplast composites

    Institute of Scientific and Technical Information of China (English)

    陈福泉; 赵永青; 冯彦洪; 瞿金平

    2014-01-01

    Lignin is mixed into thermoplast as organic particulate filler, which resolves the tough problems of resource utilization of black liquor from paper industry, growing tension of petroleum feedstock and increasing environmental pollution. The compatibility between lignin and thermoplast is directly related to application and development of lignin in the plastics industry. This paper begins with an overview of the structure and properties of lignin and performance analysis of lignin/thermoplastic composites, and then elaborates the methods and principles of interfacial compatibilization between lignin and thermoplast. The methods of compatibilization are divided into adding compatibilizer, modifying lignin and modifying thermoplastics, and the three methods are compared and analyzed. The methods of adding compatibilizer and modifying thermoplastics are more commonly used than the modifying lignin for interfacial compatibilizing of the composites. Esterified lignin has better compatibilization than alkylated lignin. Then alternate and compounded use of the compatibilizing methods for lignin-based composites are reviewed. Finally, future research directions and ideas of compatibilization in lignin/thermoplastic composites are discussed.%将木质素作为一种有机颗粒填料添加到热塑性塑料中,可解决造纸黑液资源化利用、石油原料日渐紧张以及环境污染加剧等严峻问题。而木质素与热塑性塑料之间相容性直接影响木质素在塑料工业中的应用与发展。首先简要概述了木质素结构与性质和木质素/热塑性塑料复合材料的性能分析,然后系统地阐述国内外研究木质素/热塑性塑料复合材料界面增容方法及其原理;增容方法按添加相容剂、改性木质素和改性塑料进行归类,并对3种增容方法进行比较分析;接着综述了木质素复合材料中增容方法的交叉复合使用;最后对未来木质素/热塑性塑

  4. Lignin-based carbon fibers: Carbon nanotube decoration and superior thermal stability

    KAUST Repository

    Xu, Xuezhu

    2014-08-23

    Lignin-based carbon fibers (CFs) decorated with carbon nanotubes (CNTs) were synthesized and their structure, thermal stability and wettability were systematically studied. The carbon fiber precursors were produced by electrospinning lignin/polyacrylonitrile solutions. CFs were obtained by pyrolyzing the precursors and CNTs were subsequently grown on the CFs to eventually achieve a CF–CNT hybrid structure. The processes of pyrolysis and CNT growth were conducted in a tube furnace using different conditions and the properties of the resultant products were studied and compared. The CF–CNT hybrid structure produced at 850 °C using a palladium catalyst showed the highest thermal stability, i.e., 98.3% residual weight at 950 °C. A mechanism for such superior thermal stability was postulated based on the results from X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, and electron energy loss spectroscopy analyses. The dense CNT decoration was found to increase the hydrophobicity of the CFs.

  5. 白蚁肠道微生物降解木质素研究进展%Research Progress on the Degradation of Lignin by Termites Intestinal Microflora

    Institute of Scientific and Technical Information of China (English)

    张来丽; 李刚; 毛润乾

    2011-01-01

    It is of great sigificance to study the lignin degradation mechanism of termite, one of the most important wood-eating insect in nature, as degradation of lignin is the biggest obstacle in fiber ethanol production.The internal structure of termites and the place the intestinal microflora plays in lignin degradation were summarized in this paper.%降解木质素是制造纤维乙醇的最大障碍,而白蚁是自然界中最重要的食木昆虫,研究白蚁降解木质素的机制意义重大.系统概述白蚁的内部结构及其肠道微生物在木质素降解中所起的作用.

  6. Application of Lignin as Antioxidant in Styrene Butadiene Rubber Composite

    Science.gov (United States)

    Liu, Shusheng; Cheng, Xiansu

    2010-11-01

    Lignin isolated from enzymatic hydrolyzed cornstalks (EHL) is a renewable natural polymer, and rubber is one of the most important polymer materials. The application of EHL in rubber industry is of great significance. The influence of EHL and antioxidant RD on the vulcanizing characteristics, thermal oxidative aging stability under free condition, and water extraction resistance of styrene-butadiene rubber (SBR) were investigated. The effect of EHL/antioxidant D composite antioxidant on the thermal oxidative ageing of SBR was also evaluated. Results showed that the protection of SBR from thermal oxidative aging by EHL/antioxidant D composite antioxidant was superior to that of antioxidant D. This is because EHL molecules have hindered phenol group and have excellent auxiliary antioxidant role with antioxidant D. Moreover, the influence of EHL on the vulcanizing characteristics of SBR compounds was better than that of antioxidant RD, and EHL can reduce the cure rate and increase the optimum cure time. It is because that the EHL molecules have hindered phenol group and methoxy group, which can form a special structure to capture free radical and terminate the chain reaction. The retained tensile strength of SBR compounds with EHL was similar to that of the samples with antioxidant RD, while the retained elongation at break of SBR compounds with EHL was higher than that of the samples with antioxidant RD. In addition, the SBR compounds with EHL have a good water extraction resistance property, which was similar to the samples with antioxidant RD. This is because EHL have large molecular weight, good stability and low solubility in water. In conclusion, due to the low price, abundant resources, non-toxic and pollution-free, etc., EHL will have broad application prospect.

  7. Fast microwave-assisted acidolysis: a new biorefinery approach for the zero-waste utilisation of lignocellulosic biomass to produce high quality lignin and fermentable saccharides.

    Science.gov (United States)

    Zhou, Long; Santomauro, Fabio; Fan, Jiajun; Macquarrie, Duncan; Clark, James; Chuck, Christopher J; Budarin, Vitaliy

    2017-09-21

    Generally, biorefineries convert lignocellulosic biomass into a range of biofuels and further value added chemicals. However, conventional biorefinery processes focus mainly on the cellulose and hemicellulose fractions and therefore produce only low quality lignin, which is commonly burnt to provide process heat. To make full use of the biomass, more attention needs to be focused on novel separation techniques, where high quality lignin can be isolated that is suitable for further valorisation into aromatic chemicals and fuel components. In this paper, three types of lignocellulosic biomass (softwood, hardwood and herbaceous biomass) were processed by microwave-assisted acidolysis to produce high quality lignin. The lignin from the softwood was isolated largely intact in the solid residue after acidolysis. For example, a 10 min microwave-assisted acidolysis treatment produced lignin with a purity of 93% and in a yield of 82%, which is superior to other conventional separation methods reported. Furthermore, py-GC/MS analysis proved that the isolated lignin retained the original structure of native lignin in the feedstock without severe chemical modification. This is a large advantage, and the purified lignin is suitable for further chemical processing. To assess the suitability of this methodology as part of a biorefinery system, the aqueous phase, produced after acidolysis of the softwood, was characterised and assessed for its suitability for fermentation. The broth contained some mono- and di-saccharides but mainly contained organic acids, oligosaccharides and furans. While this is unsuitable for S. cerevisiae and other common ethanol producing yeasts, two oleaginous yeasts with known inhibitor tolerances were selected: Cryptococcus curvatus and Metschnikowia pulcherrima. Both yeasts could grow on the broth, and demonstrated suitable catabolism of the oligosaccharides and inhibitors over 7 days. In addition, both yeasts were shown to be able to produce an oil

  8. A comparison of various lignin-extraction methods to enhance the accessibility and ease of enzymatic hydrolysis of the cellulosic component of steam-pretreated poplar.

    Science.gov (United States)

    Tian, Dong; Chandra, Richard P; Lee, Jin-Suk; Lu, Canhui; Saddler, Jack N

    2017-01-01

    subsequent enzymatic hydrolysis. The second-stage pretreatments varied in their ability to solubilize and extract the lignin component of steam-pretreated poplar while enhancing the enzymatic hydrolysis of the resulting cellulose-rich residual fractions. Although DES extraction was more selective in extracting lignin from the steam-pretreated substrates, the organosolv and soda/AQ post treatments disrupted the cellulose structure to a greater extent while enhancing the ease of enzymatic hydrolysis. Graphical abstractEffective hemicellulose removal via steam pretreatment followed by subsequent lignin extraction under acidic, alkaline or solvolytic conditions results in a highly accessible, more readily hydrolysed cellulose fraction.

  9. Surface properties of woody thin boards composed of commercially available lignin and cellulose: Relationship between the orientation of lignin and water repellency

    Energy Technology Data Exchange (ETDEWEB)

    Shimanouchi, Toshinori; Kamba, Tomoya; Yang, Wei [Graduate School of Environmental and Life Science, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530 (Japan); Aoyagi, Satoka [Department of Material and Lie Science, Seikei University, 3-3-1 Musashino, Tokyo 180-8633 (Japan); Kimura, Yukitaka, E-mail: yktkkimu@cc.okayama-u.ac.jp [Graduate School of Environmental and Life Science, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530 (Japan)

    2015-08-30

    Highlights: • Woody thin boards were formed by adequate ratio of lignin/cellulose/moisture. • Component ratio of lignin/cellulose/moisture determined water repellency. • Increase of water repellency resulted from the surface orientation of lignin. - Abstract: Woody thin boards were prepared from lignin, cellulose, and water by compression molding at 180 °C and 25 MPa for 10 min. Boards with higher contact angles gave lower values of relative permittivity on their surface. Attenuated-total reflection Fourier transfer infrared spectroscopy suggested that more lignin existed on the surface of the boards with the high contact angle, which was also supported by scanning electron microscopy and atomic force microscopy. Our findings thus revealed that the orientation of lignin at the surface resulted in increased hydrophobicity of the surface and contributed to the enhancement of water repellency.

  10. Switchgrass contains two cinnamyl alcohol dehydrogenases involved in lignin formation

    Science.gov (United States)

    Switchgrass (Panicum virgatum L.) is a perennial polyploid grass with considerable potential as a bioenergy species. Many aspects of its biology and cell wall development are yet to be elucidated. Lignin content of cell walls is one of the key determinants of biomass quality and is a negative trai...<