Biodegradation of phenol-formaldehyde resins modified with commercial lignins

Energy Technology Data Exchange (ETDEWEB)

Bernard, M.; Nicolau, V. V. [Universidad Tecnologica Nacional (UTN), Cordoba (Argentina); Sponon, M.; Estenoz, D.A. [Instituto de Desarrollo Tecnologico para la Industria Quimica (INTEC/UNL/CONICET), Santa Fe (Argentina)

2014-07-01

Full text: In this work the biodegradation of partially-modified resols with 10% w/w of sodium lignosulfonate and 10 and 20 % w/w of Kraft lignin type is studied. The experimental work involved preliminary studies of biodegradation in Petri dish (clear zones), the degradation of resols by enzymatic attack of Pseudomonas aeruginosa under aerobic conditions for a period of 200 days and the characterization of the polymers before and after biodegradation by FT-IR and RMN spectroscopy, gas chromatography (GC) and scanning electron microscopy (SEM). The number of viable cells showed a significant increase during the process. However, the gravimetric analysis was not sufficient to check the biodegradation. The results indicated that endocellular enzymes could be involved. It was observed that the presence of low concentrations of toxic substances released during degradation of the material may have inhibitory effects. Resoles were synthesized in Centro S. A. San Francisco Cordoba, Argentina. (author)

Large-Scale Membrane- and Lignin-Modified Adsorbent-Assisted Extraction and Preconcentration of Triazine Analogs and Aflatoxins

OpenAIRE

Hu, Shun-Wei; Chen, Shushi

2017-01-01

The large-scale simultaneous extraction and concentration of aqueous solutions of triazine analogs, and aflatoxins, through a hydrocarbon-based membrane (e.g., polyethylene, polyethylene/polypropylene copolymer) under ambient temperature and atmospheric pressure is reported. The subsequent adsorption of analyte in the extraction chamber over the lignin-modified silica gel facilitates the process by reducing the operating time. The maximum adsorption capacity values for triazine analogs and af...

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.

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

Science.gov (United States)

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. © 2015 American Society of Plant Biologists. All rights reserved.

The comparative kinetic analysis of Acetocell and Lignoboost® lignin pyrolysis: the estimation of the distributed reactivity models.

Science.gov (United States)

Janković, Bojan

2011-10-01

The non-isothermal pyrolysis kinetics of Acetocell (the organosolv) and Lignoboost® (kraft) lignins, in an inert atmosphere, have been studied by thermogravimetric analysis. Using isoconversional analysis, it was concluded that the apparent activation energy for all lignins strongly depends on conversion, showing that the pyrolysis of lignins is not a single chemical process. It was identified that the pyrolysis process of Acetocell and Lignoboost® lignin takes place over three reaction steps, which was confirmed by appearance of the corresponding isokinetic relationships (IKR). It was found that major pyrolysis stage of both lignins is characterized by stilbene pyrolysis reactions, which were subsequently followed by decomposition reactions of products derived from the stilbene pyrolytic process. It was concluded that non-isothermal pyrolysis of Acetocell and Lignoboost® lignins can be best described by n-th (n>1) reaction order kinetics, using the Weibull mixture model (as distributed reactivity model) with alternating shape parameters. Copyright © 2011 Elsevier Ltd. All rights reserved.

Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products

International Nuclear Information System (INIS)

Zhou, Shuai; Pecha, Brennan; Kuppevelt, Michiel van; McDonald, Armando G.; Garcia-Perez, Manuel

2014-01-01

The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Pseudotsuga menziesii) wood was extracted using the milled wood enzyme lignin isolation method. Slow pyrolysis using a microscope with hot-stage captured the liquid formation (>150 °C), shrinking, swelling (foaming), and evaporation behavior of lignin intermediates. The activation energy (E a ) for 5–80% conversions was 213 kJ mol −1 , and the pre-exponential factor (log A) was 24.34. Fast pyrolysis tests in a wire mesh reactor were conducted (300–650 °C). The formation of the liquid intermediate was visualized with a fast speed camera (250 Hz), showing the existence of three well defined steps: formation of lignin liquid intermediates, foaming and liquid intermediate swelling, and evaporation and droplet shrinking. GC/MS and UV-Fluorescence of the mesh reactor condensate revealed lignin oligomer formation but no mono-phenols were seen. An increase in pyrolytic lignin yield was observed as temperature increased. The molar mass determined by ESI-MS was not affected by pyrolysis temperature. SEM of the char showed a smooth surface with holes, evidence of a liquid intermediate with foaming; bursting from these foams could be responsible for the removal of lignin oligomers. Py-GC/MS studies showed the highest yield of guaiacol compounds at 450–550 °C. - Highlights: • The formation of a liquid intermediate phase is a critical step during lignin pyrolysis. • The lignin oligomers are thermally ejected from the liquid intermediate phase. • The mono-phenols are formed mainly from the secondary reactions of lignin oligomers

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.

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.

Enzymatic Synthesis of Lignin-Based Concrete Dispersing Agents.

Science.gov (United States)

Jankowska, Dagmara; Heck, Tobias; Schubert, Mark; Yerlikaya, Alpaslan; Weymuth, Christophe; Rentsch, Daniel; Schober, Irene; Richter, Michael

2018-03-15

Lignin is the most abundant aromatic biopolymer, functioning as an integral component of woody materials. In its unmodified form it shows limited water solubility and is relatively unreactive, so biotechnological lignin valorisation for high-performance applications is greatly underexploited. Lignin can be obtained from the pulp and paper industry as a by-product. To expand its application, a new synthesis route to new dispersing agents for use as concrete additives was developed. The route is based on lignin functionalisation by enzymatic transformation. Screening of lignin-modifying systems resulted in functionalised lignin polymers with improved solubility in aqueous systems. Through grafting of sulfanilic acid or p-aminobenzoic acid by fungal laccases, lignin became soluble in water at pH≤4 or pH≤7, respectively. Products were analysed and evaluated in miniaturised application tests in cement paste and mortar. Their dispersing properties match the performance criteria of commercially available lignosulfonates. The study provides examples of new perspectives for the use of lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of Different Lignin Fractions on Saccharification Efficiency in Diverse Species of the Bioenergy Crop Miscanthus

NARCIS (Netherlands)

Weijde, van der Tim; Torres Salvador, Andres Francisco; Dolstra, Oene; Dechesne, Annemarie; Visser, Richard G.F.; Trindade, Luisa M.

2016-01-01

Lignin is a key factor limiting saccharification of lignocellulosic feedstocks. In this comparative study, various lignin methods—including acetyl bromide lignin (ABL), acid detergent lignin (ADL), Klason lignin (KL), and modified ADL and KL determination methods—were evaluated for their

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.

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

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

International Nuclear Information System (INIS)

El-Zawawy, Waleed K.; Ibrahim, Maha M.; Belgacem, Mohamed Naceur; Dufresne, Alain

2011-01-01

Highlights: ► 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. ► 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. ► 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 the change of color for the resulting polymer film.

Nitroxyl-mediated oxidation of lignin and polycarboxylated products

Energy Technology Data Exchange (ETDEWEB)

Stahl, Shannon S.; Rafiee, Mohammad

2018-02-27

Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Understanding the fast pyrolysis of lignin.

Science.gov (United States)

Patwardhan, Pushkaraj R; Brown, Robert C; Shanks, Brent H

2011-11-18

In the present study, pyrolysis of corn stover lignin was investigated by using a micro-pyrolyzer coupled with a GC-MS/FID (FID=flame ionization detector). The system has pyrolysis-vapor residence times of 15-20 ms, thus providing a regime of minimal secondary reactions. The primary pyrolysis product distribution obtained from lignin is reported. Over 84 % mass balance and almost complete closure on carbon balance is achieved. In another set of experiments, the pyrolysis vapors emerging from the micro-pyrolyzer are condensed to obtain lignin-derived bio-oil. The chemical composition of the bio-oil is analyzed by using GC-MS and gel permeation chromatography techniques. The comparison between results of two sets of experiments indicates that monomeric compounds are the primary pyrolysis products of lignin, which recombine after primary pyrolysis to produce oligomeric compounds. Further, the effect of minerals (NaCl, KCl, MgCl(2), and CaCl(2)) and temperature on the primary pyrolysis product distribution is investigated. The study provides insights into the fundamental mechanisms of lignin pyrolysis and a basis for developing more descriptive models of biomass pyrolysis. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural characterization of lignin from grape stalks (Vitis vinifera L.).

Science.gov (United States)

Prozil, Sónia O; Evtuguin, Dmitry V; Silva, Artur M S; Lopes, Luísa P C

2014-06-18

The chemical structure of lignin from grape stalks, an abundant waste of winemaking, has been studied. The dioxane lignin was isolated from extractive- and protein-free grape stalks (Vitis vinifera L.) by modified acidolytic procedure and submitted to a structural analysis by wet chemistry (nitrobenzene and permanganate oxidation (PO)) and spectroscopic techniques. The results obtained suggest that grape stalk lignin is an HGS type with molar proportions of p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) units of 3:71:26. Structural analysis by (1)H and (13)C NMR spectroscopy and PO indicates the predominance of β-O-4' structures (39% mol) in grape stalk lignin together with moderate amounts of β-5', β-β, β-1', 5-5', and 4-O-5' structures. NMR studies also revealed that grape lignin should be structurally associated with tannins. The condensation degree of grape stalks lignin is higher than that of conventional wood lignins and lignins from other agricultural residues.

Coconut coir pith lignin: A physicochemical and thermal characterization.

Science.gov (United States)

Asoka Panamgama, L; Peramune, P R U S K

2018-07-01

The structural and thermal features of coconut coir pith lignin, isolated by three different extraction protocols incorporating two different energy supply sources, were characterized by different analytical tools. The three different chemical extraction protocols were alkaline - 7.5% (w/v) NaOH, organosolv - 85% (v/v) formic and acetic acids at 7:3 (v/v) ratio and polyethylene glycol (PEG): water ratio at 80:20wt%. The two sources of energy were thermal or microwave. Raw lignins were modified by epichlorohydrin to enhance reactivity, and the characteristics of raw and modified lignins were comparatively analysed. Using the thermal energy source, the alkaline and organosolv processes obtained the highest and lowest lignin yields of 26.4±1.5wt% and 3.4±0.2wt%, respectively, as shown by wet chemical analysis. Specific functional group analysis by Fourier transform infrared spectra (FTIR) revealed that significantly different amounts of hydroxyl and carbonyl groups exist in alkaline, organosolv and PEG lignins. Thermogravimetric analysis (TGA) illustrated that the lowest degradation onset temperature was recorded for organosolv lignin, and the overall order was organosolvlignin extraction from coir pith can be performed efficiently with several protocols and that those methods offer practical value to industry. Copyright © 2018 Elsevier B.V. All rights reserved.

Advances in the chemical utilization of alkali lignin

International Nuclear Information System (INIS)

Van der Klashorst, G.H.

1985-06-01

Large quantities of alkali lignin are produced as by-products by the South African pulping industry. The potential utilization of industrial soda/anthraquinone (soda/AQ) eucalyptus, kraft pine and soda bagasse lignin was subsequently investigated. The molecular mass distributions of the three lignins were similar when determined by high pressure gel permeation chromatography (HP-GPC). The quantitative and quanlitative occurrence of various low molecular mass lignin fragments in the different spent liquors, on the other hand, indicated that the three lignins have substantial chemical differences. Analysis of the purified degraded lignins by NMR, methoxyl content determinations, elemental analysis, carbohydrate content determinations etc., quantified various of the chemical properties of the lignin. The properties of the three lignins were ultimately used to make recommendations regarding the potential use of each lignin. One such application was investigated and it was shown that soda bagasse lignin can be used successfully in phenol formaldehyde resin applications. The reaction of formaldehyde with lignin model compounds in acidic medium was also investigated. This reaction was shown to give fast crosslinking of alkyl substituted phenolic and etherified phenolic lignin model compounds at positions meta to the aromatic hydroxy groups

Demonstration of Lignin-to-Peroxidase Direct Electron Transfer

Science.gov (United States)

Sáez-Jiménez, Verónica; Baratto, Maria Camilla; Pogni, Rebecca; Rencoret, Jorge; Gutiérrez, Ana; Santos, José Ignacio; Martínez, Angel T.; Ruiz-Dueñas, Francisco Javier

2015-01-01

Versatile peroxidase (VP) is a high redox-potential peroxidase of biotechnological interest that is able to oxidize phenolic and non-phenolic aromatics, Mn2+, and different dyes. The ability of VP from Pleurotus eryngii to oxidize water-soluble lignins (softwood and hardwood lignosulfonates) is demonstrated here by a combination of directed mutagenesis and spectroscopic techniques, among others. In addition, direct electron transfer between the peroxidase and the lignin macromolecule was kinetically characterized using stopped-flow spectrophotometry. VP variants were used to show that this reaction strongly depends on the presence of a solvent-exposed tryptophan residue (Trp-164). Moreover, the tryptophanyl radical detected by EPR spectroscopy of H2O2-activated VP (being absent from the W164S variant) was identified as catalytically active because it was reduced during lignosulfonate oxidation, resulting in the appearance of a lignin radical. The decrease of lignin fluorescence (excitation at 355 nm/emission at 400 nm) during VP treatment under steady-state conditions was accompanied by a decrease of the lignin (aromatic nuclei and side chains) signals in one-dimensional and two-dimensional NMR spectra, confirming the ligninolytic capabilities of the enzyme. Simultaneously, size-exclusion chromatography showed an increase of the molecular mass of the modified residual lignin, especially for the (low molecular mass) hardwood lignosulfonate, revealing that the oxidation products tend to recondense during the VP treatment. Finally, mutagenesis of selected residues neighboring Trp-164 resulted in improved apparent second-order rate constants for lignosulfonate reactions, revealing that changes in its protein environment (modifying the net negative charge and/or substrate accessibility/binding) can modulate the reactivity of the catalytic tryptophan. PMID:26240145

Corn stover lignin is modified differently by acetic acid compared to sulfuric acid

NARCIS (Netherlands)

Mouthier, Thibaut; Appeldoorn, Maaike M.; Pel, Herman; Schols, Henk A.; Gruppen, Harry; Kabel, Mirjam A.

2018-01-01

In this study, two acid catalysts, acetic acid (HAc) and sulfuric acid (H2SO4), were compared in thermal pretreatments of corn stover, in particular to assess the less understood fate of lignin. HAc-insoluble lignin, analyzed by pyrolysis GC–MS, showed decreasing levels (%) of Cα-oxidized (from 3.7

Reactivity improvement of cellulolytic enzyme lignin via mild hydrothermal modification.

Science.gov (United States)

Ma, Zhuoming; Tang, Jiafa; Li, Shujun; Suo, Enxiang

2017-12-01

Isolated by the cellulolytic enzyme lignin (CEL) process, water-alcohol (1:1, v/v) was introduced as co-solvent in the process of the hydrothermal treatment. The modification parameters such as reaction temperature and time, solid-to-liquid ratio, and catalysts (NaOH and NaOAlO 2 ) have been investigated in terms of the specific lignin properties, such as the phenolic hydroxyl content (OH phen ), DPPH free radical scavenging rate, and formaldehyde value. The CELs were also characterized by GPC, FT-IR and 1 H NMR spectroscopy, and Py-GC/MS. The key data are under optimal lignin modification conditions (solid-to-liquid ratio of 1:10 (w/v) and a temperature of 250°C for 60min) are: OH phen content: 2.50mmol/g; half maximal inhibitory concentration (IC 50 ) towards DPPH free radicals: 88.2mg/L; formaldehyde value: 446.9g/kg). Both base catalysts decrease the residue rate, but phenol reactivities of the products were also detracted. Py-GC/MS results revealed that modified lignin had a higher phenolic composition than the CEL did, especially the modified lignin without catalyst (ML), which represented 74.51% phenolic content. Copyright © 2017. Published by Elsevier Inc.

Polymerization reactivity of sulfomethylated alkali lignin modified with horseradish peroxidase.

Science.gov (United States)

Yang, Dongjie; Wu, Xiaolei; Qiu, Xueqing; Chang, Yaqi; Lou, Hongming

2014-03-01

Alkali lignin (AL) was employed as raw materials in the present study. Sulfomethylation was conducted to improve the solubility of AL, while sulfomethylated alkali lignin (SAL) was further polymerized by horseradish peroxidase (HRP). HRP modification caused a significant increase in molecular weight of SAL which was over 20 times. It was also found to increase the amount of sulfonic and carboxyl groups while decrease the amount of phenolic and methoxyl groups in SAL. The adsorption quantity of self-assembled SAL film was improved after HRP modification. Sulfonation and HRP modification were mutually promoted. The polymerization reactivity of SAL in HRP modification was increased with its sulfonation degree. Meanwhile, HRP modification facilitated SAL's radical-sulfonation reaction. Copyright © 2014. Published by Elsevier Ltd.

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.

Comparison studies on soda lignin and soda-anthraquinone lignin

International Nuclear Information System (INIS)

Ibrahim, M.N.M; Yusof, N.N.M.; Hashim, A.

2007-01-01

Soda lignin and soda anthraquinone lignin were compared in this study. The physico-chemical properties and structural features of the isolated lignin were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet (UV), ash test, Carbon-Hydrogen-Nitrogen (CHN) analyzer, Nuclear Magnetic Resonance ( 13 C-NMR) and High Performance Liquid Chromatography (HPLC). Nitrobenzene oxidation was performed on these two types of lignin especially for the HPLC analysis. Based on the CHN, 13 C-NMR and UV results there were no significant differences between soda lignin and soda anthraquinone lignin. The FTIR results also showed that there were no significant differences in terms of functional groups that exist in both lignins. (author)

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Thermosetting Epoxies Based on Fractionated and Well-Characterized Lignins.

Science.gov (United States)

Gioia, Claudio; Lo Re, Giada; Lawoko, Martin; Berglund, Lars

2018-03-21

Here we report the synthesis of thermosetting resins from low molar mass Kraft lignin fractions of high functionality, refined by solvent extraction. Such fractions were fully characterized by 31 P NMR, 2D-HSQC NMR, SEC, and DSC in order to obtain a detailed description of the structures. Reactive oxirane moieties were introduced on the lignin backbone under mild reaction conditions and quantified by simple 1 H NMR analysis. The modified fractions were chemically cross-linked with a flexible polyether diamine ( M n ≈ 2000), in order to obtain epoxy thermosets. Epoxies from different lignin fractions, studied by DSC, DMA, tensile tests, and SEM, demonstrated substantial differences in terms of thermo-mechanical properties. For the first time, strong relationships between lignin structures and epoxy properties could be demonstrated. The suggested approach provides unprecedented possibilities to tune network structure and properties of thermosets based on real lignin fractions, rather than model compounds.

Lignin-Modified Carbon Nanotube/Graphene Hybrid Coating as Efficient Flame Retardant

Directory of Open Access Journals (Sweden)

Kunlin Song

2017-11-01

Full Text Available To reduce fire hazards and expand high-value applications of lignocellulosic materials, thin films comprising graphene nanoplatelets (GnPs and multi-wall carbon nanotubes (CNTs pre-adsorbed with alkali lignin were deposited by a Meyer rod process. Lightweight and highly flexible papers with increased gas impermeability were obtained by coating a protective layer of carbon nanomaterials in a randomly oriented and overlapped network structure. Assessment of the thermal and flammability properties of papers containing as low as 4 wt % carbon nanomaterials exhibited self-extinguishing behavior and yielded up to 83.5% and 87.7% reduction in weight loss and burning area, respectively, compared to the blank papers. The maximum burning temperature as measured by infrared pyrometry also decreased from 834 °C to 705 °C with the presence of flame retardants. Furthermore, papers coated with composites of GnPs and CNTs pre-adsorbed with lignin showed enhanced thermal stability and superior fire resistance than samples treated with either component alone. These outstanding flame-retardant properties can be attributed to the synergistic effects between GnPs, CNTs and lignin, enhancing physical barrier characteristics, formation of char and thermal management of the material. These results provide great opportunities for the development of efficient, cost-effective and environmentally sustainable flame retardants.

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.

A strategy to synthesize graphene-incorporated lignin polymer composite materials with uniform graphene dispersion and covalently bonded interface engineering

Science.gov (United States)

Wang, Mei; Duong, Le Dai; Ma, Yifei; Sun, Yan; Hong, Sung Yong; Kim, Ye Chan; Suhr, Jonghwan; Nam, Jae-Do

2017-08-01

Graphene-incorporated polymer composites have been demonstrated to have excellent mechanical and electrical properties. In the field of graphene-incorporated composite material synthesis, there are two main obstacles: Non-uniform dispersion of graphene filler in the matrix and weak interface bonding between the graphene filler and polymer matrix. To overcome these problems, we develop an in-situ polymerization strategy to synthesize uniformly dispersed and covalently bonded graphene/lignin composites. Graphene oxide (GO) was chemically modified by 4,4'-methylene diphenyl diisocyanate (MDI) to introduce isocyanate groups and form the urethane bonds with lignin macromonomers. Subsequential polycondensation reactions of lignin groups with caprolactone and sebacoyl chloride bring about a covalent network of modified GO and lignin-based polymers. The flexible and robust lignin polycaprolactone polycondensate/modified GO (Lig-GOm) composite membranes are achieved after vacuum filtration, which have tunable hydrophilicity and electrical resistance according to the contents of GOm. This research transforms lignin from an abundant biomass into film-state composite materials, paving a new way for the utilization of biomass wastes.

Reactivity of main components and substituent distribution in esterified sugarcane bagasse prepared by effective solid phase reaction.

Science.gov (United States)

Gan, Tao; Zhang, Yanjuan; Chen, Yane; Hu, Huayu; Yang, Mei; Huang, Zuqiang; Chen, Dong; Huang, Aimin

2018-02-01

Three main components of lignocellulose (cellulose, hemicellulose, and lignin isolated from sugarcane bagasse (SCB)) as well as holocellulose and SCB were modified with maleic acid by mechanical activation (MA)-assisted solid phase reaction (MASPR) technology. The order of reactivity was found to be lignin>hemicellulose>cellulose. The amorphous structure of lignin and hemicellulose mainly attributed to their better reactivity, and the modified lignin could reach a maximum degree of esterification (DE) of 93.45%. MA improved the accessibility and reactivity of cellulose, as the DE of modified cellulose gradually increased with milling time and reached the maximum value of 57.30% at 120min, which had significant effect on structure changes and DE of modified holocellulose and SCB. MA enhanced the esterification of all three components in lignocellulose with relatively high substituent distribution in them, and maleated SCB with a maximum DE of 64.17% was successfully prepared by this simple, green, and effective MASPR technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

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

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.

Chemoselective Methylation of Phenolic Hydroxyl Group Prevents Quinone Methide Formation and Repolymerization During Lignin Depolymerization

Energy Technology Data Exchange (ETDEWEB)

Kim, Kwang Ho; Dutta, Tanmoy; Walter, Eric D.; Isern, Nancy G.; Cort, John R.; Simmons, Blake A.; Singh, Seema

2017-03-30

Chemoselective blocking of the phenolic hydroxyl (Ar-OH) group by methylation was found to suppress secondary repolymerization and charring during lignin depolymerization. Methylation of Ar-OH prevents formation of reactive quinone methide intermediates, which are partly responsible for undesirable secondary repolymerization reactions. Instead, this structurally modified lignin produces more relatively low molecular weight products from lignin depolymerization compared to unmodified lignin. This result demonstrates that structural modification of lignin is desirable for production of low molecular weight phenolic products. This approach could be directed toward alteration of natural lignification processes to produce biomass more amenable to chemical depolymerization.

Effect of lignin chemistry on the enzymatic hydrolysis of woody biomass.

Science.gov (United States)

Yu, Zhiying; Gwak, Ki-Seob; Treasure, Trevor; Jameel, Hasan; Chang, Hou-min; Park, Sunkyu

2014-07-01

The impact of lignin-derived inhibition on enzymatic hydrolysis is investigated by using lignins isolated from untreated woods and pretreated wood pulps. A new method, biomass reconstruction, for which isolated lignins are precipitated onto bleached pulps to mimic lignocellulosic biomass, is introduced, for the first time, to decouple the lignin distribution issue from lignin chemistry. Isolated lignins are physically mixed and reconstructed with bleached pulps. Lignins obtained from pretreated woods adsorb two to six times more cellulase than lignins obtained from untreated woods. The higher adsorption of enzymes on lignin correlates with decreased carbohydrate conversion in enzymatic hydrolysis. In addition, the reconstructed softwood substrate has a lower carbohydrate conversion than the reconstructed hardwood substrate. The degree of condensation of lignin increases significantly after pretreatment, especially with softwood lignins. In this study, the degree of condensation of lignin (0.02 to 0.64) and total OH groups in lignin (1.7 to 1.1) have a critical impact on cellulase adsorption (9 to 70%) and enzymatic hydrolysis (83.2 to 58.2%); this may provide insights into the more recalcitrant nature of softwood substrates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Topochemical distribution of lignin and hydroxycinnamic acids in sugar-cane cell walls and its correlation with the enzymatic hydrolysis of polysaccharides

Directory of Open Access Journals (Sweden)

Koch Gerald

2011-03-01

Full Text Available Abstract Background Lignin and hemicelluloses are the major components limiting enzyme infiltration into cell walls. Determination of the topochemical distribution of lignin and aromatics in sugar cane might provide important data on the recalcitrance of specific cells. We used cellular ultraviolet (UV microspectrophotometry (UMSP to topochemically detect lignin and hydroxycinnamic acids in individual fiber, vessel and parenchyma cell walls of untreated and chlorite-treated sugar cane. Internodes, presenting typical vascular bundles and sucrose-storing parenchyma cells, were divided into rind and pith fractions. Results Vascular bundles were more abundant in the rind, whereas parenchyma cells predominated in the pith region. UV measurements of untreated fiber cell walls gave absorbance spectra typical of grass lignin, with a band at 278 nm and a pronounced shoulder at 315 nm, assigned to the presence of hydroxycinnamic acids linked to lignin and/or to arabino-methylglucurono-xylans. The cell walls of vessels had the highest level of lignification, followed by those of fibers and parenchyma. Pith parenchyma cell walls were characterized by very low absorbance values at 278 nm; however, a distinct peak at 315 nm indicated that pith parenchyma cells are not extensively lignified, but contain significant amounts of hydroxycinnamic acids. Cellular UV image profiles scanned with an absorbance intensity maximum of 278 nm identified the pattern of lignin distribution in the individual cell walls, with the highest concentration occurring in the middle lamella and cell corners. Chlorite treatment caused a rapid removal of hydroxycinnamic acids from parenchyma cell walls, whereas the thicker fiber cell walls were delignified only after a long treatment duration (4 hours. Untreated pith samples were promptly hydrolyzed by cellulases, reaching 63% of cellulose conversion after 72 hours of hydrolysis, whereas untreated rind samples achieved only 20

Horizontal and vertical distribution of lignin in surface sediments of the Gdansk Basin

Directory of Open Access Journals (Sweden)

Andrzej Staniszewski

2001-12-01

Full Text Available The aim of this study was to identify and quantify lignin transported from the River Vistula to the accumulation area in the Gdansk Basin. Sediment samples collected along the Vistula mouth - Gdansk Deep transect were analysed for lignin. Lignin was characterised by oxidative degradation, cupric oxide being chosen as the most suitable oxidising agent. The polar functional groups of the oxidation products were silylated and the derivatives analysed by capillary gas chromatography on fused capillary silica columns with flame ionisation detection. Lignin-derived oxidation products were quantified in the range from 3 to 20 µg g-1 dry wt. for phenolic acids and from 6 to 12 µg g-1 dry wt. for phenolic aldehydes. Differences in oxidation products contents are assigned to different lignin sources in the marine environment. The horizontal and vertical gradients of these compounds in the sediments of the Gdansk Basin are documented. The results are discussed in terms of the origin and fate of organic matter in the Gdansk Basin. The measured differences in quality and quantity of the identified oxidation products provide insight into diagenetic processes in the surface marine sediments.

Lignin Valorization: Emerging Approaches

Energy Technology Data Exchange (ETDEWEB)

Beckham, Gregg T [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2018-04-03

Lignin, an aromatic biopolymer found in plant cell walls, is a key component of lignocellulosic biomass and generally utilized for heat and power. However, lignin's chemical composition makes it an attractive source for biological and catalytic conversion to fuels and chemicals. Bringing together experts from biology, catalysis, engineering, analytical chemistry, and techno-economic/life-cycle analysis, Lignin Valorization presents a comprehensive, interdisciplinary picture of how lignocellulosic biorefineries could potentially employ lignin valorization technologies. Chapters will specifically focus on the production of fuels and chemicals from lignin and topics covered include (i) methods for isolating lignin in the context of the lignocellulosic biorefinery, (ii) thermal, chemo-catalytic, and biological methods for lignin depolymerization, (iii) chemo-catalytic and biological methods for upgrading lignin, (iv) characterization of lignin, and (v) techno-economic and life-cycle analysis of integrated processes to utilize lignin in an integrated biorefinery. The book provides the latest breakthroughs and challenges in upgrading lignin to fuels and chemicals for graduate students and researchers in academia, governmental laboratories, and industry interested in biomass conversion.

Molar mass determination of lignins by size-exclusion chromatography: towards standardisation of the method

NARCIS (Netherlands)

Baumberger, S.; Abaecherli, A.; Fasching, M.; Gellerstedt, G.; Gosselink, R.J.A.; Hortling, B.; Li, J.; Saake, B.; Jong, de E.

2007-01-01

The reactivity and physicochemical properties of lignins are partly governed by their molar mass distribution. The development of reliable standard methods for determination of the molar mass distribution is not only relevant for designing technical lignins for specific applications, but also for

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.

Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

Energy Technology Data Exchange (ETDEWEB)

Das, Lalitendu [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States); Xu, Siquan [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States); College of Chemical Engineering, Nanjing Forestry University, Nanjing (China); Shi, Jian, E-mail: j.shi@uky.edu [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States)

2017-08-10

Lignin is an integral part of the plant cell wall, which provides rigidity to plants, also contributes to the recalcitrance of the lignocellulosic biomass to biochemical and biological deconstruction. Lignin is a promising renewable feedstock for aromatic chemicals; however, an efficient and economic lignin depolymerization method needs to be developed to enable the conversion. In this study, we investigated the depolymerization of alkaline lignin in aqueous 1-ethyl-3-methylimidazolium acetate [C{sub 2}C{sub 1}Im][OAc] under oxidizing conditions. Seven different transition metal catalysts were screened in presence of H{sub 2}O{sub 2} as oxidizing agent in a batch reactor. CoCl{sub 2} and Nb{sub 2}O{sub 5} proved to be the most effective catalysts in degrading lignin to aromatic compounds. A central composite design was used to optimize the catalyst loading, H{sub 2}O{sub 2} concentration, and temperature for product formation. Results show that lignin was depolymerized, and the major degradation products found in the extracted oil were guaiacol, syringol, vanillin, acetovanillone, and homovanillic acid. Lignin streams were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography to determine effects of the experimental parameters on lignin depolymerization. The weight-average molecular weight (M{sub w}) of liquid stream lignin after oxidation, for CoCl{sub 2} and Nb{sub 2}O{sub 5} catalysts were 1,202 and 1,520 g mol{sup −1}, respectively, lower than that of Kraft lignin. Polydispersity index of the liquid stream lignin increased as compared with Kraft lignin, indicating wide span of the molecular weight distribution as a result of lignin depolymerization. Results from this study provide insights into the role of oxidant and transition metal catalysts and the oxidative degradation reaction sequence of lignin toward product formation in presence of aqueous ionic liquid.

Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

International Nuclear Information System (INIS)

Das, Lalitendu; Xu, Siquan; Shi, Jian

2017-01-01

Lignin is an integral part of the plant cell wall, which provides rigidity to plants, also contributes to the recalcitrance of the lignocellulosic biomass to biochemical and biological deconstruction. Lignin is a promising renewable feedstock for aromatic chemicals; however, an efficient and economic lignin depolymerization method needs to be developed to enable the conversion. In this study, we investigated the depolymerization of alkaline lignin in aqueous 1-ethyl-3-methylimidazolium acetate [C 2 C 1 Im][OAc] under oxidizing conditions. Seven different transition metal catalysts were screened in presence of H 2 O 2 as oxidizing agent in a batch reactor. CoCl 2 and Nb 2 O 5 proved to be the most effective catalysts in degrading lignin to aromatic compounds. A central composite design was used to optimize the catalyst loading, H 2 O 2 concentration, and temperature for product formation. Results show that lignin was depolymerized, and the major degradation products found in the extracted oil were guaiacol, syringol, vanillin, acetovanillone, and homovanillic acid. Lignin streams were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography to determine effects of the experimental parameters on lignin depolymerization. The weight-average molecular weight (M w ) of liquid stream lignin after oxidation, for CoCl 2 and Nb 2 O 5 catalysts were 1,202 and 1,520 g mol −1 , respectively, lower than that of Kraft lignin. Polydispersity index of the liquid stream lignin increased as compared with Kraft lignin, indicating wide span of the molecular weight distribution as a result of lignin depolymerization. Results from this study provide insights into the role of oxidant and transition metal catalysts and the oxidative degradation reaction sequence of lignin toward product formation in presence of aqueous ionic liquid.

Fast Pyrolysis of Lignin Using a Pyrolysis Centrifuge Reactor

DEFF Research Database (Denmark)

Trinh, Ngoc Trung; Jensen, Peter Arendt; Sárossy, Zsuzsa

2013-01-01

Fast pyrolysis of lignin from an ethanol plant was investigated on a lab scale pyrolysis centrifuge reactor (PCR) with respect to pyrolysis temperature, reactor gas residence time, and feed rate. A maximal organic oil yield of 34 wt % dry basis (db) (bio-oil yield of 43 wt % db) is obtained...... at temperatures of 500−550 °C, reactor gas residence time of 0.8 s, and feed rate of 5.6 g/min. Gas chromatography mass spectrometry and size-exclusion chromatography were used to characterize the Chemical properties of the lignin oils. Acetic acid, levoglucosan, guaiacol, syringols, and p-vinylguaiacol are found...... components and molecular mass distribution of the lignin oils. The obtained lignin oil has a very different components composition when compared to a beech wood oil....

The McDonald Modified Weibull Distribution: Properties and Applications

OpenAIRE

Merovci, Faton; Elbatal, Ibrahim

2013-01-01

A six parameter distribution so-called the McDonald modified Weibull distribution is defined and studied. The new distribution contains, as special submodels, several important distributions discussed in the literature, such as the beta modified Weibull, Kumaraswamy modified Weibull, McDonald Weibull and modified Weibull distribution,among others. The new distribution can be used effectively in the analysis of survival data since it accommodates monotone, unimodal and bathtub-shaped hazard fu...

Visualising recalcitrance by colocalisation of cellulase, lignin and cellulose in pretreated pine biomass using fluorescence microscopy

Science.gov (United States)

Donaldson, Lloyd; Vaidya, Alankar

2017-03-01

Mapping the location of bound cellulase enzymes provides information on the micro-scale distribution of amenable and recalcitrant sites in pretreated woody biomass for biofuel applications. The interaction of a fluorescently labelled cellulase enzyme cocktail with steam-exploded pine (SEW) was quantified using confocal microscopy. The spatial distribution of Dylight labelled cellulase was quantified relative to lignin (autofluorescence) and cellulose (Congo red staining) by measuring their colocalisation using Pearson correlations. Correlations were greater in cellulose-rich secondary cell walls compared to lignin-rich middle lamella but with significant variations among individual biomass particles. The distribution of cellulose in the pretreated biomass accounted for 30% of the variation in the distribution of enzyme after correcting for the correlation between lignin and cellulose. For the first time, colocalisation analysis was able to quantify the spatial distribution of amenable and recalcitrant sites in relation to the histochemistry of cellulose and lignin. This study will contribute to understanding the role of pretreatment in enzymatic hydrolysis of recalcitrant softwood biomass.

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

The synthesis and analysis of lignin-bound Hibbert ketone structures in technical lignins.

Science.gov (United States)

Miles-Barrett, Daniel M; Neal, Andrew R; Hand, Calum; Montgomery, James R D; Panovic, Isabella; Ojo, O Stephen; Lancefield, Christopher S; Cordes, David B; Slawin, Alexandra M Z; Lebl, Tomas; Westwood, Nicholas J

2016-10-25

Understanding the structure of technical lignins resulting from acid-catalysed treatment of lignocellulosic biomass is important for their future applications. Here we report an investigation into the fate of lignin under acidic aqueous organosolv conditions. In particular we examine in detail the formation and reactivity of non-native Hibbert ketone structures found in isolated organosolv lignins from both Douglas fir and beech woods. Through the use of model compounds combined with HSQC, HMBC and HSQC-TOCSY NMR experiments we demonstrate that, depending on the lignin source, both S and G lignin-bound Hibbert ketone units can be present. We also show that these units can serve as a source of novel mono-aromatic compounds following an additional lignin depolymerisation reaction.

Electrochemical Determination of Caffeine Content in Ethiopian Coffee Samples Using Lignin Modified Glassy Carbon Electrode

Directory of Open Access Journals (Sweden)

Meareg Amare

2017-01-01

Full Text Available Lignin film was deposited at the surface of glassy carbon electrode potentiostatically. In contrast to the unmodified glassy carbon electrode, an oxidative peak with an improved current and overpotential for caffeine at modified electrode showed catalytic activity of the modifier towards oxidation of caffeine. Linear dependence of peak current on caffeine concentration in the range 6×10-6 to 100×10-6 mol L−1 with determination coefficient and method detection limit (LoD = 3 s/slope of 0.99925 and 8.37×10-7 mol L−1, respectively, supplemented by recovery results of 93.79–102.17% validated the developed method. An attempt was made to determine the caffeine content of aqueous coffee extracts of Ethiopian coffees grown in four coffee cultivating localities (Wonbera, Wolega, Finoteselam, and Zegie and hence to evaluate the correlation between users preference and caffeine content. In agreement with reported works, caffeine contents (w/w% of 0.164 in Wonbera coffee; 0.134 in Wolega coffee; 0.097 in Finoteselam coffee; and 0.089 in Zegie coffee were detected confirming the applicability of the developed method for determination of caffeine in a complex matrix environment. The result indicated that users’ highest preference for Wonbera and least preference for Zegie cultivated coffees are in agreement with the caffeine content.

Electrochemical Determination of Caffeine Content in Ethiopian Coffee Samples Using Lignin Modified Glassy Carbon Electrode.

Science.gov (United States)

Amare, Meareg; Aklog, Senait

2017-01-01

Lignin film was deposited at the surface of glassy carbon electrode potentiostatically. In contrast to the unmodified glassy carbon electrode, an oxidative peak with an improved current and overpotential for caffeine at modified electrode showed catalytic activity of the modifier towards oxidation of caffeine. Linear dependence of peak current on caffeine concentration in the range 6 × 10 -6 to 100 × 10 -6  mol L -1 with determination coefficient and method detection limit (LoD = 3 s/slope) of 0.99925 and 8.37 × 10 -7  mol L -1 , respectively, supplemented by recovery results of 93.79-102.17% validated the developed method. An attempt was made to determine the caffeine content of aqueous coffee extracts of Ethiopian coffees grown in four coffee cultivating localities (Wonbera, Wolega, Finoteselam, and Zegie) and hence to evaluate the correlation between users preference and caffeine content. In agreement with reported works, caffeine contents (w/w%) of 0.164 in Wonbera coffee; 0.134 in Wolega coffee; 0.097 in Finoteselam coffee; and 0.089 in Zegie coffee were detected confirming the applicability of the developed method for determination of caffeine in a complex matrix environment. The result indicated that users' highest preference for Wonbera and least preference for Zegie cultivated coffees are in agreement with the caffeine content.

A Comparison of Lignin, Macroalgae, Wood and Straw Fast Pyrolysis

DEFF Research Database (Denmark)

Trinh, Ngoc Trung; Jensen, Peter Arendt; Dam-Johansen, Kim

2013-01-01

these biomasses. The fast pyrolysis of macroalgae showed a promising result with a bio-oil yield of 65 wt% dry ash free basis (daf) and 76 % energy recovery in the bio-oil while the lignin fast pyrolysis provides a bio-oil yield of 47 wt% daf and energy recovery in bio-oil of 45 %. The physiochemical properties...... of the bio-oils were characterized with respect to higher heating value (HHV), molecular mass distribution, viscosity, pH, density, thermal behaviors, elemental concentrations, phase separation and aging. The lignin and macroalgae oil properties were different compared to those of the wood and straw oils......A fast pyrolysis study on lignin and macroalgae (non-conventional biomass) and wood and straw (conventional biomass) were carried out in a pyrolysis centrifugal reactor at pyrolysis temperature of 550 ºC. The product distributions and energy recoveries were measured and compared among...

Symmetric supercapacitors using urea-modified lignin derived N-doped porous carbon as electrode materials in liquid and solid electrolytes

Science.gov (United States)

Wang, Keliang; Xu, Ming; Gu, Yan; Gu, Zhengrong; Fan, Qi Hua

2016-11-01

N-doped porous carbon materials derived from urea-modified lignin were prepared via efficient KOH activation under carbonization. The synthesized N-doped carbon materials, which displayed a well-developed porous morphology with high specific surface area of 3130 m2 g-1, were used as electrode materials in symmetric supercapacitors with aqueous and solid electrolytes. In consistent with the observed physical structures and properties, the supercapacitors exhibited specific capacitances of 273 and 306 F g-1, small resistances of 2.6 and 7.7 Ω, stable charge/discharge at different current densities for over 5000 cycles and comparable energy and power density in 6 mol L-1 KOH liquid and KOH-PVA solid electrolytes, respectively.

Genetic Modification of Lignin in Hybrid Poplar (Populus alba × Populus tremula) Does Not Substantially Alter Plant Defense or Arthropod Communities.

Science.gov (United States)

Buhl, Christine; Meilan, Richard; Lindroth, Richard L

2017-05-01

Lignin impedes access to cellulose during biofuel production and pulping but trees can be genetically modified to improve processing efficiency. Modification of lignin may have nontarget effects on mechanical and chemical resistance and subsequent arthropod community responses with respect to pest susceptibility and arthropod biodiversity. We quantified foliar mechanical and chemical resistance traits in lignin-modified and wild-type (WT) poplar (Populus alba × Populus tremula) grown in a plantation and censused arthropods present on these trees to determine total abundance, as well as species richness, diversity and community composition. Our results indicate that mechanical resistance was not affected by lignin modification and only one genetic construct resulted in a (modest) change in chemical resistance. Arthropod abundance and community composition were consistent across modified and WT trees, but transgenics produced using one construct exhibited higher species richness and diversity relative to the WT. Our findings indicate that modification of lignin in poplar does not negatively affect herbivore resistance traits or arthropod community response, and may even result in a source of increased genetic diversity in trees and arthropod communities. © The Authors 2017. Published by Oxford University Press on behalf of Entomological Society of America.

New techniques for the characterization of lignins

International Nuclear Information System (INIS)

Javor, T.

2001-09-01

...12 are used, which gives information about the charge/mass distribution of the analytes. It is possible to distinguish between lignins of different origin and between ligninsulfonates with different degree of sulfonation. Furthermore, preliminary investigations with APCI (atmospheric pressure chemical ionisation) MS and MALDI (matrix assisted laser desorption) MS are carried out. Unfortunately, the significance of the results for lignins and ligninsulfonates limited. Finally, new capillary electrophoretic techniques are described, which are an efficient alternative to existing gas chromatographic methods for the analysis on lignin degradation products after oxidation with permanganate. Herewith information about kind and quantity of various linkages in the lignin molecule is possible. An important advantage is the fact, that in contrast to GC it is not necessary to prepare esters of the oxidation products (aromatic acids), which saves time and work. The selectivity and sensitivity of the UV detection for the CE method is adequate and makes it suited for fast routine analysis of lignins. If necessary, the CE method can be coupled with ESI-MS in order to make a clear assignment of the peaks. (author)

Lignin monomer composition affects Arabidopsis cell-wall degradability after liquid hot water pretreatment

Directory of Open Access Journals (Sweden)

Ladisch Michael

2010-12-01

Full Text Available Abstract Background Lignin is embedded in the plant cell wall matrix, and impedes the enzymatic saccharification of lignocellulosic feedstocks. To investigate whether enzymatic digestibility of cell wall materials can be improved by altering the relative abundance of the two major lignin monomers, guaiacyl (G and syringyl (S subunits, we compared the degradability of cell wall material from wild-type Arabidopsis thaliana with a mutant line and a genetically modified line, the lignins of which are enriched in G and S subunits, respectively. Results Arabidopsis tissue containing G- and S-rich lignins had the same saccharification performance as the wild type when subjected to enzyme hydrolysis without pretreatment. After a 24-hour incubation period, less than 30% of the total glucan was hydrolyzed. By contrast, when liquid hot water (LHW pretreatment was included before enzyme hydrolysis, the S-lignin-rich tissue gave a much higher glucose yield than either the wild-type or G-lignin-rich tissue. Applying a hot-water washing step after the pretreatment did not lead to a further increase in final glucose yield, but the initial hydrolytic rate was doubled. Conclusions Our analyses using the model plant A. thaliana revealed that lignin composition affects the enzymatic digestibility of LHW pretreated plant material. Pretreatment is more effective in enhancing the saccharification of A. thaliana cell walls that contain S-rich lignin. Increasing lignin S monomer content through genetic engineering may be a promising approach to increase the efficiency and reduce the cost of biomass to biofuel conversion.

Depolymerization and hydrodeoxygenation of switchgrass lignin with formic acid.

Science.gov (United States)

Xu, Weiyin; Miller, Stephen J; Agrawal, Pradeep K; Jones, Christopher W

2012-04-01

Organosolv switchgrass lignin is depolymerized and hydrodeoxygenated with a formic acid hydrogen source, 20 wt % Pt/C catalyst, and ethanol solvent. The combination of formic acid and Pt/C is found to promote production of higher fractions of lower molecular weight compounds in the liquid products. After 4 h of reaction, all of the switchgrass lignin is solubilized and 21 wt % of the biomass is shown to be converted into seven prominent molecular species that are identified and quantified. Reaction time is shown to be an important variable in affecting changes in product distributions and bulk liquid product properties. At 20 h of reaction, the lignin is significantly depolymerized to form liquid products with a 76 % reduction in the weighted average molecular weight. Elemental analysis also shows that the resultant liquid products have a 50 % reduction in O/C and 10 % increase in H/C molar ratios compared to the switchgrass lignin after 20 h. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of Lignins from Sugarcane Bagasse for Assembling Microparticles Loaded with Azadirachta indica Extracts for Use as Neem-Based Organic Insecticides

OpenAIRE

Costa, Eveline S.; Perlatti, Bruno; Silva, Everton M. da; Matos, Andreia P.; Silva, Maria Fátima G. F. da; Fernandes, João B.; Zuin, Vânia G.; Silva, Caio M. P. da; Forim, Moacir R.

2017-01-01

Microcapsules of sugarcane bagasse lignin loaded with organic extracts of neem (Azadirachta indica) were prepared and evaluated as potential bioinsecticides. Lignins were extracted and modified by oxidation and acetylation reactions providing different biopolymers. Afterwards, they were characterized through several analytical techniques. The formulations were initially prepared as colloidal suspension of lignin nanoparticles, which were then spray-dried. The products were submitted to qualit...

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.

Phase distribution of products of radiation and post-radiation distillation of biopolymers: Cellulose, lignin and chitin

International Nuclear Information System (INIS)

Ponomarev, A.V.; Kholodkova, E.M.; Metreveli, A.K.; Metreveli, P.K.; Erasov, V.S.; Bludenko, A.V.; Chulkov, V.N.

2011-01-01

Influence of both the absorbed dose and the dose rate of 8 MeV electron-beam radiation on destruction of microcrystalline cellulose, pine lignin and krill chitin was investigated. Two conversion modes were compared: (1) post-radiation distillation PRD and (2) electron-beam distillation EBD. Cellulose, chitin and lignin demonstrate different responses to irradiation and distillation in PRD and EBD modes. Treatment in EBD mode transforms biopolymers to organic liquid more productively than conventional dry distillation and treatment in PRD mode. Both radiation heating and an irradiation without heating intensify chitin and cellulose decomposition and distillation. At the same time lignin decaying rather efficiently in EBD mode appears to be insensitive to a preliminary irradiation in PRD mode up to a dose of 2.4 MGy. - Highlights: → Direct conversion of cellulose, chitin and lignin to organic liquid is intensified by electron-beam irradiation. → Alternative approach to bio-oil production. → Both electron-beam distillation mode and post-radiation distillation mode are effective for cellulose and chitin conversion. → Electron-beam distillation mode is preferable for lignin conversion. → Preliminary deep dehydration of biopolymers is realizable at low dose rates.

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Manipulation Of Lignin Biosynthesis To Maximize Ethanol Production From Populus Feedstocks

Energy Technology Data Exchange (ETDEWEB)

Dr. Clint Chapple; Dr. Rick Lindroth; Dr. Burce Dien; Dr. Glen Stanosz; Dr. Alex Wiedenhoeft; Dr. Fu Zhao; Dr. Duane Wegener; Dr. Janice Kelly; Dr. Leigh Raymond; Dr. Wallace Tyner

2012-05-15

Our research focuses on transgenic strategies for modifying lignification to improve biomass quality, without leading to deleterious effects on plant performance. In order to accomplish this objective, we designed molecular strategies and selected appropriate transgenes for manipulating the expression of lignification-associated genes; we generated poplar engineered for altered lignin content and/or monomer composition, and field-tested them for fitness; we analyzed the impact of these transgenic strategies on metabolism in general and lignin biosynthesis in particular; and evaluated the ease with which cell wall deconstruction can be accomplished using both chemical and enzymatic means using wild-type and high syringyl poplar.

Radiotracer experiments on lignin reactions, 2

International Nuclear Information System (INIS)

Terashima, Noritsugu; Araki, Hiroshi; Suganuma, Nobuo.

1977-01-01

The behavior of the specific carbon atoms of lignin during the cooking process was studied. Pine wood meal containing the protolignin labelled with 14-C was prepared, and treated under sulfate cooking conditions. The incorporation and distribution of radioactivity were traced in three fractions separated from the black liquor according to their solubilities and molecular weights. The gamma position carbon at the end of side chain of phenylpropane unit in lignin was eliminated easily from the high molecular weight portion in considerable extent during the cooking process, and a part of the eliminated carbon condenses again with the aromatic ring. However, a large portion of the eliminated gamma-carbon was found in the low molecular fraction of water soluble part of the black liquor. The radioactivity of alpha-carbons in the side chains adjacent to aromatic rings was found to be distributed in three fractions similarly to that of beta-carbons, except that the incorporation of radioactivity of alpha-carbons was slightly low in high molecular fraction, and slightly high in low molecular water soluble fraction as compared with that of beta-carbons and aromatic ring carbons. The number of residual carbon atoms per one monomer unit in high molecular kraft lignin was calculated from the specific incorporation ratio of radioactivity. The carbon skelton was estimated and the molecular formula was given by the elementary analysis and molecular weight determination. (Iwakiri, K.)

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.

Lignin Macromolecule

Indian Academy of Sciences (India)

plant or a structural component of a mature plant which is detected by certain colour reactions. An enzymologist has termed lignin as the ... a phenyl-propanoid structure. A soil chemist considers lignin to be the residue of .... refer to the hardness of wood, but to the botanical classifications. They are aptly called gymnosperms ...

Physico-Chemical Properties and Biodegradability of Genetically Modified Populus trichocarpa and Pinus taeda

Science.gov (United States)

Edmunds, Charles Warren

Increasing concerns over greenhouse gas emissions and the finite supply of fossil fuels lead to the goal of utilizing lignocellulosic feedstocks for biofuels, platform chemicals, and biocomposites. Lignin is responsible for the recalcitrance of lignocellulosic biomass and is a major barrier to its deconstruction. Great progress has been made in mapping and modifying the lignin biosynthetic pathway. However, the link between the genetic modification, resulting chemical and physical properties of the wood, and how these properties influence the thermomechanical and recalcitrance to biological and chemical degradation needs further investigation. In this dissertation, the study of modified Populus trichocarpa and Pinus taeda were utilized to accomplish this goal. Thermo-mechanical properties of genetically modified P. trichocarpa with altered lignin content and/or lignin structure were measured with a series of tools including; dynamic mechanical analysis, nuclear magnetic resonance, and wet chemistry techniques. Results demonstrated lignin content and lignin structure likely influence the glass transition temperature (Tg), and that decreased lignin content and the corresponding higher proportion of cell wall carbohydrates may contribute to increased molecular mobility in the wood polymer structure. The effect of lignin biosynthetic pathway modification on biological degradation of these transgenic wood specimens was of interest. However, experimental methods for fungal treatment on small young greenhouse-grown wood specimens are not well established. Therefore, a project was undertaken to develop a method for fungal inoculation and incubation for these unique specimens. Several parameters were tested, and a fungal treatment method was identified with sufficient weight loss after decay and significant reduction in variation of weight loss between replicates compared to previous experiments by direct inoculation of wood with liquid malt extract fungal culture

Identification and thermochemical analysis of high-lignin feedstocks for biofuel and biochemical production

Directory of Open Access Journals (Sweden)

Mendu Venugopal

2011-10-01

Full Text Available Abstract Background Lignin is a highly abundant biopolymer synthesized by plants as a complex component of plant secondary cell walls. Efforts to utilize lignin-based bioproducts are needed. Results Herein we identify and characterize the composition and pyrolytic deconstruction characteristics of high-lignin feedstocks. Feedstocks displaying the highest levels of lignin were identified as drupe endocarp biomass arising as agricultural waste from horticultural crops. By performing pyrolysis coupled to gas chromatography-mass spectrometry, we characterized lignin-derived deconstruction products from endocarp biomass and compared these with switchgrass. By comparing individual pyrolytic products, we document higher amounts of acetic acid, 1-hydroxy-2-propanone, acetone and furfural in switchgrass compared to endocarp tissue, which is consistent with high holocellulose relative to lignin. By contrast, greater yields of lignin-based pyrolytic products such as phenol, 2-methoxyphenol, 2-methylphenol, 2-methoxy-4-methylphenol and 4-ethyl-2-methoxyphenol arising from drupe endocarp tissue are documented. Conclusions Differences in product yield, thermal decomposition rates and molecular species distribution among the feedstocks illustrate the potential of high-lignin endocarp feedstocks to generate valuable chemicals by thermochemical deconstruction.

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

Lignin is a major polymer in the secondary plant cell wall and composed of hydrophobic interlinked hydroxyphenylpropanoid units. The presence of lignin hampers conversion of plant biomass into biofuels; plants with modified lignin are therefore being investigated for increased digestibility....... The bacterium Sphingomonas paucimobilis produces lignin-degrading enzymes including LigD, LigF and LigG involved in cleaving the most abundant lignin inter-unit linkage, the β-aryl ether bond. In this study, we expressed the LigD, LigF and LigG (LigDFG) genes in Arabidopsis thaliana to introduce post...

Lignin blockers and uses thereof

Science.gov (United States)

Yang, Bin [West Lebanon, NH; Wyman, Charles E [Norwich, VT

2011-01-25

Disclosed is a method for converting cellulose in a lignocellulosic biomass. The method provides for a lignin-blocking polypeptide and/or protein treatment of high lignin solids. The treatment enhances cellulase availability in cellulose conversion and allows for the determination of optimized pretreatment conditions. Additionally, ethanol yields from a Simultaneous Saccharification and Fermentation process are improved 5-25% by treatment with a lignin-blocking polypeptide and/or protein. Thus, a more efficient and economical method of processing lignin containing biomass materials utilizes a polypeptide/protein treatment step that effectively blocks lignin binding of cellulase.

Improvement of linerboard compressive strength by hot-pressing and addition of recovered lignin from spent pulping liquor

Directory of Open Access Journals (Sweden)

Saidan Motasem N.

2015-01-01

Full Text Available This paper evaluates the effect of addition of precipitated lignin, from spent pulping black liquor, to a wet single-ply linerboard handsheet followed by hot-pressing at different temperatures, on the improvement of its compressive strength. Linerboard handsheets for testing the effect of lignin addition were prepared so that the lignin-modified sheets would have the same basis weights as the control handsheets. Both the commercial and the black liquor lignin were added as a powder to wet handsheets after couching from the handsheet mold. The experiments and testing of the physical and strength properties of dried handsheets were conducted according to TAPPI test methods. The results revealed that the addition of the recovered lignin (at pH of 2 to the wet handsheet followed by hot-pressing at 150°C increased the compressive strength of linerboard handsheets by 10% to 20% above that for handsheets made without the addition of lignin. The same results were achieved using purchased lignin. However, with a 16% addition to linerboard, purchased lignin would be too expensive. These results indicate that inclusion of kraft lignin in linerboard sheets could be proved as an attractive option to reduce linerboard basis weight.

Towards development of lignin reinforced elastomeric compounds with reduced energy dissipation

Science.gov (United States)

Bahl, Kushal

This research deals with development of lignin as reinforcing filler for elastomeric compounds. Lignins are naturally abundant and cost competitive wood derivatives possessing strong mechanical properties and offering reactive functional groups on their surfaces. The presence of the functional groups imparts polarity to the lignin molecules and makes them incompatible with non-polar elastomers. Also, the large particle size of lignin does not produce desired mechanical reinforcement. The present study deals with solving the outstanding issues associated with the use of lignin as fillers for polymeric compounds. In addition, the work specifically focuses on producing rubber compounds with reduced energy dissipation via partial replacement of carbon black with lignin. The first part of this study is devoted to suppression of the polarity of lignin and achievement of compatibility with rubber matrix via modification of lignosulfonates (LS) with cyclohexylamine (CA). CA reduces the polarity of lignin via interactions originating from proton transfer and hydrogen bonding. X-ray Photoelectron Spectroscopy (XPS) confirms the attachment of CA on the surfaces of lignin. The mechanical properties of rubber compounds increase substantially along with improvement in cure properties and increase in crosslink density in the presence of LS particles modified with CA. The tensile strength and storage modulus show an increase by 45% and 41% respectively. The values of the 100% modulus and elongation at break also improve by 35% and 60% respectively. The second part of this study exploits the non-covalent interactions between lignin and carbon black (CB) for the design of novel hybrid filler particles exhibiting lower energy loss in rubber compounds. The hybrid fillers offer unique morphology consisting of coating layers of lignin on carbon black particle aggregates. It is found that such coating layers are formed due to pi-pi interactions between lignin and carbon black. Raman

Ferricyanide-based analysis of aqueous lignin suspension revealed sequestration of water-soluble lignin moieties

OpenAIRE

Joshua, CJ; Simmons, BA; Singer, SW

2016-01-01

© 2016 The Royal Society of Chemistry. This study describes the application of a ferricyanide-based assay as a simple and inexpensive assay for rapid analysis of aqueous lignin samples. The assay measures the formation of Prussian blue from the redox reaction between a mixture of potassium ferricyanide and ferric chloride, and phenolic hydroxyl groups of lignin or lignin-derived phenolic moieties. This study revealed that soluble lignin moieties exhibited stronger ferricyanide reactivity than...

Reactivity of lignin and lignin models towards UV-assisted peroxide

International Nuclear Information System (INIS)

Sun, Y.P.; Wallis, A.F.A.; Nguyen, K.L.

1997-01-01

The comparative reactivities of a series of guaiacyl and syringyl lignin model compounds and their methylated analogues towards alkaline peroxide and UV-alkaline peroxide were investigated. The overall reaction was followed by monitoring the reduction of the substrate as a function of time, and in every case, the reaction showed pseudo-first-order kinetics. The reaction rates of most lignin models having identical sidechains with alkaline peroxide and with UV-alkaline peroxide were in the order syringyl guaiacyl 3,4,5-trimethoxyphenyl veratryl. Thus phenols react faster than their methyl ethers, and an extra ortho methoxyl group promotes the reaction. Lignin models possessing electron-donating sidechains had generally higher reaction rates than those with electron-withdrawing sidechains. The reaction rates of the series of benzoic acids were 2-4 times higher at pH 11 than at pH 5. UV-peroxide degradation of a eucalypt kraft lignin was faster than that of a pine kraft lignin, and degradation was 1.4-1.6 times faster at pH 11 than at pH 5. The data are consistent with the formation of higher amounts of reactive radicals under alkaline conditions, and aromatic rings with greater electronegativities promoting reactions with the radicals

Exploring bacterial lignin degradation.

Science.gov (United States)

Brown, Margaret E; Chang, Michelle C Y

2014-04-01

Plant biomass represents a renewable carbon feedstock that could potentially be used to replace a significant level of petroleum-derived chemicals. One major challenge in its utilization is that the majority of this carbon is trapped in the recalcitrant structural polymers of the plant cell wall. Deconstruction of lignin is a key step in the processing of biomass to useful monomers but remains challenging. Microbial systems can provide molecular information on lignin depolymerization as they have evolved to break lignin down using metalloenzyme-dependent radical pathways. Both fungi and bacteria have been observed to metabolize lignin; however, their differential reactivity with this substrate indicates that they may utilize different chemical strategies for its breakdown. This review will discuss recent advances in studying bacterial lignin degradation as an approach to exploring greater diversity in the environment. Copyright © 2013 Elsevier Ltd. All rights reserved.

Lignin as a Binder Material for Eco-Friendly Li-Ion Batteries

Science.gov (United States)

Lu, Huiran; Cornell, Ann; Alvarado, Fernando; Behm, Mårten; Leijonmarck, Simon; Li, Jiebing; Tomani, Per; Lindbergh, Göran

2016-01-01

The industrial lignin used here is a byproduct from Kraft pulp mills, extracted from black liquor. Since lignin is inexpensive, abundant and renewable, its utilization has attracted more and more attention. In this work, lignin was used for the first time as binder material for LiFePO4 positive and graphite negative electrodes in Li-ion batteries. A procedure for pretreatment of lignin, where low-molecular fractions were removed by leaching, was necessary to obtain good battery performance. The lignin was analyzed for molecular mass distribution and thermal behavior prior to and after the pretreatment. Electrodes containing active material, conductive particles and lignin were cast on metal foils, acting as current collectors and characterized using scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge cycles. Good reversible capacities were obtained, 148 mAh·g−1 for the positive electrode and 305 mAh·g−1 for the negative electrode. Fairly good rate capabilities were found for both the positive electrode with 117 mAh·g−1 and the negative electrode with 160 mAh·g−1 at 1C. Low ohmic resistance also indicated good binder functionality. The results show that lignin is a promising candidate as binder material for electrodes in eco-friendly Li-ion batteries. PMID:28773252

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

Lignin-degrading enzyme activities.

Science.gov (United States)

Chen, Yi-ru; Sarkanen, Simo; Wang, Yun-Yan

2012-01-01

Over the past three decades, the activities of four kinds of enzyme have been purported to furnish the mechanistic foundations for macromolecular lignin depolymerization in decaying plant cell walls. The pertinent fungal enzymes comprise lignin peroxidase (with a relatively high redox potential), manganese peroxidase, an alkyl aryl etherase, and laccase. The peroxidases and laccase, but not the etherase, are expressed extracellularly by white-rot fungi. A number of these microorganisms exhibit a marked preference toward lignin in their degradation of lignocellulose. Interestingly, some white-rot fungi secrete both kinds of peroxidase but no laccase, while others that are equally effective express extracellular laccase activity but no peroxidases. Actually, none of these enzymes has been reported to possess significant depolymerase activity toward macromolecular lignin substrates that are derived with little chemical modification from the native biopolymer. Here, the assays commonly employed for monitoring the traditional fungal peroxidases, alkyl aryl etherase, and laccase are described in their respective contexts. A soluble native polymeric substrate that can be isolated directly from a conventional milled-wood lignin preparation is characterized in relation to its utility in next-generation lignin-depolymerase assays.

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.

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

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.

Comparison of the acetyl bromide spectrophotometric method with other analytical lignin methods for determining lignin concentration in forage samples.

Science.gov (United States)

Fukushima, Romualdo S; Hatfield, Ronald D

2004-06-16

Present analytical methods to quantify lignin in herbaceous plants are not totally satisfactory. A spectrophotometric method, acetyl bromide soluble lignin (ABSL), has been employed to determine lignin concentration in a range of plant materials. In this work, lignin extracted with acidic dioxane was used to develop standard curves and to calculate the derived linear regression equation (slope equals absorptivity value or extinction coefficient) for determining the lignin concentration of respective cell wall samples. This procedure yielded lignin values that were different from those obtained with Klason lignin, acid detergent acid insoluble lignin, or permanganate lignin procedures. Correlations with in vitro dry matter or cell wall digestibility of samples were highest with data from the spectrophotometric technique. The ABSL method employing as standard lignin extracted with acidic dioxane has the potential to be employed as an analytical method to determine lignin concentration in a range of forage materials. It may be useful in developing a quick and easy method to predict in vitro digestibility on the basis of the total lignin content of a sample.

Cytocompatible cellulose hydrogels containing trace lignin

International Nuclear Information System (INIS)

Nakasone, Kazuki; Kobayashi, Takaomi

2016-01-01

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 12 h. 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 0.43 N/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. - Highlights: • Cellulose hydrogel films with trace lignin were obtained from sugarcane bagasse. • Lignin content was found to be in the range of 1.62 − 0.68% by UV–Vis spectroscopy. • Higher lignin content strengthened mechanical properties of the hydrogel films. • Trace lignin affected the hydrogel morphology such as roughness and porosity. • High cell proliferation was observed in the hydrogel containing 1.68% lignin.

Cytocompatible cellulose hydrogels containing trace lignin

Energy Technology Data Exchange (ETDEWEB)

Nakasone, Kazuki; Kobayashi, Takaomi, E-mail: takaomi@nagaoakut.ac.jp

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 12 h. 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 0.43 N/mm{sup 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. - Highlights: • Cellulose hydrogel films with trace lignin were obtained from sugarcane bagasse. • Lignin content was found to be in the range of 1.62 − 0.68% by UV–Vis spectroscopy. • Higher lignin content strengthened mechanical properties of the hydrogel films. • Trace lignin affected the hydrogel morphology such as roughness and porosity. • High cell proliferation was observed in the hydrogel containing 1.68% lignin.

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.

Enzymatically and chemically oxidized lignin nanoparticles for biomaterial applications.

Science.gov (United States)

Mattinen, Maija-Liisa; Valle-Delgado, Juan José; Leskinen, Timo; Anttila, Tuomas; Riviere, Guillaume; Sipponen, Mika; Paananen, Arja; Lintinen, Kalle; Kostiainen, Mauri; Österberg, Monika

2018-04-01

Cross-linked and decolorized lignin nanoparticles (LNPs) were prepared enzymatically and chemically from softwood Kraft lignin. Colloidal lignin particles (CLPs, ca. 200 nm) in a non-malodorous aqueous dispersion could be dried and redispersed in tetrahydrofuran (THF) or in water retaining their stability i.e. spherical shape and size. Two fungal laccases, Trametes hirsuta (ThL) and Melanocarpus albomyces (MaL) were used in the cross-linking reactions. Reactivity of ThL and MaL on Lignoboost™ lignin and LNPs was confirmed by high performance size exclusion chromatography (HPSEC) and oxygen consumption measurements with simultaneous detection of red-brown color due to the formation of quinones. Zeta potential measurements verified oxidation of LNPs via formation of surface-oriented carboxylic acid groups. Dynamic light scattering (DLS) revealed minor changes in the particle size distributions of LNPs after laccase catalyzed radicalization, indicating preferably covalent intraparticular cross-linking over polymerization. Changes in the surface morphology of laccase treated LNPs were imaged by atomic force (AFM) and transmission emission (TEM) microscopy. Furthermore, decolorization of LNPs without degradation was obtained using ultrasonication with H 2 O 2 in alkaline reaction conditions. The research results have high impact for the utilization of Kraft lignin as nanosized colloidal particles in advanced bionanomaterial applications in medicine, foods and cosmetics including different sectors from chemical industry. Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.

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.

Fast pyrolysis of lignin, macroalgae and sewage sludge

DEFF Research Database (Denmark)

Trinh, Ngoc Trung

effect on the product distributions of the lignin and sewage sludge PCR pyrolysis, as well as their bio-oil properties with respect to molecular mass distribution, identified GC-MS component compositions, water-insoluble fraction, viscosity, and HHV. A maximum of organic oil yields of lignin and sewage...... samples of wood, char and grinded char with respect to phase transitions, rheological properties, elemental composition, and energy density were investigated. Also pumping properties were investigated at temperatures of 25, 40 and 60 ºC and the solids loading of 0 - 20 wt%. The bioslurries obtained...... of the condenser nozzle and high rotor speed for obtaining high bio-oil. The recognized limitations lead to that the old PCR set-up cannot be safely scaled up and perform well in a continuous mode. Thus a new set-up with significant modifications of reactor and bio-condenser has been manufactured to overcome...

Red Xylem and Higher Lignin Extractability by Down-Regulating a Cinnamyl Alcohol Dehydrogenase in Poplar.

Science.gov (United States)

Baucher, M.; Chabbert, B.; Pilate, G.; Van Doorsselaere, J.; Tollier, M. T.; Petit-Conil, M.; Cornu, D.; Monties, B.; Van Montagu, M.; Inze, D.; Jouanin, L.; Boerjan, W.

1996-12-01

Cinnamyl alcohol dehydrogenase (CAD) catalyzes the last step in the biosynthesis of the lignin precursors, the monolignols. We have down-regulated CAD in transgenic poplar (Populus tremula X Populus alba) by both antisense and co-suppression strategies. Several antisense and sense CAD transgenic poplars had an approximately 70% reduced CAD activity that was associated with a red coloration of the xylem tissue. Neither the lignin amount nor the lignin monomeric composition (syringyl/guaiacyl) were significantly modified. However, phloroglucinol-HCl staining was different in the down-regulated CAD plants, suggesting changes in the number of aldehyde units in the lignin. Furthermore, the reactivity of the cell wall toward alkali treatment was altered: a lower amount of lignin was found in the insoluble, saponified residue and more lignin could be precipitated from the soluble alkali fraction. Moreover, large amounts of phenolic compounds, vanillin and especially syringaldehyde, were detected in the soluble alkali fraction of the CAD down-regulated poplars. Alkaline pulping experiments on 3-month-old trees showed a reduction of the kappa number without affecting the degree of cellulose degradation. These results indicate that reducing the CAD activity in trees might be a valuable strategy to optimize certain processes of the wood industry, especially those of the pulp and paper industry.

Raman spectra of lignin model compounds

Science.gov (United States)

Umesh P. Agarwal; Richard S. Reiner; Ashok K. Pandey; Sally A. Ralph; Kolby C. Hirth; Rajai H. Atalla

2005-01-01

To fully exploit the value of Raman spectroscopy for analyzing lignins and lignin containing materials, a detailed understanding of lignins’ Raman spectra needs to be achieved. Although advances made thus far have led to significant growth in application of Raman techniques, further developments are needed to improve upon the existing knowledge. Considering that lignin...

Lignin from Micro- to Nanosize: Applications

Directory of Open Access Journals (Sweden)

Stefan Beisl

2017-11-01

Full Text Available Micro- and nanosize lignin has recently gained interest due to improved properties compared to standard lignin available today. As the second most abundant biopolymer after cellulose, lignin is readily available but used for rather low-value applications. This review focuses on the application of micro- and nanostructured lignin in final products or processes that all show potential for high added value. The fields of application are ranging from improvement of mechanical properties of polymer nanocomposites, bactericidal and antioxidant properties and impregnations to hollow lignin drug carriers for hydrophobic and hydrophilic substances. Also, a carbonization of lignin nanostructures can lead to high-value applications such as use in supercapacitors for energy storage. The properties of the final product depend on the surface properties of the nanomaterial and, therefore, on factors like the lignin source, extraction method, and production/precipitation methods, as discussed in this review.

Fabrication of environmentally biodegradable lignin nanoparticles.

Science.gov (United States)

Frangville, Camille; Rutkevičius, Marius; Richter, Alexander P; Velev, Orlin D; Stoyanov, Simeon D; Paunov, Vesselin N

2012-12-21

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 first method is based on precipitation of low-sulfonated lignin from an ethylene glycol solution by using diluted acidic aqueous solutions, which yields lignin NPs that are stable over a wide range of pH. The second approach is based on the acidic precipitation of lignin from a high-pH aqueous solution which produces NPs stable only at low pH. Our study reveals that lignin NPs from the ethylene glycol-based precipitation contain densely packed lignin domains which explain the stability of the NPs even at high pH. We characterised the properties of the produced lignin NPs and determined their loading capacities with hydrophilic actives. The results suggest that these NPs are highly porous and consist of smaller lignin domains. Tests with microalgae like Chlamydomonas reinhardtii and yeast incubated in lignin NP dispersions indicated that these NPs lack measurable effect on the viability of these microorganisms. Such biodegradable and environmentally compatible NPs can find applications as drug delivery vehicles, stabilisers of cosmetic and pharmaceutical formulations, or in other areas where they may replace more expensive and potentially toxic nanomaterials. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of lignin biotransformation by Aspergillus fumigatus and white-rot fungi using 14C-labeled and unlabeled kraft lignins

International Nuclear Information System (INIS)

Kadam, K.K.; Drew, S.W.

1986-01-01

The biodegradation of lignin by fungi was studied in shake flasks using 14 C-labeled kraft lignin and in a deep-tank fermentor using unlabeled kraft lignin. Among the fungi screened, A. fumigatus - isolated in our laboratories - was most potent in lignin biotransformation. Dialysis-type fermentation, designed to study possible accumulation of low MW lignin-derived products, showed no such accumulation. Recalcitrant carbohydrates like microcrystalline cellulose supported higher lignolytic activity than easily metabolized carbohydrates like cellobiose. An assay developed to distinguish between CO 2 evolved from lignin and carbohydrate substrates demonstrated no stoichiometric correlation between the metabolism of the two cosubstrates. The submerged fermentations with unlabeled liqnin are difficult to monitor since chemical assays do not give accurate and true results. Lignolytic efficiencies that allowed monitoring of such fermentations were defined. Degraded lignins were clearly superior to C. versicolor in all aspects of lignin degradation; A fumigatus brought about substantial demethoxylation and dehydroxylation, whereas C. versicolor degraded lignins closely resembled undegraded kraft lignin. There was a good agreement among the different indices of lignin degradation, namely, 14 CO evolution, OCH 3 loss, OH loss, and monomer and dimer yield after permanganate oxidation

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

Engineering a Monolignol 4-O-Methyltransferase with High Selectivity for the Condensed Lignin Precursor Coniferyl Alcohol*

Science.gov (United States)

Cai, Yuanheng; Bhuiya, Mohammad-Wadud; Shanklin, John; Liu, Chang-Jun

2015-01-01

Lignin, a rigid biopolymer in plant cell walls, is derived from the oxidative polymerization of three monolignols. The composition of monolignol monomers dictates the degree of lignin condensation, reactivity, and thus the degradability of plant cell walls. Guaiacyl lignin is regarded as the condensed structural unit. Polymerization of lignin is initiated through the deprotonation of the para-hydroxyl group of monolignols. Therefore, preferentially modifying the para-hydroxyl of a specific monolignol to deprive its dehydrogenation propensity would disturb the formation of particular lignin subunits. Here, we test the hypothesis that specific remodeling the active site of a monolignol 4-O-methyltransferase would create an enzyme that specifically methylates the condensed guaiacyl lignin precursor coniferyl alcohol. Combining crystal structural information with combinatorial active site saturation mutagenesis and starting with the engineered promiscuous enzyme, MOMT5 (T133L/E165I/F175I/F166W/H169F), we incrementally remodeled its substrate binding pocket by the addition of four substitutions, i.e. M26H, S30R, V33S, and T319M, yielding a mutant enzyme capable of discriminately etherifying the para-hydroxyl of coniferyl alcohol even in the presence of excess sinapyl alcohol. The engineered enzyme variant has a substantially reduced substrate binding pocket that imposes a clear steric hindrance thereby excluding bulkier lignin precursors. The resulting enzyme variant represents an excellent candidate for modulating lignin composition and/or structure in planta. PMID:26378240

Anaerobic biodegradation of the lignin and polysaccharide components of lignocellulose and synthetic lignin by sediment microflora

Energy Technology Data Exchange (ETDEWEB)

Benner, R.; Maccubbin, A.E.; Hodson, R.E.

1984-05-01

Specifically radiolabeled (/sup 14/C-lignin)lignocelluloses and (/sup 14/C-polysaccharide)lignocelluloses were prepared from a variety of marine and freshwater wetland plants including a grass, a sedge, a rush, and a hardwood. These (/sup 14/C)lignocellulose preparations and synthetic (/sup 14/C)lignin were incubated anaerobically with anoxic sediments collected from a salt marsh, a freshwater marsh, and a mangrove swamp. During long-term incubations lasting up to 300 days, the lignin and polysaccharide components of the lignocelluloses were slowly degraded anaerobically to /sup 14/CO/sub 2/ and /sup 14/CH/sub 4/. Lignocelluloses derived from herbaceous plants were degraded more rapidly than lignocellulose derived from the hardwood. After 294 days, 16.9% of the lignin component and 30.0% of the polysaccharide component of lignocellulose derived from the grass used (Spartina alterniflora) were degraded to gaseous end products. In contrast, after 246 days, only 1.5% of the lignin component and 4.1% of the polysaccharide component of lignocellulose derived from the hardwood used (Rhizophora mangle) were degraded to gaseous end products. Synthetic (/sup 14/C) lignin was degraded anaerobically faster than the lignin component of the hardwood lignocellulose; after 276 days 3.7% of the synthetic lignin was degraded to gaseous end products. Contrary to previous reports, these results demonstrate that lignin and lignified plant tissues are biodegradable in the absence of oxygen. Although lignocelluloses are recalcitrant to anaerobic biodegradation, rates of degradation measured in aquatic sediments are significant and have important implications for the biospheric cycling of carbon from these abundant biopolymers. 31 references.

Effect of lignin content on a GH11 endoxylanase acting on glucuronoarabinoxylan-lignin nanocomposites.

Science.gov (United States)

Boukari, Imen; Rémond, Caroline; O'Donohue, Michael; Chabbert, Brigitte

2012-06-20

The effects of lignin content on the activity and action pattern of GH11 endoxylanase from Thermobacillus xylanilyticus were investigated using in vitro reconstituted non-covalent glucuronoarabinoxylan-model lignin (GAX-DHP) nanocomposites. Four types of nanocomposites were prepared, each displaying different lignin contents. Variations in the DHP (model lignin) polymerization process were induced by increasing the coniferyl alcohol concentration. Examination of the morphology of the nanocomposites revealed globular particles enrobed in a matrix. The size of these particles increased in line with the lignin concentration. Physicochemical characterization of the in vitro reconstituted GAX-DHPs strongly suggested that increased particle size is directly related to the solubility and reactivity of coniferyl alcohol, as reflected by changes in the amount of β-O-4 linkages. Evaluation of the impact of the GH11 endoxylanase on the GAX-DHP nanocomposites revealed a negative correlation between the proportion and organization patterns of DHP in the nanocomposites and enzyme activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Proposal for Modified Damage Probability Distribution Functions

DEFF Research Database (Denmark)

Pedersen, Preben Terndrup; Hansen, Peter Friis

1996-01-01

Immidiately following the Estonia disaster, the Nordic countries establishe a project entitled "Safety of Passenger/RoRo Vessels" As part of this project the present proposal for modified damage stability probability distribution functions has been developed. and submitted to "Sub-committee on st......Immidiately following the Estonia disaster, the Nordic countries establishe a project entitled "Safety of Passenger/RoRo Vessels" As part of this project the present proposal for modified damage stability probability distribution functions has been developed. and submitted to "Sub...

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.

Lignin biodegradation by the ascomycete Chrysonilia sitophila.

Science.gov (United States)

Rodríguez, J; Ferraz, A; Nogueira, R F; Ferrer, I; Esposito, E; Durán, N

1997-01-01

The lignin biodegradation process has an important role in the carbon cycle of the biosphere. The study of this natural process has developed mainly with the use of basidiomycetes in laboratory investigations. This has been a logical approach since most of the microorganisms involved in lignocellulosic degradation belong to this class of fungi. However, other microorganisms such as ascomycetes and also some bacteria, are involved in the lignin decaying process. This work focuses on lignin biodegradation by a microorganism belonging to the ascomycete class, Chrysonilia sitophila. Lignin peroxidase production and characterization, mechanisms of lignin degradation (lignin model compounds and lignin in wood matrix) and biosynthesis of veratryl alcohol are outstanding. Applications of C. sitophila for effluent treatment, wood biodegradation and single-cell protein production are also discussed.

Lignin recovery. A resource to value

International Nuclear Information System (INIS)

Zimbardi, P.; Cardinale, G.; Demichele, M.; Nanna, F.; Viggiano, D.; Bonini, C.; D'Alessio, L.; D'Auria, M.; Teghil, R.; Tofani, D.

1999-01-01

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 [it

Development of lignin in Themeda triandra, Cymbopogon plurinodis ...

African Journals Online (AJOL)

The amount and distribution of lignin in three grass species was determined. Two climax species, Themeda triandra and Cymbopogon plurinodis and one pioneer species, Eragrostis lehmanniana were used in the investigation. Leaf samples of the three grass species were taken at four stages of growth and samples of the ...

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

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

Engineering a monolignol 4-O-methyltransferase with high selectivity for the condensed lignin precursor coniferyl alcohol.

Science.gov (United States)

Cai, Yuanheng; Bhuiya, Mohammad-Wadud; Shanklin, John; Liu, Chang-Jun

2015-10-30

Lignin, a rigid biopolymer in plant cell walls, is derived from the oxidative polymerization of three monolignols. The composition of monolignol monomers dictates the degree of lignin condensation, reactivity, and thus the degradability of plant cell walls. Guaiacyl lignin is regarded as the condensed structural unit. Polymerization of lignin is initiated through the deprotonation of the para-hydroxyl group of monolignols. Therefore, preferentially modifying the para-hydroxyl of a specific monolignol to deprive its dehydrogenation propensity would disturb the formation of particular lignin subunits. Here, we test the hypothesis that specific remodeling the active site of a monolignol 4-O-methyltransferase would create an enzyme that specifically methylates the condensed guaiacyl lignin precursor coniferyl alcohol. Combining crystal structural information with combinatorial active site saturation mutagenesis and starting with the engineered promiscuous enzyme, MOMT5 (T133L/E165I/F175I/F166W/H169F), we incrementally remodeled its substrate binding pocket by the addition of four substitutions, i.e. M26H, S30R, V33S, and T319M, yielding a mutant enzyme capable of discriminately etherifying the para-hydroxyl of coniferyl alcohol even in the presence of excess sinapyl alcohol. The engineered enzyme variant has a substantially reduced substrate binding pocket that imposes a clear steric hindrance thereby excluding bulkier lignin precursors. The resulting enzyme variant represents an excellent candidate for modulating lignin composition and/or structure in planta. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

The role of lignin sulfonate in flotation of bastnasite from barite

International Nuclear Information System (INIS)

Gerdel, M.A.; Smith, R.W.

1988-01-01

In carboxylate collector flotation of bastnasite from other semisoluble salt type minerals such as barite various modifiers must be added in order to achieve selective flotation. One such modifier is a lignin sulfonate. It may function in part by acting as a sequestrant for metal ions present, preventing autoactivation in the system by metal ions derived from the minerals themselves. It also functions as a depressant for barite than for bastnasite. The authors suggest that the strong depressing action on barite is related to a good fit of the sulfonate into the barite structure

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. PMID:26436656

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.

Demonstration of Lignin-to-Peroxidase Direct Electron Transfer: A TRANSIENT-STATE KINETICS, DIRECTED MUTAGENESIS, EPR, AND NMR STUDY.

Science.gov (United States)

Sáez-Jiménez, Verónica; Baratto, Maria Camilla; Pogni, Rebecca; Rencoret, Jorge; Gutiérrez, Ana; Santos, José Ignacio; Martínez, Angel T; Ruiz-Dueñas, Francisco Javier

2015-09-18

Versatile peroxidase (VP) is a high redox-potential peroxidase of biotechnological interest that is able to oxidize phenolic and non-phenolic aromatics, Mn(2+), and different dyes. The ability of VP from Pleurotus eryngii to oxidize water-soluble lignins (softwood and hardwood lignosulfonates) is demonstrated here by a combination of directed mutagenesis and spectroscopic techniques, among others. In addition, direct electron transfer between the peroxidase and the lignin macromolecule was kinetically characterized using stopped-flow spectrophotometry. VP variants were used to show that this reaction strongly depends on the presence of a solvent-exposed tryptophan residue (Trp-164). Moreover, the tryptophanyl radical detected by EPR spectroscopy of H2O2-activated VP (being absent from the W164S variant) was identified as catalytically active because it was reduced during lignosulfonate oxidation, resulting in the appearance of a lignin radical. The decrease of lignin fluorescence (excitation at 355 nm/emission at 400 nm) during VP treatment under steady-state conditions was accompanied by a decrease of the lignin (aromatic nuclei and side chains) signals in one-dimensional and two-dimensional NMR spectra, confirming the ligninolytic capabilities of the enzyme. Simultaneously, size-exclusion chromatography showed an increase of the molecular mass of the modified residual lignin, especially for the (low molecular mass) hardwood lignosulfonate, revealing that the oxidation products tend to recondense during the VP treatment. Finally, mutagenesis of selected residues neighboring Trp-164 resulted in improved apparent second-order rate constants for lignosulfonate reactions, revealing that changes in its protein environment (modifying the net negative charge and/or substrate accessibility/binding) can modulate the reactivity of the catalytic tryptophan. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Chapter 1: A Brief Introduction to Lignin Structure

Energy Technology Data Exchange (ETDEWEB)

Katahira, Rui [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Beckham, Gregg T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Elder, Thomas J. [USDA-Forest Service

2018-04-03

Lignin is an alkyl-aromatic polymer found in the cell walls of terrestrial plants. Lignin provides structure and rigidity to plants, is a natural, highly effective barrier against microbial attack, and enables water and nutrient transport through plant tissues. Depending on the plant species, the constituents of lignin can vary considerably, leading to substantial diversity in lignin chemistry and structure. Despite nearly a century of research and development attempting to convert lignin into valuable products, lignin in most current and planned biorefinery contexts remains underutilized, most often being burned to generate heat and power. However, the drive towards effective lignin valorization processes has witnessed a significant resurgence in the past decade, catalyzed by advances in improved understanding of lignin chemistry, structure, and plasticity in parallel with new catalytic and biological approaches to valorize this important, prevalent biopolymer. As a preface to the subsequent chapters in this book, this chapter briefly highlights the known aspects of lignin structure.

Structural Redesigning Arabidopsis Lignins into Alkali-Soluble Lignins through the Expression of p-Coumaroyl-CoA:Monolignol Transferase PMT1

Science.gov (United States)

Sibout, Richard; Le Bris, Philippe; Cézard, Laurent

2016-01-01

Grass lignins can contain up to 10% to 15% by weight of p-coumaric esters. This acylation is performed on monolignols under the catalysis of p-coumaroyl-coenzyme A monolignol transferase (PMT). To study the impact of p-coumaroylation on lignification, we first introduced the Brachypodium distachyon Bradi2g36910 (BdPMT1) gene into Arabidopsis (Arabidopsis thaliana) under the control of the constitutive maize (Zea mays) ubiquitin promoter. The resulting p-coumaroylation was far lower than that of lignins from mature grass stems and had no impact on stem lignin content. By contrast, introducing either the BdPMT1 or the Bradi1g36980 (BdPMT2) gene into Arabidopsis under the control of the Arabidopsis cinnamate-4-hydroxylase promoter boosted the p-coumaroylation of mature stems up to the grass lignin level (8% to 9% by weight), without any impact on plant development. The analysis of purified lignin fractions and the identification of diagnostic products confirmed that p-coumaric acid was associated with lignins. BdPMT1-driven p-coumaroylation was also obtained in the fah1 (deficient for ferulate 5-hydroxylase) and ccr1g (deficient for cinnamoyl-coenzyme A reductase) lines, albeit to a lower extent. Lignins from BdPMT1-expressing ccr1g lines were also found to be feruloylated. In Arabidopsis mature stems, substantial p-coumaroylation of lignins was achieved at the expense of lignin content and induced lignin structural alterations, with an unexpected increase of lignin units with free phenolic groups. This higher frequency of free phenolic groups in Arabidopsis lignins doubled their solubility in alkali at room temperature. These findings suggest that the formation of alkali-leachable lignin domains rich in free phenolic groups is favored when p-coumaroylated monolignols participate in lignification in a grass in a similar manner. PMID:26826222

Cationic electrodepositable coating composition comprising lignin

Science.gov (United States)

Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

2013-07-30

A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

The physical properties, lignin distribution, chemical composition of fibers and gas exchange rate of kenaf (Hibiscus cannabinus L.) varieties under prolonged water deficiency

OpenAIRE

Khalatbari, A.M; Jaafar, Z.E; Khalatbari, A. A; Hazandy, A.H; Mohd Ridzwan, A. H

2016-01-01

The fundamental characteristics and physical properties of kenaf (Hibiscus cannabinus L.) fibers cultivated and subjected to three different water frequencies in Universiti Putra Malaysia, were analyzed. For deep analysis, which includes micro-scale viewing for identification of kenaf cell wall structure, fibers were viewed in order to study the physical characteristics, anatomy, and lignin distribution. The chemical composition was determined considering Technical Association of Pulp and Pap...

Lignin Biodegradation with Laccase-Mediator Systems

International Nuclear Information System (INIS)

Christopher, Lew Paul; Yao, Bin; Ji, Yun

2014-01-01

Lignin has a significant and largely unrealized potential as a source for the sustainable production of fuels and bulk high-value chemicals. It can replace fossil-based oil as a renewable feedstock that would bring about socio-economic and environmental benefits in our transition to a biobased economy. The efficient utilization of lignin however requires its depolymerization to low-molecular weight phenolics and aromatics that can then serve as the building blocks for chemical syntheses of high-value products. The ability of laccase to attack and degrade lignin in conjunction with laccase mediators is currently viewed as one of the potential “breakthrough” applications for lignin valorization. Here, we review the recent progress in lignin biodegradation with laccase-mediator systems, and research needs that need to be addressed in this field.

Lignin Biodegradation with Laccase-Mediator Systems

Energy Technology Data Exchange (ETDEWEB)

Christopher, Lew Paul, E-mail: lew.christopher@sdsmt.edu [Center for Bioprocessing Research and Development, South Dakota School of Mines & Technology, Rapid City, SD (United States); Department of Civil and Environmental Engineering, South Dakota School of Mines & Technology, Rapid City, SD (United States); Yao, Bin [Center for Bioprocessing Research and Development, South Dakota School of Mines & Technology, Rapid City, SD (United States); Ji, Yun [Department of Chemical Engineering, University of North Dakota, Grand Forks, ND (United States)

2014-03-31

Lignin has a significant and largely unrealized potential as a source for the sustainable production of fuels and bulk high-value chemicals. It can replace fossil-based oil as a renewable feedstock that would bring about socio-economic and environmental benefits in our transition to a biobased economy. The efficient utilization of lignin however requires its depolymerization to low-molecular weight phenolics and aromatics that can then serve as the building blocks for chemical syntheses of high-value products. The ability of laccase to attack and degrade lignin in conjunction with laccase mediators is currently viewed as one of the potential “breakthrough” applications for lignin valorization. Here, we review the recent progress in lignin biodegradation with laccase-mediator systems, and research needs that need to be addressed in this field.

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

NARCIS (Netherlands)

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

2016-01-01

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

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.

Biosynthesis and incorporation of side-chain-truncated lignin monomers to reduce lignin polymerization and enhance saccharification

OpenAIRE

Eudes, Aymerick; George, Anthe; Mukerjee, Purba; Kim, J.S.; Pollet, B.; Bnke, P.I.; Persil Çetinkol, Özgül

2012-01-01

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 Arab...

Radical nature of C- lignin

Science.gov (United States)

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

2016-01-01

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...

Dissolution of lignin in green urea aqueous solution

Science.gov (United States)

Wang, Jingyu; Li, Ying; Qiu, Xueqing; Liu, Di; Yang, Dongjie; Liu, Weifeng; Qian, Yong

2017-12-01

The dissolution problem is the main obstacle for the value-added modification and depolymerization of industrial lignin. Here, a green urea aqueous solution for complete dissolution of various lignin is presented and the dissolution mechanism is analyzed by AFM, DLS and NMR. The results show that the molecular interaction of lignin decreases from 32.3 mN/m in pure water to 11.3 mN/m in urea aqueous solution. The immobility of 1H NMR spectra and the shift of 17O NMR spectra of urea in different lignin/urea solutions indicate that the oxygen of carbonyl in urea and the hydrogen of hydroxyl in lignin form new hydrogen bonds and break the original hydrogen bonds among lignin molecules. The shift of 1H NMR spectra of lignin and the decrease of interactions in model compound polystyrene indicate that urea also breaks the π-π interactions between aromatic rings of lignin. Lignin dissolved in urea aqueous has good antioxidant activity and it can scavenge at least 63% free radicals in 16 min.

Lignin derivatives from desilicated rice straw soda black liquor

Energy Technology Data Exchange (ETDEWEB)

El-Taraboulsi, M A; Nasser, M M

1979-01-01

Carboxymethyl lignin, cyanoethyl lignin, carboxyethyl lignin, and aminopropyl lignin were prepared from alkali lignin of rice straw black liquor (after disilication by storage for 1 wk to 1 yr) and used as sizes for paper, drilling fluid additives and flocculants.

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.

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�

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

NMR characterization of altered lignins extracted from tobacco plants down-regulated for lignification enzymes cinnamylalcohol dehydrogenase and cinnamoyl-CoA reductase.

Science.gov (United States)

Ralph, J; Hatfield, R D; Piquemal, J; Yahiaoui, N; Pean, M; Lapierre, C; Boudet, A M

1998-10-27

Homologous antisense constructs were used to down-regulate tobacco cinnamyl-alcohol dehydrogenase (CAD; EC 1.1.1.195) and cinnamoyl-CoA reductase (CCR; EC 1.2.1.44) activities in the lignin monomer biosynthetic pathway. CCR converts activated cinnamic acids (hydroxycinnamoyl-SCoAs) to cinnamaldehydes; cinnamaldehydes are then reduced to cinnamyl alcohols by CAD. The transformations caused the incorporation of nontraditional components into the extractable tobacco lignins, as evidenced by NMR. Isolated lignin of antisense-CAD tobacco contained fewer coniferyl and sinapyl alcohol-derived units that were compensated for by elevated levels of benzaldehydes and cinnamaldehydes. Products from radical coupling of cinnamaldehydes, particularly sinapaldehyde, which were barely discernible in normal tobacco, were major components of the antisense-CAD tobacco lignin. Lignin content was reduced in antisense-CCR tobacco, which displayed a markedly reduced vigor. That lignin contained fewer coniferyl alcohol-derived units and significant levels of tyramine ferulate. Tyramine ferulate is a sink for the anticipated build-up of feruloyl-SCoA, and may be up-regulated in response to a deficit of coniferyl alcohol. Although it is not yet clear whether the modified lignins are true structural components of the cell wall, the findings provide further indications of the metabolic plasticity of plant lignification. An ability to produce lignin from alternative monomers would open new avenues for manipulation of lignin by genetic biotechnologies.

Adsorption Properties of Lignin-derived Activated Carbon Fibers (LACF)

Energy Technology Data Exchange (ETDEWEB)

Contescu, Cristian I. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Gallego, Nidia C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Thibaud-Erkey, Catherine [United Technologies Research Center (UTRC), East Hartford, CT (United States); Karra, Reddy [United Technologies Research Center (UTRC), East Hartford, CT (United States)

2016-04-01

The object of this CRADA project between Oak Ridge National Laboratory (ORNL) and United Technologies Research Center (UTRC) is the characterization of lignin-derived activated carbon fibers (LACF) and determination of their adsorption properties for volatile organic compounds (VOC). Carbon fibers from lignin raw materials were manufactured at Oak Ridge National Laboratory (ORNL) using the technology previously developed at ORNL. These fibers were physically activated at ORNL using various activation conditions, and their surface area and pore-size distribution were characterized by gas adsorption. Based on these properties, ORNL did down-select five differently activated LACF materials that were delivered to UTRC for measurement of VOC adsorption properties. UTRC used standard techniques based on breakthrough curves to measure and determine the adsorption properties of indoor air pollutants (IAP) - namely formaldehyde and carbon dioxide - and to verify the extent of saturated fiber regenerability by thermal treatments. The results are summarized as follows: (1) ORNL demonstrated that physical activation of lignin-derived carbon fibers can be tailored to obtain LACF with surface areas and pore size distributions matching the properties of activated carbon fibers obtained from more expensive, fossil-fuel precursors; (2) UTRC investigated the LACF potential for use in air cleaning applications currently pursued by UTRC, such as building ventilation, and demonstrated their regenerability for CO2 and formaldehyde, (3) Both partners agree that LACF have potential for possible use in air cleaning applications.

Hydroxide catalysts for lignin depolymerization

Science.gov (United States)

Beckham, Gregg T; Biddy, Mary J.; Kruger, Jacob S.; Chmely, Stephen C.; Sturgeon, Matthew

2017-10-17

Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

Hydroxide catalysts for lignin depolymerization

Energy Technology Data Exchange (ETDEWEB)

Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

2017-04-25

Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

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.

Large-Scale Membrane- and Lignin-Modified Adsorbent-Assisted Extraction and Preconcentration of Triazine Analogs and Aflatoxins.

Science.gov (United States)

Hu, Shun-Wei; Chen, Shushi

2017-04-11

The large-scale simultaneous extraction and concentration of aqueous solutions of triazine analogs, and aflatoxins, through a hydrocarbon-based membrane (e.g., polyethylene, polyethylene/polypropylene copolymer) under ambient temperature and atmospheric pressure is reported. The subsequent adsorption of analyte in the extraction chamber over the lignin-modified silica gel facilitates the process by reducing the operating time. The maximum adsorption capacity values for triazine analogs and aflatoxins are mainly adsorption mechanism-dependent and were calculated to be 0.432 and 0.297 mg/10 mg, respectively. The permeation, and therefore the percentage of analyte extracted, ranges from 1% to almost 100%, and varies among the solvents examined. It is considered to be vapor pressure- and chemical polarity-dependent, and is thus highly affected by the nature and thickness of the membrane, the discrepancy in the solubility values of the analyte between the two liquid phases, and the amount of adsorbent used in the process. A dependence on the size of the analyte was observed in the adsorption capacity measurement, but not in the extraction process. The theoretical interaction simulation and FTIR data show that the planar aflatoxin molecule releases much more energy when facing toward the membrane molecule when approaching it, and the mechanism leading to the adsorption.

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.

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.

added pressure is: 1) cleavage of ethers (via hydrolysis) to form smaller methoxy-substituted phenolic monomers with aldehyde- or ketone-substituents representative of lignin monomers; 2) cleavage of the methoxy-, aldehyde- and/or ketone-substituents to form primarily methoxy-substituted phenolic monomers; 3) rearrangement of these phenolic monomers due to the enhanced pressure at reaction temperature; 4) formation of oligomers due to interaction amongst the methoxy-substituted phenolic monomers, which is also due to the enhanced pressure at reaction temperature; and 5) repolymerization of the monomers and oligomers to form high molecular weight compounds (i.e., longer reactions times or different pressures seemed to enhance these reactions). Under these conditions, depolymerization seems to be the dominant reaction pathway versus repolymerization. Reactions with lignin and H2O at 365°C have not been previously reported nor has the reaction chemistry for lignin depolymerization at these conditions been established. The results with lignin (or lignin model compounds), subcritical H2O and CO also show that the desired product slate can be modified with different pressure and time conditions. In particular, increasing reaction time (from 15 to 60 min.) caused lignin conversion to decrease, and the products appeared to be reacting with each other. However, the longer reaction time also showed that more methanol is generated (along with more solids).

Lignin Contribution to the Global Carbon Pool: Investigating the Abiotic Modification of Lignin by Reactive Oxygen Species

Science.gov (United States)

Waggoner, Derek Charles

Evidence suggests that reactive oxygen species (ROS), largely generated through photochemical processes, are important in transforming the chemical composition of the large pool of terrestrially-derived dissolved organic matter (DOM) exported from land to water annually. However, due to the challenges inherent in isolating the effects of individual ROS on DOM composition, the role of ROS in the photochemical alteration of DOM remains poorly characterized. The main focus of the studies within this dissertation aim to more thoroughly characterize the alterations to lignin, used as an analog for terrestrial DOM, resulting from reactions with ROS. To investigate the possibility that the alteration of lignin, through reactions involving ROS, could lead to the production of compounds not recognized as having terrestrial origin, lignin-derived DOM was prepared from a sample of Atlantic white cedar (Chamaecyparis thyoides) and used for a number of studies. Lignin-derived DOM was independently exposed to hydroxyl radical (•OH) generated by Fenton reaction, singlet oxygen (1O2) produced using the photosensitizer Rose Bengal, and superoxide (O2-•) via stable potassium superoxide solution, under controlled laboratory conditions to accentuate how each ROS is responsible for the alteration of lignin. Advanced analytical techniques including high performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR), and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), were employed to characterize alteration to lignin taking place following various ROS treatments. Results of these studies have shown distinct differences in the types of new compounds observed from exposure to each ROS as well as ROS reactivity. The alteration of lignin to compounds not typically associated with terrestrial DOM has been demonstrated upon exposure to ROS. It is also suggested that ROS could selectively react with different fractions of lignin like compounds based

Formation and action of lignin-modifying enzymes in cultures of Phlebia radiata supplemented with veratric acid

International Nuclear Information System (INIS)

Lundell, T.; Hatakka, A.; Leonowicz, A.; Rogalski, J.

1990-01-01

Transformation of veratric (3,4-dimethoxybenzoic) acid by the white rot fungus Phlebia radiata was studied to elucidate the role of ligninolytic, reductive, and demeth(ox)ylating enzymes. Under both air and a 100% O 2 atmosphere, with nitrogen limitation and glucose as a carbon source, reducing activity resulted in the accumulation of veratryl alcohol in the medium. When the fungus was cultivated under air, veratric acid caused a rapid increase in laccase (benzenediol:oxygen oxidoreductase; EC 1.10.3.2) production, which indicated that veratic acid was first demethylated, thus providing phenolic compounds for laccase. After a rapid decline in laccase activity, elevated lignin peroxidase (ligninase) activity and manganese-dependent peroxidase production were detected simultaneously with extracellular release of methanol. This indicated apparent demethoxylation. When the fungus was cultivated under a continuous 100% O 2 flow and in the presence of veratric acid, laccase production was markedly repressed, whereas production of lignin peroxidase and degradation of veratryl compounds were clearly enhanced. In all cultures, the increases in lignin peroxidase titers were directly related to veratryl alcohol accumulation. Evolution of 14 CO 2 from 3-O 14 CH 3 -and 4-O 14 CH 3 -labeled veratric acids showed that the position of the methoxyl substituent in the aromatic ring only slightly affected demeth(ox)ylation activity. In both cases, more than 60% of the total 14 C was converted to 14 CO 2 under air in 4 weeks, and oxygen flux increased the degradation rate of the 14 C-labeled veratric acids just as it did with unlabeled cultures

Quantification of Lignin and Its Structural Features in Plant Biomass Using 13C Lignin as Internal Standard for Pyrolysis-GC-SIM-MS.

Science.gov (United States)

van Erven, Gijs; de Visser, Ries; Merkx, Donny W H; Strolenberg, Willem; de Gijsel, Peter; Gruppen, Harry; Kabel, Mirjam A

2017-10-17

Understanding the mechanisms underlying plant biomass recalcitrance at the molecular level can only be achieved by accurate analyses of both the content and structural features of the molecules involved. Current quantification of lignin is, however, majorly based on unspecific gravimetric analysis after sulfuric acid hydrolysis. Hence, our research aimed at specific lignin quantification with concurrent characterization of its structural features. Hereto, for the first time, a polymeric 13 C lignin was used as internal standard (IS) for lignin quantification via analytical pyrolysis coupled to gas chromatography with mass-spectrometric detection in selected ion monitoring mode (py-GC-SIM-MS). In addition, relative response factors (RRFs) for the various pyrolysis products obtained were determined and applied. First, 12 C and 13 C lignin were isolated from nonlabeled and uniformly 13 C labeled wheat straw, respectively, and characterized by heteronuclear single quantum coherence (HSQC), nuclear magnetic resonance (NMR), and py-GC/MS. The two lignin isolates were found to have identical structures. Second, 13 C-IS based lignin quantification by py-GC-SIM-MS was validated in reconstituted biomass model systems with known contents of the 12 C lignin analogue and was shown to be extremely accurate (>99.9%, R 2 > 0.999) and precise (RSD corn stover, and sugar cane bagasse), and lignin contents were in good agreement with the total gravimetrically determined lignin contents. Our robust method proves to be a promising alternative for the high-throughput quantification of lignin in milled biomass samples directly and simultaneously provides a direct insight into the structural features of lignin.

Converting lignin to aromatics: step by step

NARCIS (Netherlands)

Strassberger, Z.I.

2014-01-01

Lignin, the glue that holds trees together, is the most abundant natural resource of aromatics. In that respect, it is a far more advanced resource than crude oil. This is because lignin already contains the aromatic functional groups. Thus, catalytic conversion of lignin to high-value aromatics is

Iron addition to soil specifically stabilized lignin

Science.gov (United States)

Steven J. Hall; Whendee L. Silver; Vitaliy I. Timokhin; Kenneth E. Hammel

2016-01-01

The importance of lignin as a recalcitrant constituent of soil organic matter (SOM) remains contested. Associations with iron (Fe) oxides have been proposed to specifically protect lignin from decomposition, but impacts of Fe-lignin interactions on mineralization rates remain unclear. Oxygen (O2) fluctuations characteristic of humid tropical...

Flash pyrolysis properties of algae and lignin residue

DEFF Research Database (Denmark)

Trinh, Ngoc Trung; Jensen, Peter Arendt; Sørensen, Hanne Risbjerg

of macroalgae showed a promising result with on yield of 54 wt% dry ash free basis (daf) and 78% energy recovery in the bio-oil. The physiochemical properties of the bio-oils were characterized with respect to higher heating value, molecular mass distribution, viscosity, pH, density and elemental compositions......A fast pyrolysis study on lignin and macroalgae (non-conventional biomass) and wood and straw (conventional biomass) were carried out in a pyrolysis centrifugal reactor. The product distributions and energy recoveries were measured and compared among these biomasses. The fast pyrolysis...

Hydrothermal Liquefaction of Enzymatic Hydrolysis Lignin: Biomass Pretreatment Severity Affects Lignin Valorization

DEFF Research Database (Denmark)

Jensen, Mads M.; Djajadi, Demi T.; Torri, Cristian

2018-01-01

Alkalinehydrothermal liquefaction (HTL) of lignin-rich enzymatichydrolysis residues (EnzHR) from wheat straw and Miscanthusx giganteus was performed at 255, 300, and 345 °C to investigate valorization of this side-stream from second-generation bioethanol production. The EnzHR were from biomass...... contributed with additional chemical information as well as confirming trends seen from quantified monomers. This work is relevant for future lignin valorization in biorefineries based on current second-generation bioethanol production....

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...... in batch autoclaves assessing the effects of varying reaction temperature, reaction time, and solvent:lignin ratio, it is shown that hydrothermally pretreated enzymatic hydrolysis lignin solvolysis in supercritical ethanol can produce a heptane soluble bio-oil without the need for exhaustive deoxygenation....... The process does not require addition of catalyst or a reducing agent such as hydrogen. The process is advantageously carried out with a low reaction period ((ethanol:lignin (w/w) ratio of 2:1) which is a previously unexplored domain for lignin...

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

Rheological and thermo-mechanical properties of poly(lactic acid)/lignin-coated cellulose nanocrystal composites

Science.gov (United States)

Anju Gupta; William Simmons; Gregory T. Schueneman; Donald Hylton; Eric A. Mintz

2017-01-01

Improving the processability and physical properties of sustainable biobased polymers and biobased fillers is essential to preserve its biodegradability and make them suitable for different end user applications. Herein, we report the use of spray-dried lignin-coated cellulose nanocrystals (L-CNCs), a biobased filler, to modify the rheological and thermos-mechanical...

Solvothermal conversion of technical lignins over NiMo catalysts

DEFF Research Database (Denmark)

Ghafarnejad Parto, Soheila; Christensen, Jakob Munkholt; Pedersen, Lars Saaby

Scope: Lignin, cellulose and hemicellulose are the main constituents of plants cell walls. Lignin is an aromatic rich compound, composed of phenolic building blocks. Depending on the method used for isolation of lignin from cellulose and hemicellulose, several types of technical lignin are availa......Scope: Lignin, cellulose and hemicellulose are the main constituents of plants cell walls. Lignin is an aromatic rich compound, composed of phenolic building blocks. Depending on the method used for isolation of lignin from cellulose and hemicellulose, several types of technical lignin...... of the range of available technical lignins. In this work, catalytic conversion of different types of lignin using an alumina supported NiMo catalyst (provided by Haldor Topsøe A/S) is conducted in ethanol at 310 ˚C with initial hydrogen pressure of 25 barg. The reaction time was set to 3 hours. Proton......, attributed as ‘bio-oil’. GC-MS-FID analysis was used for identification and quantification of the bio-oil and ethanol rich light fraction. The molecular weight of the oil fraction was determined by size exclusion chromatography (SEC). Elemental analysis (Eurovector EuroEA3000) was conducted for measuring...

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...... to solvent. Comparatively impure, crude lignin- rich solid residual can be directly converted by supercritical alcohol treatment to significantly diesel-soluble lignin oil without requirement for pre-extraction or pre- solubilisation of lignin or for added reaction promoters such as catalysts, hydrogen donor...... co-solvents, acids, based or H2 gas. O:C ratio of product oil can readily be obtained using crude lignin residual in such a process at levels 0.20 or lower....

Studies on the biosynthesis of lignins and their production in plant cell cultures. [Forsythia intermedia; Podophyllum hexandrum; Podophyllum peltatum

Energy Technology Data Exchange (ETDEWEB)

Abdul-Rahman, M.M.

1988-01-01

Phytochemical analysis of Forsythia intermedia tissues has demonstrated the presence of lignins of the dibenzylbutyrolactone and dioxabicyclo(3,3,0)octane classes, together with their O-glucosides. Lignin distribution in different parts of the part, and variation with the season has been recorded. Cell suspension cultures from F. intermedia were developed. These also synthesized lignins, though not the full range as found in the fresh tissues. Culture lines synthesizing either matairesinol 4{prime}-O-glucoside and major lignin components were established. These cultures rapidly metabolized exogenous lignins without producing detectable lignin transformation products. The seasonal variation in aryltetralin lactone levels in young plants Podophyllum hexandrum and P. peltatum has been investigated. Cell cultures of the plants were established, but no lignins were detectable in them. However, a protocol for micropropagation via embryoid production was obtained. Feeding experiments in P. hexandrum plants showed that matairesinol was a precursor of both podophyllotoxin and 4{prime}-demethylpodophyllotoxin, thus indicating it to be a common precursor of the trimethoxy and hydroxydimethoxy series of lignins in this plant. Precursor feeding experiments with {sup 3}H/{sup 14}C-labeled coniferyl alcohol showed an unexpected increase in {sup 3}H/{sup 14}C ratio when incorporated into both Forsythia and Podophyllum lignins.

Changes in soil lignin by the conversion of forest to silvopastoral systems in hill-lands of Appalachia

Science.gov (United States)

Establishment of silvopastoral systems in Appalachia has potential to increase farm income. Required fertilization and liming for the silvopastoral systems modifies soil chemical properties, including formation and stabilization of soil organic matter (SOM) though the impact is unknown. Lignin is ...

Oxidative polymerization of lignins by laccase in water-acetone mixture.

Science.gov (United States)

Fiţigău, Ionița Firuța; Peter, Francisc; Boeriu, Carmen Gabriela

2013-01-01

The enzymatic oxidative polymerization of five technical lignins with different molecular properties, i.e. Soda Grass/Wheat straw Lignin, Organosolv Hardwood Lignin, Soda Wheat straw Lignin, Alkali pretreated Wheat straw Lignin, and Kraft Softwood was studied. All lignins were previously fractionated by acetone/water 50:50 (v/v) and the laccase-catalyzed polymerization of the low molecular weight fractions (Mw Reactivity of lignin substrates in laccase-catalyzed reactions was determined by monitoring the oxygen consumption. The oxidation reactions in 50% acetone in water mixture proceed with high rate for all tested lignins. Polymerization products were analyzed by size exclusion chromatography, FT-IR, and (31)P-NMR and evidence of important lignin modifications after incubation with laccase. Lignin polymers with higher molecular weight (Mw up to 17500 g/mol) were obtained. The obtained polymers have potential for applications in bioplastics, adhesives and as polymeric dispersants.

Polyurethane foam impregnated with lignin as a filler for the removal of crude oil from contaminated water

Energy Technology Data Exchange (ETDEWEB)

Santos, O.S.H. [Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais, Belo Horizonte, Minas Gerais, CEP: 31.270-901 (Brazil); Coelho da Silva, Mercês [Engenharia de Materiais, Universidade Federal de Itajubá—UNIFEI, Campus Universitário de Itabira. Itabira, Minas Gerais, CEP: 35.903-087 (Brazil); Silva, V.R.; Mussel, W.N. [Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais, Belo Horizonte, Minas Gerais, CEP: 31.270-901 (Brazil); Yoshida, M.I., E-mail: mirene@ufmg.br [Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais, Belo Horizonte, Minas Gerais, CEP: 31.270-901 (Brazil)

2017-02-15

Highlights: • The presence of lignin in polyurethane foams increased oil sorption capacity. • The presence of lignin resulted in a decrease in the hydrophobicity of the foams. • Langmuir isotherm predicted a maximum oil adsorption of 28.9 g g{sup −1} by the PUF-10. • ΔG° (−4.4 kJ mol{sup −1}) indicated that adsorption process by PUF-10 was spontaneous. • The recyclability of the foam showed efficiency greater than 95% after five cycles. - Abstract: The present study describes the influence of the concentration of lignin when used as a filler in polyurethane foam for crude oil sorption. The foams (lignin 0–20 wt%) were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis, contact angle and density. The FTIR analysis confirmed urethane linkage formation, showing that the chemical structure of the polymer was preserved, despite the addition of different lignin concentrations. Thermogravimetric analysis showed that the presence of lignin has altered the onset temperature (T{sub onset}) of the foams, decreasing as the concentration of lignin is increased. The contact angle analysis showed a decrease in the hydrophobicity of the foams with increasing lignin concentration. All modified foams showed an improvement in the oil sorption capacity in a PUF/oil/water system, and the PUF-10 showed an improvement of about 35.5% compared to the PUF-blank. The Langmuir isotherm showed a better fit to the data and predicted a maximum oil adsorption of 28.9 g g{sup −1} by the PUF-10. The ΔG° value of −4.4 kJ mol{sup −1} indicated that crude oil adsorption process by PUF-10 was spontaneous. The results of reuse of the PUF-10 showed that oil removal efficiency remained greater than 95% after five consecutive cycles.

Theoretical Approaches to Lignin Chemistry

OpenAIRE

Shevchenko, Sergey M.

1994-01-01

A critical review is presented of the applications of theoretical methods to the studies of the structure and chemical reactivity of lignin, including simulation of macromolecular properties, conformational calculations, quantum chemical analyses of electronic structure, spectra and chemical reactivity. Modern concepts of spatial organization and chemical reactivity of lignins are discussed.

Enzymatic synthesis of lignin-siloxane hybrid functional polymers.

Science.gov (United States)

Prasetyo, Endry Nugroho; Kudanga, Tukayi; Fischer, Roman; Eichinger, Reinhard; Nyanhongo, Gibson S; Guebitz, Georg M

2012-02-01

This study combines the properties of siloxanes and lignin polymers to produce hybrid functional polymers that can be used as adhesives, coating materials, and/or multifunctionalized thin-coating films. Lignin-silica hybrid copolymers were synthesized by using a sol-gel process. Laccases from Trametes hirsuta were used to oxidize lignosulphonates to enhance their reactivity towards siloxanes and then were incorporated into siloxane precursors undergoing a sol-gel process. In vitro copolymerization studies using pure lignin monomers with aminosilanes or ethoxytrimethylsilane and analysis by ²⁹Si NMR spectroscopy revealed hybrid products. Except for kraft lignin, an increase in lignin concentration positively affected the tensile strength in all samples. Similarly, the viscosity generally increased in all samples with increasing lignin concentration and also affected the curing time. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast pyrolysis of lignin, macroalgae and sewage sludge

Energy Technology Data Exchange (ETDEWEB)

Trinh, N.T.

2013-04-15

macronutrients as N, P, K, S, Mg and Ca and this could make the chars most valuable as raw materials for fertilizer production. The sewage sludge waste bulk volume (the char compared to the sludge) was reduced with 52 % by pyrolysis at 575 deg. C. It is seen that the fast pyrolysis process provides a promising method to reduce cost for landfilling and produce a bio-oil that can be used as a fuel. The pyrolysis temperature has a considerable effect on the product distributions of the lignin and sewage sludge PCR pyrolysis, as well as their bio-oil properties with respect to molecular mass distribution, identified GC-MS component compositions, water-insoluble fraction, viscosity, and HHV. A maximum of organic oil yields of lignin and sewage sludge PCR pyrolysis were obtained at optimal temperatures of 550 - 575 deg. C. In this work, the behaviors of slurry samples of wood, char and grinded char with respect to phase transitions, rheological properties, elemental composition, and energy density were investigated. Also pumping properties were investigated at temperatures of 25, 40 and 60 deg. C and the solids loading of 0 - 20 wt%. The bioslurries obtained a volume energy density of 21-23 GJ/m{sup 3} and an energy densification factor of 4.5 - 5 (when compared to beech wood). Their apparent viscosities were significantly influenced by the solid loading levels (0 - 20 wt %) and temperatures (25 - 60 deg. C). The slurry samples with 10 wt% char (having d80 of 276 {mu}m) and 20 wt% grinded char (having d80 of 118 {mu}m) were successfully pumped into a pressurized chamber (0 - 6 bar). (LN)

Lignin-blocking treatment of biomass and uses thereof

Science.gov (United States)

Yang, Bin [Hanover, NH; Wyman, Charles E [Norwich, VT

2009-10-20

Disclosed is a method for converting cellulose in a lignocellulosic biomass. The method provides for a lignin-blocking polypeptide and/or protein treatment of high lignin solids. The treatment enhances cellulase availability in cellulose conversion. Cellulase efficiencies are improved by the protein or polypeptide treatment. The treatment may be used in combination with steam explosion and acid prehydrolysis techniques. Hydrolysis yields from lignin containing biomass are enhanced 5-20%, and enzyme utilization is increased from 10% to 50%. Thus, a more efficient and economical method of processing lignin containing biomass materials utilizes a polypeptide/protein treatment step that effectively blocks lignin binding of cellulase.

Identifying new lignin bioengineering targets: 1. Monolignol-substitute impacts on lignin formation and cell wall fermentability

Directory of Open Access Journals (Sweden)

Lu Fachuang

2010-06-01

Full Text Available Abstract Background Recent discoveries highlighting the metabolic malleability of plant lignification indicate that lignin can be engineered to dramatically alter its composition and properties. Current plant biotechnology efforts are primarily aimed at manipulating the biosynthesis of normal monolignols, but in the future apoplastic targeting of phenolics from other metabolic pathways may provide new approaches for designing lignins that are less inhibitory toward the enzymatic hydrolysis of structural polysaccharides, both with and without biomass pretreatment. To identify promising new avenues for lignin bioengineering, we artificially lignified cell walls from maize cell suspensions with various combinations of normal monolignols (coniferyl and sinapyl alcohols plus a variety of phenolic monolignol substitutes. Cell walls were then incubated in vitro with anaerobic rumen microflora to assess the potential impact of lignin modifications on the enzymatic degradability of fibrous crops used for ruminant livestock or biofuel production. Results In the absence of anatomical constraints to digestion, lignification with normal monolignols hindered both the rate and extent of cell wall hydrolysis by rumen microflora. Inclusion of methyl caffeate, caffeoylquinic acid, or feruloylquinic acid with monolignols considerably depressed lignin formation and strikingly improved the degradability of cell walls. In contrast, dihydroconiferyl alcohol, guaiacyl glycerol, epicatechin, epigallocatechin, and epigallocatechin gallate readily formed copolymer-lignins with normal monolignols; cell wall degradability was moderately enhanced by greater hydroxylation or 1,2,3-triol functionality. Mono- or diferuloyl esters with various aliphatic or polyol groups readily copolymerized with monolignols, but in some cases they accelerated inactivation of wall-bound peroxidase and reduced lignification; cell wall degradability was influenced by lignin content and the degree

Preparation of lignin-based carbon aerogels as biomaterials for nano-supercapacitor

Science.gov (United States)

Yang, Bong Suk; Kang, Kyu-Young; Jeong, Myung-Joon

2017-10-01

Kraft and organosolv lignins, generally produced in chemical pulping and bio-refinery processes of lignocellulosic biomass, were used to prepare lignin-based carbon aerogels for supercapacitors as raw materials. The difference between lignins and lignin-based aerogels were compared by analyzing physical and chemical properties, including molecular weight, polydispersity, and reactivity with formaldehyde. Also, density, shrinkage, Brunauer-Emmett-Teller (BET) surface area and scanning electron microscope (SEM) images of the lignin-based aerogel were investigated. Kraft lignin consisting of coniferyl alcohol (G) and p-coumaryl alcohol (H) increased the reactivity of formaldehyde, formed a hydrogel well (porosity > 0.45), and specific surface area higher than organosolv lignin. In the case of kraft lignin, there were irregular changes such as oxidation and condensation in the pulping process. However, reaction sites with aromatic rings in lignin impacted the production of aerogel and required a long gelation period. The molecular weight of lignin influences the gelation time in producing lignin-based aerogel, and lignin composition affects the BET surface area and pore structures of the lignin-based carbon aerogels.

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.

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).

Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol: Influence of Reaction Temperature and Feedstock.

Science.gov (United States)

Huang, Xiaoming; Atay, Ceylanpinar; Zhu, Jiadong; Palstra, Sanne W L; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

2017-11-06

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while char-forming reactions become significant at high reaction temperature (>380 °C). At preferred intermediate temperatures (300-340 °C), char-forming reactions are effectively suppressed by alkylation and Guerbet and esterification reactions. This shifts the reaction toward depolymerization, explaining high monomeric aromatics yield. Carbon-14 dating analysis of the lignin residue revealed that a substantial amount of the carbon in the lignin residue originates from reactions of lignin with ethanol. Recycling tests show that the activity of the regenerated catalyst was strongly decreased due to a loss of basic sites due to hydrolysis of the MgO function and a loss of surface area due to spinel oxide formation of the Cu and Al components. The utility of this one-step approach for upgrading woody biomass was also demonstrated. An important observation is that conversion of the native lignin contained in the lignocellulosic matrix is much easier than the conversion of technical lignin.

Chemical factors that control lignin polymerization.

Science.gov (United States)

Sangha, Amandeep K; Davison, Brian H; Standaert, Robert F; Davis, Mark F; Smith, Jeremy C; Parks, Jerry M

2014-01-09

Lignin is a complex, branched polymer that reinforces plant tissue. Understanding the factors that govern lignin structure is of central importance to the development of technologies for converting lignocellulosic biomass into fuels because lignin imparts resistance to chemical, enzymatic, and mechanical deconstruction. Lignin is formed by enzymatic oxidation of phenolic monomers (monolignols) of three main types, guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H) subunits. It is known that increasing the relative abundance of H subunits results in lower molecular weight lignin polymers and hence more easily deconstructed biomass, but it is not known why. Here, we report an analysis of frontier molecular orbitals in mono-, di-, and trilignols, calculated using density functional theory, which points to a requirement of strong p-electron density on the reacting phenolic oxygen atom of the neutral precursor for enzymatic oxidation to occur. This model is consistent with a proton-coupled electron transfer (PCET) mechanism and for the first time explains why H subunits in certain linkages (β-β or β-5) react poorly and tend to "cap" the polymer. In general, β-5 linkages with either a G or H terminus are predicted to inhibit elongation. More broadly, the model correctly accounts for the reactivity of the phenolic groups in a diverse set of dilignols comprising H and G subunits. Thus, we provide a coherent framework for understanding the propensity toward growth or termination of different terminal subunits in lignin.

Mn(II) regulation of lignin peroxidases and manganese-dependent peroxidases from lignin-degrading white rot fungi

International Nuclear Information System (INIS)

Bonnarme, P.; Jeffries, T.W.

1990-01-01

Two families of peroxidases-lignin peroxidase (LiP) and manganese-dependent lignin peroxidase (MnP)-are formed by the lignin-degrading white rot basidiomycete Phanerochaete chrysosporium and other white rot fungi. Isoenzymes of these enzyme families carry out reactions important to the biodegradation of lignin. This research investigated the regulation of LiP and MnP production by Mn(II). In liquid culture, LiP titers varied as an inverse function of and MnP titers varied as a direct function of the Mn(II) concentration. The extracellular isoenzyme profiles differed radically at low and high Mn(II) levels, whereas other fermentation parameters, including extracellular protein concentrations, the glucose consumption rate, and the accumulation of cell dry weight, did not change significantly with the Mn(II) concentration. In the absence of Mn(II), extracellular LiP isoenzymes predominated, whereas in the presence of Mn(II), MnP isoenzymes were dominant. The release of 14 CO 2 from 14 C-labeled dehydrogenative polymerizate lignin was likewise affected by Mn(II). The rate of 14 CO 2 release increased at low Mn(II) and decreased at high Mn(II) concentrations. This regulatory effect of Mn(II) occurred with five strains of P. chrysosporium, two other species of Phanerochaete, three species of Phlebia, Lentinula edodes, and Phellinus pini

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

Characteristics of Lignin from Flax Shives as Affected by Extraction Conditions

Science.gov (United States)

Ross, Kelly; Mazza, Giuseppe

2010-01-01

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

Reinforcing styrene butadiene rubber with lignin-novolac epoxy resin networks

Directory of Open Access Journals (Sweden)

P. Yu

2015-01-01

Full Text Available In this study, lignin-novolac epoxy resin networks were fabricated in the styrene butadiene rubber (SBR matrix by combination of latex compounding and melt mixing. Firstly, SBR/lignin compounds were co-coagulated by SBR latex and lignin aqueous solution. Then the novolac epoxy resin (F51 was added in the SBR/lignin compounds by melt compounding method. F51 was directly cured by lignin via the ring-opening reaction of epoxy groups of F51 and OH groups (or COOH groups of lignin during the curing process of rubber compounds, as was particularly evident from Fourier transform infrared spectroscopy (FTIR studies and maximum torque of the curing analysis. The existence of lignin-F51 networks were also detected by scanning electron microscope (SEM and dynamic mechanical analysis (DMA. The structure of the SBR/lignin/F51 was also characterized by rubber process analyzer (RPA, thermogravimetric analysis (TGA and determination of crosslinking density. Due to rigid lignin-F51 networks achieved in SBR/lignin/F51 composites, it was found that the hardness, modulus, tear strength, crosslinking density, the temperature of 5 and 10% weight-loss were significantly enhanced with the loading of F51.

Environmental economics of lignin derived transport fuels

OpenAIRE

Obydenkova, SV; Kouris, P Panagiotis; Hensen, EJM Emiel; Heeres, Hero J; Boot, MD Michael

2017-01-01

This paper explores the environmental and economic aspects of fast pyrolytic conversion of lignin, obtained from 2G ethanol plants, to transport fuels for both the marine and automotive markets. Various scenarios are explored, pertaining to aggregation of lignin from several sites, alternative energy carries to replace lignin, transport modalities, and allocation methodology. The results highlight two critical factors that ultimately determine the economic and/or environmental fuel viability....

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.

Alkali-treated kraft lignin as a component in flakeboard eesins

Science.gov (United States)

Mon-Lin Kuo; Chung-Yun Hse; Dee-Hua Huang

1991-01-01

Southern pine kraft lignin was reacted with NaOH (15 and 20% based on dry lignin) at 170, 200, and 250°C for 30 and 60 min. Sweetgum flake boards bonded with phenolic resins containing 50% hydroxymethylated lignin prepared from some of the alkali treated lignins were compared with boards bonded with a neat PF resin. Results indicate that boards bonded with lignin-...

Sources and transformations of dissolved lignin phenols and chromophoric dissolved organic matter in Otsuchi Bay, Japan

Directory of Open Access Journals (Sweden)

Chia-Jung eLu

2016-06-01

Full Text Available Dissolved lignin phenols and optical properties of dissolved organic matter (DOM were measured to investigate the sources and transformations of terrigenous DOM (tDOM in Otsuchi Bay, Japan. Three rivers discharge into the bay, and relatively high values of syringyl:vanillyl phenols (0.73 ± 0.07 and cinnamyl:vanillyl phenols (0.33 ± 0.10 indicated large contributions of non-woody angiosperm tissues to lignin and tDOM. The physical mixing of river and seawater played an important role in controlling the concentrations and distributions of lignin phenols and chromophoric DOM (CDOM optical properties in the bay. Lignin phenol concentrations and the CDOM absorption coefficient at 350 nm, a(350, were strongly correlated in river and bay waters. Measurements of lignin phenols and CDOM in bay waters indicated a variety of photochemical and biological transformations of tDOM, including oxidation reactions, photobleaching and a decrease in molecular weight. Photodegradation and biodegradation of lignin and CDOM were investigated in decomposition experiments with river water and native microbial assemblages exposed to natural sunlight or kept in the dark. There was a rapid and substantial removal of lignin phenols and CDOM during the first few days in the light treatment, indicating transformations of tDOM and CDOM can occur soon after discharge of buoyant river water into the bay. The removal of lignin phenols was slightly greater in the dark (34% than in the light (30% during the remaining 59 days of the incubation. Comparison of the light and dark treatments indicated biodegradation was responsible for 67% of total lignin phenol removal during the 62-day incubation exposed to natural sunlight, indicating biodegradation is a dominant removal process in Otsuchi Bay.

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

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 (NMR), size exclusion chromatography (SEC), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). SEC data revealed a narrow molecular weight distribution with a small polydispersity index in the lignin sample – all desirable features...

Effective release of lignin fragments from lignocellulose by lewis acid metal triflates in the lignin-first approach

NARCIS (Netherlands)

Huang, X.; Zhu, J.; Koranyi, T.I.; Boot, M.D.; Hensen, E.J.M.

2016-01-01

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

Pyrolysis-gas chromatography-mass spectrometry of isolated, synthetic and degraded lignins

Energy Technology Data Exchange (ETDEWEB)

Saiz-Jimenez, C.; De Leeuw, J.W.

1984-01-01

Curie-point pyrolysis-gas chromatography-mass spectrometry was applied to study the chemical structure of sound and fungus degraded, industrial and synthetic lignins. Pyrolysis products reflected in some detail the structural units present in the lignin polymer. Thus, sound spruce lignin yielded trans-isoeugenol coniferaldehyde and trans-coniferyl alcohol as major pyrolysis products. Biodegraded lignin yielded oxidized units, including vanillin, acetoguaiacone, methyl vanillate, propioguaiacone, vanilloyl methyl ketone and vanillic acid as major products. Kraft lignin also showed evidence of oxidation, although not as much as the biodegraded lignin. Major products from this industrial lignin were guaiacol, methylguaiacol, vinylguaiacol and homovanillic acid. Results indicated that synthetic lignin duplicates fairly well the structure of natural lignin. However, coniferylaldehyde and trans-coniferyl alcohol were the dominant products only from the synthetic lignin, indicating the presence of large amounts of coniferyl alcohol and coniferylaldehyde end groups. 21 references.

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

2017-02-04

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.

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

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.

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 �

Characterization of electrospun lignin based carbon fibers

International Nuclear Information System (INIS)

Poursorkhabi, Vida; Mohanty, Amar; Misra, Manjusri

2015-01-01

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

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.

NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins.

Science.gov (United States)

Kim, Hoon; Ralph, John; Lu, Fachuang; Ralph, Sally A; Boudet, Alain M; MacKay, John J; Sederoff, Ronald R; Ito, Takashi; Kawai, Shingo; Ohashi, Hideo; Higuchi, Takayoshi

2003-01-21

Peroxidase/H2O2-mediated radical coupling of 4-hydroxycinnamaldehydes produces 8-O-4-, 8-5-, and 8-8-coupled dehydrodimers as has been documented earlier, as well as the 5-5-coupled dehydrodimer. The 8-5-dehydrodimer is however produced kinetically in its cyclic phenylcoumaran form at neutral pH. Synthetic polymers produced from mixtures of hydroxycinnamaldehydes and normal monolignols provide the next level of complexity. Spectral data from dimers, oligomers, and synthetic polymers have allowed a more substantive assignment of aldehyde components in lignins isolated from a CAD-deficient pine mutant and an antisense-CAD-downregulated transgenic tobacco. CAD-deficient pine lignin shows enhanced levels of the typical benzaldehyde and cinnamaldehyde end-groups, along with evidence for two types of 8-O-4-coupled coniferaldehyde units. The CAD-downregulated tobacco also has higher levels of hydroxycinnamaldehyde and hydroxybenzaldehyde (mainly syringaldehyde) incorporation, but the analogous two types of 8-O-4-coupled products are the dominant features. 8-8-Coupled units are also clearly evident. There is clear evidence for coupling of hydroxycinnamaldehydes to each other and then incorporation into the lignin, as well as for the incorporation of hydroxycinnamaldehyde monomers into the growing lignin polymer. Coniferaldehyde and sinapaldehyde (as well as vanillin and syringaldehyde) co-polymerize with the traditional monolignols into lignins and do so at enhanced levels when CAD-deficiency has an impact on the normal monolignol production. The implication is that, particularly in angiosperms, the aldehydes behave like the traditional monolignols and should probably be regarded as authentic lignin monomers in normal and CAD-deficient plants.

Effect of hypergravity on lignin formation and expression of lignin-related genes in inflorescence stems of an ethylene-insensitive Arabidopsis mutant ein3-1

Science.gov (United States)

Karahara, Ichirou; Kobayashi, Mai; Tamaoki, Daisuke; Kamisaka, Seiichiro

Our previous studies have shown that hypergravity inhibits growth and promotes lignin forma-tion in inflorescence stems of Arabidopsis thaliana by up-regulation of genes involved in lignin biosynthesis (Tamaoki et al. 2006, 2009). In the present study, we have examined whether ethylene is involved in these responses using an ethylene-insensitive Arabidopsis mutant ein3-1. Our results revealed that hypergravity treatment at 300 G for 24 h significantly inhibited growth of inflorescence stems, promoted both deposition of acetyl bromide extractable lignin and gene expression involved in lignin formation in inflorescence stems of wild type plants. Growth inhibition of inflorescence stems was also observed in ein3-1. However, the effects of hypergravity on the promotion of the deposition of acetyl bromide lignin and the expression of genes involved in lignin formation were not observed in ein3-1, indicating that ethylene sig-naling is involved in the up-regulation of the expression of lignin-related genes as well as the promotion of deposition of lignin by hypergravity in Arabidopsis inflorescence stems.

Selective Oxidation of Lignin Model Compounds.

Science.gov (United States)

Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K; Ralph, John

2018-05-02

Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of aromatic products at radiation-thermal destruction of lignin

International Nuclear Information System (INIS)

Metreveli, P.K.; Bludenko, A.V.; Ponomarev, A.V.

2012-01-01

Influence of electron irradiation on lignin destruction is studied. Hydrolyzed lignin and mixture of fatty acid triglycerides (FATG) have been irradiated by 8.5 MeV electrons. Comparative study of four variants of lignin destruction is carried out, they are pyrogenic distillation, post-radiation dry distillation, electron-beam distillation (EBD) and EBD at combined heating. The mechanism of lignin radiation-thermal transformation with guaiacol and creosol formation is considered. Lignin EBD is investigated depending on dose rate, absorbed dose, electroheating power and addition (FATG and chitin) content. It is pointed out, that lignin stimulates radiation-thermal conversion of FATG into low-viscosity diesel fuel. The conclusion is made, that lignin EBD at radiation and combined heating can be perspective effective method of vegetal polyphenols conversion into liquid phenols [ru

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.

Characterization of Trapped Lignin-Degrading Microbes in Tropical Forest Soil

Energy Technology Data Exchange (ETDEWEB)

DeAngelis, Kristen; Allgaier, Martin; Chavarria, Yaucin; Fortney, Julian; Hugenholtz, Phillip; Simmons, Blake; Sublette, Kerry; Silver, Whendee; Hazen, Terry

2011-07-14

Lignin is often the most difficult portion of plant biomass to degrade, with fungi generally thought to dominate during late stage decomposition. Lignin in feedstock plant material represents a barrier to more efficient plant biomass conversion and can also hinder enzymatic access to cellulose, which is critical for biofuels production. Tropical rain forest soils in Puerto Rico are characterized by frequent anoxic conditions and fluctuating redox, suggesting the presence of lignin-degrading organisms and mechanisms that are different from known fungal decomposers and oxygen-dependent enzyme activities. We explored microbial lignin-degraders by burying bio-traps containing lignin-amended and unamended biosep beads in the soil for 1, 4, 13 and 30 weeks. At each time point, phenol oxidase and peroxidase enzyme activity was found to be elevated in the lignin-amended versus the unamended beads, while cellulolytic enzyme activities were significantly depressed in lignin-amended beads. Quantitative PCR of bacterial communities showed more bacterial colonization in the lignin-amended compared to the unamended beads after one and four weeks, suggesting that the lignin supported increased bacterial abundance. The microbial community was analyzed by small subunit 16S ribosomal RNA genes using microarray (PhyloChip) and by high-throughput amplicon pyrosequencing based on universal primers targeting bacterial, archaeal, and eukaryotic communities. Community trends were significantly affected by time and the presence of lignin on the beads. Lignin-amended beads have higher relative abundances of representatives from the phyla Actinobacteria, Firmicutes, Acidobacteria and Proteobacteria compared to unamended beads. This study suggests that in low and fluctuating redox soils, bacteria could play a role in anaerobic lignin decomposition.

Characterization of trapped lignin-degrading microbes in tropical forest soil

Energy Technology Data Exchange (ETDEWEB)

DeAngelis, K.M.; Allgaier, M.; Chavarria, Y.; Fortney, J.L.; Hugenholz, P.; Simmons, B.; Sublette, K.; Silver, W.L.; Hazen, T.C.

2011-03-01

Lignin is often the most difficult portion of plant biomass to degrade, with fungi generally thought to dominate during late stage decomposition. Lignin in feedstock plant material represents a barrier to more efficient plant biomass conversion and can also hinder enzymatic access to cellulose, which is critical for biofuels production. Tropical rain forest soils in Puerto Rico are characterized by frequent anoxic conditions and fluctuating redox, suggesting the presence of lignin-degrading organisms and mechanisms that are different from known fungal decomposers and oxygen-dependent enzyme activities. We explored microbial lignin-degraders by burying bio-traps containing lignin-amended and unamended biosep beads in the soil for 1, 4, 13 and 30 weeks. At each time point, phenol oxidase and peroxidase enzyme activity was found to be elevated in the lignin-amended versus the unamended beads, while cellulolytic enzyme activities were significantly depressed in lignin-amended beads. Quantitative PCR of bacterial communities showed more bacterial colonization in the lignin-amended compared to the unamended beads after one and four weeks, suggesting that the lignin supported increased bacterial abundance. The microbial community was analyzed by small subunit 16S ribosomal RNA genes using microarray (PhyloChip) and by high-throughput amplicon pyrosequencing based on universal primers targeting bacterial, archaeal, and eukaryotic communities. Community trends were significantly affected by time and the presence of lignin on the beads. Lignin-amended beads have higher relative abundances of representatives from the phyla Actinobacteria, Firmicutes, Acidobacteria and Proteobacteria compared to unamended beads. This study suggests that in low and fluctuating redox soils, bacteria could play a role in anaerobic lignin decomposition.

Kraft Lignin Depolymerization in an Ionic Liquid without a Catalyst

Directory of Open Access Journals (Sweden)

Amadou Diop

2015-06-01

Full Text Available In this paper, the depolymerization of lignin was successfully achieved by the thermal treatment of kraft lignin in butyl-1,8-diazabicyclo[5.4.0]undec-7-enium chloride ([DBUC4+][Cl-] without a catalyst. The thermal treatment experiments were performed in an oven at 150, 200, and 250 °C for 1 h. The changes in kraft lignin structure over the course of depolymerization were characterized by gel permeation chromatography (GPC, Fourier transform infrared (FTIR spectroscopy, and 1H / 31P NMR analyses. GPC chromatograms indicated that the retention time of the original kraft lignin had shifted toward higher values after the thermal treatment, which indicated lignin depolymerization. The average molecular weight of the lignin obtained after 1 h reaction time decreased by 23, 70, and 58 wt% for the treatment at 150, 200, and 250 °C, respectively. FTIR spectra indicated the cleavage of β-O-4 bonds of kraft lignin. The 1H NMR spectra showed demethylation of all treated kraft lignins. Moreover, the 31P NMR analysis demonstrated that the demethylation phenomenon of the treated kraft lignin contributed to the formation of catechol groups.

Syringyl-Rich Lignin Renders Poplars More Resistant to Degradation by Wood Decay Fungi

Science.gov (United States)

Skyba, Oleksandr; Douglas, Carl J.

2013-01-01

In order to elucidate the effects of lignin composition on the resistance of wood to degradation by decay fungi, wood specimens from two transgenic poplar lines expressing an Arabidopsis gene encoding ferulate 5-hydroxylase (F5H) driven by the cinnimate-4-hydroxylase promoter (C4H::F5H) that increased syringyl/guaiacyl (S/G) monolignol ratios relative to those in the untransformed control wood were incubated with six different wood decay fungi. Alterations in wood weight and chemical composition were monitored over the incubation period. The results showed that transgenic poplar lines extremely rich in syringyl lignin exhibited a drastically improved resistance to degradation by all decay fungi evaluated. Lignin monomer composition and its distribution among cell types and within different cell layers were the sole wood chemistry parameters determining wood durability. Since transgenic poplars with exceedingly high syringyl contents were recalcitrant to degradation, where wood durability is a critical factor, these genotypes may offer improved performance. PMID:23396333

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

Biological and Catalytic Conversion of Sugars and Lignin Publications |

Science.gov (United States)

biorefinery lignins, ACS Sust. Chem. Eng. Lignin depolymerization with nitrate-intercalated hydrotalcite catalysts, ACS Catalysis Pyrolysis reaction networks for lignin model compounds: Unraveling thermal Free Energy, J. Amer. Chem. Soc. Process Design and Economics for the Conversion of Lignocellulosic

Production of Flocculants, Adsorbents, and Dispersants from Lignin.

Science.gov (United States)

Chen, Jiachuan; Eraghi Kazzaz, Armin; AlipoorMazandarani, Niloofar; Hosseinpour Feizi, Zahra; Fatehi, Pedram

2018-04-10

Currently, lignin is mainly produced in pulping processes, but it is considered as an under-utilized chemical since it is being mainly used as a fuel source. Lignin contains many hydroxyl groups that can participate in chemical reactions to produce value-added products. Flocculants, adsorbents, and dispersants have a wide range of applications in industry, but they are mainly oil-based chemicals and expensive. This paper reviews the pathways to produce water soluble lignin-based flocculants, adsorbents, and dispersants. It provides information on the recent progress in the possible use of these lignin-based flocculants, adsorbents, and dispersants. It also critically discusses the advantages and disadvantages of various approaches to produce such products. The challenges present in the production of lignin-based flocculants, adsorbents, and dispersants and possible scenarios to overcome these challenges for commercial use of these products in industry are discussed.

Impact of lignins isolated from pretreated lignocelluloses on enzymatic cellulose saccharification.

Science.gov (United States)

Barsberg, Søren; Selig, Michael Joseph; Felby, Claus

2013-02-01

Lignins were enzymatically isolated from corn stover and wheat straw samples and subjected to hydrothermal or wet oxidation pretreatments for enzyme adsorption experimentations. Lignin contents of the isolates ranged from 26 to 71 % (w/w); cellulose ranged from 3 to 22 % (w/w); xylan from 0.7 to 6 % (w/w) and ash was from 5.8 to 30 % (w/w). ATR-IR analyses indicated significant and similar levels of calcium in all lignin isolates. Commercial cellulase adsorption studies showed that the presence of these lignins had no significant impact on the total amount of adsorbed enzyme in cellulose and cellulose-lignin systems. Consequently, the presence of the lignins had minimal effect, if any, on enzymatic cellulose conversion. Furthermore, this result, coupled with significant calcium levels in the isolated lignins, supports previous work suggesting lignin-calcium complexes reduce enzyme-lignin interactions.

Revealing the fate of the phenylcoumaran linkage during lignin oxidation reactions.

Science.gov (United States)

Lahive, Ciaran W; Lancefield, Christopher S; Codina, Anna; Kamer, Paul C J; Westwood, Nicholas J

2018-03-14

The fate of most lignin linkages, other than the β-O-4, under selective oxidation conditions is largely unknown. In this work we use advanced β-5 lignin model compounds to identify the fate of phenylcoumaran units in a softwood lignin during oxidation with DDQ. By using model compounds combined with detailed characterisation of the oxidised lignin polymer using HSQC and HMBC NMR we show that phenylcoumarones are a major product, and therefore constitute a novel non-native β-5 linkage in oxidised lignins. Additionally, the reactivity of these units in lignin led us to further investigate their connectivity in lignin, showing that they are found as both phenolic and etherified units. The findings and approach developed here will help improve the efficiency of selective oxidative lignin depolymerisation processes, particularly those aimed at the upgrading of softwood lignin in which phenylcoumarans are a major linkage.

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.

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.

The Use of Esterified Lignin for Synthesis of Durable Composites

Science.gov (United States)

S. Olsson; E. Ostmark; R.E. Ibach; C.M. Clemons; K.B. Segerholm; F. Englund

2011-01-01

Lignin is a natural polymer and one of the most abundant materials on earth. Despite this fact, lignin is often viewed as a by-product in chemical pulp processing and the use of lignin as a sustainable material is low. However, research and public awareness of sustainability have opened up new possibilities for using lignin as a material.

Production of Flocculants, Adsorbents, and Dispersants from Lignin

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Jiachuan Chen

2018-04-01

Full Text Available Currently, lignin is mainly produced in pulping processes, but it is considered as an under-utilized chemical since it is being mainly used as a fuel source. Lignin contains many hydroxyl groups that can participate in chemical reactions to produce value-added products. Flocculants, adsorbents, and dispersants have a wide range of applications in industry, but they are mainly oil-based chemicals and expensive. This paper reviews the pathways to produce water soluble lignin-based flocculants, adsorbents, and dispersants. It provides information on the recent progress in the possible use of these lignin-based flocculants, adsorbents, and dispersants. It also critically discusses the advantages and disadvantages of various approaches to produce such products. The challenges present in the production of lignin-based flocculants, adsorbents, and dispersants and possible scenarios to overcome these challenges for commercial use of these products in industry are discussed.

Influence of Reaction Conditions on Lignin Hydrothermal Treatment

Energy Technology Data Exchange (ETDEWEB)

Erdocia, Xabier; Prado, Raquel; Corcuera, M. Ángeles; Labidi, Jalel, E-mail: jalel.labidi@ehu.es [Chemical and Environmental Engineering Department, University of the Basque Country, San Seabastian (Spain)

2014-04-01

Organosolv lignin, obtained from olive tree pruning under optimized conditions, was subjected to a hydrothermal depolymerization process catalyzed by sodium hydroxide. The depolymerization of lignin was carried out at 300°C using different reaction times (20, 40, 60, 70, 80, 90, and 100 min) in order to study the influence of this parameter on lignin depolymerization. The resulting products (oil and residual lignin) were measured and analyzed by different techniques (GC/MS, high-performance size-exclusion chromatography, and pyrolysis–GC/MS) in order to determine their nature and composition. Coke was also formed, at a lower quantity, uncompetitive repolymerization reactions during the lignin hydrothermal treatment. The maximum oil yield and concentration of monomeric phenolic compounds was obtained after 80 min of reaction time. The highest reaction time studied (100 min) had the worst results with the lowest oil yield and highest coke production.

Engineering Plant Biomass Lignin Content and Composition for Biofuels and Bioproducts

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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.

Impact of lignins isolated from pretreated lignocelluloses on enzymatic cellulose saccharification

DEFF Research Database (Denmark)

Barsberg, Søren Talbro; Selig, Michael Joseph; Felby, Claus

2013-01-01

and cellulose-lignin systems. Consequently, the presence of the lignins had minimal effect, if any, on enzymatic cellulose conversion. Furthermore, this result, coupled with significant calcium levels in the isolated lignins, supports previous work suggesting lignin-calcium complexes reduce enzyme......Lignins were enzymatically isolated from corn stover and wheat straw samples and subjected to hydrothermal or wet oxidation pretreatments for enzyme adsorption experimentations. Lignin contents of the isolates ranged from 26 to 71 % (w/w); cellulose ranged from 3 to 22 % (w/w); xylan from 0.7 to 6...

Directional synthesis of ethylbenzene through catalytic transformation of lignin.

Science.gov (United States)

Fan, Minghui; Jiang, Peiwen; Bi, Peiyan; Deng, Shumei; Yan, Lifeng; Zhai, Qi; Wang, Tiejun; Li, Quanxin

2013-09-01

Transformation of lignin to ethylbenzene can provide an important bulk raw material for the petrochemical industry. This work explored the production of ethylbenzene from lignin through the directional catalytic depolymerization of lignin into the aromatic monomers followed by the selective alkylation of the aromatic monomers. For the first step, the aromatics selectivity of benzene derived from the catalytic depolymerization of lignin reached about 90.2 C-mol% over the composite catalyst of Re-Y/HZSM-5 (25). For the alkylation of the aromatic monomers in the second step, the highest selectivity of ethylbenzene was about 72.3 C-mol% over the HZSM-5 (25) catalyst. The reaction pathway for the transformation of lignin to ethylbenzene was also addressed. Present transformation potentially provides a useful approach for the production of the basic petrochemical material and development of high-end chemicals utilizing lignin as the abundant natural aromatic resource. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biodegradation of lignin by Shiitake Lentinus edodes (berk. ) sing

Energy Technology Data Exchange (ETDEWEB)

Oki, T.; Watanabe, H.; Ishikawa, H.

1981-01-01

Each strain of L. edodes destroyed all of the structural components of wood (Fagus crenata) at almost the same rate during the loss of approximately 30% of the total weight of wood. The activities of the extracellular enzymes, i.e. peroxidase, laccase, and polyphenol oxidase, in the wood powder and lignin-containing cultures increased during the early period of mycelial growth, and then declined rapidly, while the activity of Beta-glucosidase increased gradually throughout the growth period. Functional group analysis, nitrobenzene oxidation, and spectroscopic characterization showed that dioxane lignin from F. crenata degraded by L. edodes or in crude enzyme solution isolated from wood-containing culture had a higher content of carboxyl groups than the sound dioxane lignin, whereas the content of methoxyl group was lower in the degraded dioxane lignin than in sound dioxane lignin. The building units of dioxane lignin, which yield aromatic aldehydes on nitrobenzene oxidation, were attacked preferentially by L. edodes under the above conditions.

Lignin biomass conversion into chemicals and fuels

DEFF Research Database (Denmark)

Melián Rodríguez, Mayra

Second-generation biomass or lignocellulosic biomass, which is mainly composed of cellulose, hemicellulose and lignin, is a very important and promising feedstock for the renewable production of fuels and chemicals of the future. Lignin is the second most abundant natural polymer, representing 30...... and show similar, although simplified, characteristics to the natural biopolymer. Among them, the most abundant structural unit is the β-O-4, representing approximately 60% of the bonds in hardwood and 45-50% of those in softwood. Oxidative depolymerization is one of the most viable methods for lignin...... valorization. It involves the cleavage of ether bonds, such as β-O-4 and other linkages present in lignin and its model compounds, giving aldehydes or carboxylic acids as products, depending on the reaction conditions used. In Chapter 2 of this thesis, the preparation, characterization and catalytic...

The Effect of Plant Source on the Properties of Lignin-Based Polyurethanes

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Jason M. Lang

2018-02-01

Full Text Available This work increases our understanding of the effect of plant source on the mechanical and morphological properties of lignin-based polyurethanes (PUs. Lignin is a polymer that is synthesized inside the plant cell wall and can be used as a polyol to synthesize PUs. The specific aromatic structure of the lignin is heavily reliant on the plant source from which it is extracted. These results show that the mechanical properties of lignin-based PUs differ based on lignin’s plant source. The morphology of lignin-based PUs was examined using atomic force microscopy and scanning electron microscopy and the mechanical properties of lignin-based PU samples were measured using dynamic mechanical analysis and shore hardness (Type A. The thermal analysis and morphology studies demonstrate that all PUs prepared form a multiphase morphology. In these PUs, better mixing was observed in the wheat straw lignin PU samples leading to higher moduli than in the hardwood lignin and softwood lignin PUs whose morphology was dominated by larger aggregates. Independent of the type of the lignin used, increasing the fraction of lignin increased the rigidity of PU. Among the different types of lignin studied, PU with wheat straw soda lignin exhibited storage moduli ~2-fold higher than those of PUs incorporating other lignins. This study also showed that during synthesis all hydroxyl groups in the lignin are not available to react with isocyanates, which alters the number of cross-links formed within the PU and impacts the mechanical properties of the material.

Can laccases catalyze bond cleavage in lignin?

DEFF Research Database (Denmark)

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

2015-01-01

illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin......-substituted phenols, benzenethiols, polyphenols, and polyamines, which may be oxidized. In addition, the currently available analytical methods that can be used to detect enzyme catalyzed changes in lignin are summarized, and an improved nomenclature for unequivocal interpretation of the action of laccases on lignin...

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

Imbalanced lignin biosynthesis promotes the sexual reproduction of homothallic oomycete pathogens.

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Michaël Quentin

2009-01-01

Full Text Available Lignin is incorporated into plant cell walls to maintain plant architecture and to ensure long-distance water transport. Lignin composition affects the industrial value of plant material for forage, wood and paper production, and biofuel technologies. Industrial demands have resulted in an increase in the use of genetic engineering to modify lignified plant cell wall composition. However, the interaction of the resulting plants with the environment must be analyzed carefully to ensure that there are no undesirable side effects of lignin modification. We show here that Arabidopsis thaliana mutants with impaired 5-hydroxyguaiacyl O-methyltransferase (known as caffeate O-methyltransferase; COMT function were more susceptible to various bacterial and fungal pathogens. Unexpectedly, asexual sporulation of the downy mildew pathogen, Hyaloperonospora arabidopsidis, was impaired on these mutants. Enhanced resistance to downy mildew was not correlated with increased plant defense responses in comt1 mutants but coincided with a higher frequency of oomycete sexual reproduction within mutant tissues. Comt1 mutants but not wild-type Arabidopsis accumulated soluble 2-O-5-hydroxyferuloyl-L-malate. The compound weakened mycelium vigor and promoted sexual oomycete reproduction when applied to a homothallic oomycete in vitro. These findings suggested that the accumulation of 2-O-5-hydroxyferuloyl-L-malate accounted for the observed comt1 mutant phenotypes during the interaction with H. arabidopsidis. Taken together, our study shows that an artificial downregulation of COMT can drastically alter the interaction of a plant with the biotic environment.

Imbalanced lignin biosynthesis promotes the sexual reproduction of homothallic oomycete pathogens.

Science.gov (United States)

Quentin, Michaël; Allasia, Valérie; Pegard, Anthony; Allais, Florent; Ducrot, Paul-Henri; Favery, Bruno; Levis, Caroline; Martinet, Sophie; Masur, Clarissa; Ponchet, Michel; Roby, Dominique; Schlaich, Nikolaus L; Jouanin, Lise; Keller, Harald

2009-01-01

Lignin is incorporated into plant cell walls to maintain plant architecture and to ensure long-distance water transport. Lignin composition affects the industrial value of plant material for forage, wood and paper production, and biofuel technologies. Industrial demands have resulted in an increase in the use of genetic engineering to modify lignified plant cell wall composition. However, the interaction of the resulting plants with the environment must be analyzed carefully to ensure that there are no undesirable side effects of lignin modification. We show here that Arabidopsis thaliana mutants with impaired 5-hydroxyguaiacyl O-methyltransferase (known as caffeate O-methyltransferase; COMT) function were more susceptible to various bacterial and fungal pathogens. Unexpectedly, asexual sporulation of the downy mildew pathogen, Hyaloperonospora arabidopsidis, was impaired on these mutants. Enhanced resistance to downy mildew was not correlated with increased plant defense responses in comt1 mutants but coincided with a higher frequency of oomycete sexual reproduction within mutant tissues. Comt1 mutants but not wild-type Arabidopsis accumulated soluble 2-O-5-hydroxyferuloyl-L-malate. The compound weakened mycelium vigor and promoted sexual oomycete reproduction when applied to a homothallic oomycete in vitro. These findings suggested that the accumulation of 2-O-5-hydroxyferuloyl-L-malate accounted for the observed comt1 mutant phenotypes during the interaction with H. arabidopsidis. Taken together, our study shows that an artificial downregulation of COMT can drastically alter the interaction of a plant with the biotic environment.

Progress in lignin hydrogels and nanocomposites for water purification

DEFF Research Database (Denmark)

Tamulevicius, Sigitas; Thakur, Sourbh; Govender, Penny P.

2017-01-01

-based hydrogels have shown excellent performance for removal of various pollutants from water. The adsorption properties of lignin based hydrogels can further be improved by using a combination of nanomaterials and lignin that results in promising hydrogel nanocomposites. In nature, the most abundant structures...... are formed by the combination of lignin, cellulose and hemicelluloses. In this article, we have attempted to comprehensively review the research work carried out in the direction of usage of lignin-based hydrogel for removal of toxic pollutants including metal ions and dyes....

Solid-state 29Si NMR and FTIR analyses of lignin-silica coprecipitates

DEFF Research Database (Denmark)

Cabrera Orozco, Yohanna; Cabrera, Andrés; Larsen, Flemming Hofmann

2016-01-01

When agricultural residues are processed to ethanol, lignin and silica are some of the main byproducts. Separation of these two products is difficult and the chemical interactions between lignin and silica are not well described. In the present study, the effect of lignin-silica complexing has been...... investigated by characterizing lignin and silica coprecipitates by FTIR and solid state NMR. Silica particles were coprecipitated with three different lignins, three lignin model compounds, and two silanes representing silica-in-lignin model compounds. Comparison of 29Si SP/MAS NMR spectra revealed differences...

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

Redox Fluctuations Increase the Contribution of Lignin to Soil Respiration

Science.gov (United States)

Hall, S. J.; Silver, W. L.; Timokhin, V.; Hammel, K.

2014-12-01

Lignin mineralization represents a critical flux in the terrestrial carbon (C) cycle, yet little is known about mechanisms and environmental factors controlling lignin breakdown in mineral soils. Hypoxia has long been thought to suppress lignin decomposition, yet variation in oxygen (O2) availability in surface soils accompanying moisture fluctuations could potentially stimulate this process by generating reactive oxygen species via coupled biotic and abiotic iron (Fe) redox cycling. Here, we tested the impact of redox fluctuations on lignin breakdown in humid tropical forest soils during ten-week laboratory incubations. We used synthetic lignins labeled with 13C in either of two positions (aromatic methoxyl and propyl Cβ) to provide highly sensitive and specific measures of lignin mineralization not previously employed in soils. Four-day redox fluctuations increased the percent contribution of methoxyl C to soil respiration, and cumulative methoxyl C mineralization was equivalent under static aerobic and fluctuating redox conditions despite lower total C mineralization in the latter treatment. Contributions of the highly stable Cβ to mineralization were also equivalent in static aerobic and fluctuating redox treatments during periods of O2 exposure, and nearly doubled in the fluctuating treatment after normalizing to cumulative O2 exposure. Oxygen fluctuations drove substantial net Fe reduction and oxidation, implying that reactive oxygen species generated during abiotic Fe oxidation likely contributed to the elevated contribution of lignin to C mineralization. Iron redox cycling provides a mechanism for lignin breakdown in soils that experience conditions unfavorable for canonical lignin-degrading organisms, and provides a potential mechanism for lignin depletion in soil organic matter during late-stage decomposition. Thus, close couplings between soil moisture, redox fluctuations, and lignin breakdown provide potential a link between climate variability and

Evidence for lignin oxidation by the giant panda fecal microbiome.

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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

Isolation, identification and characterization of lignin-degrading bacteria from Qinling, China.

Science.gov (United States)

Yang, C-X; Wang, T; Gao, L-N; Yin, H-J; Lü, X

2017-12-01

Lignin is an aromatic heteropolymer forming a physical barrier and it is a big challenge in biomass utilization. This paper first investigated lignin-degradation bacteria from rotten wood in Qinling Mountain. Nineteen potential strains were selected and ligninolytic enzyme activities were determined over 84 h. Strains that had higher enzyme activities were selected. Further, the biodegradation of wheat straw lignin and alkali lignin was evaluated indicating that Burkholderia sp. H1 had the highest capability. It was confirmed by gel permeation chromatography and field emission scanning electron microscope that alkali lignin was depolymerized into small fragments. The degraded products were analysed using gas chromatography-mass spectrometry. The total ion chromatograph of products treated for 7 days showed the formation of aromatic compounds, an important intermediate from lignin degradation. Interestingly, they disappeared in 15 days while the aldehyde and ester compounds increased. The results suggest that the lignin-degrading bacteria are abundant in rotten wood and strain H1 has high potential to break down lignin. The diversity of lignin-degrading bacteria in Qinling Mountain is revealed. The study of Burkholderia sp. H1 expands the range of bacteria for lignin degradation and provides novel bacteria for application to lignocellulosic biomass. © 2017 The Society for Applied Microbiology.

Valorization of lignin from biorefineries for fuels and chemicals

DEFF Research Database (Denmark)

Nielsen, Joachim Bachmann

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...... substitute fossil fuel.In this Ph.D. study the direct liquefaction of a biorefinery lignin (hydrothermallypretreated enzymatic hydrolysis lignin) is explored. The goal is to provide a bio-crude which can substitute marine diesel as the engines found aboard large ships are adapted to more crude fuels. A novel...

Environmental economics of lignin derived transport fuels

NARCIS (Netherlands)

Obydenkova, Svetlana V.; Kouris, Panos D.; Hensen, Emiel J. M.; Heeres, Hero J.; Boot, Michael D.

2017-01-01

This paper explores the environmental and economic aspects of fast pyrolytic conversion of lignin, obtained from 2G ethanol plants, to transport fuels for both the marine and automotive markets. Various scenarios are explored, pertaining to aggregation of lignin from several sites, alternative

NMR characterization of lignins isolated from fruit and vegetable insoluble dietary fiber.

Science.gov (United States)

Bunzel, Mirko; Ralph, John

2006-10-18

Compositional information for lignins in food is rare and concentrated on cereal grains and brans. As lignins are suspected to have important health roles in the dietary fiber complex, the confusing current information derived from nonspecific lignin determination methods needs to be augmented by diagnostic structural studies. For this study, lignin fractions were isolated from kiwi, pear, rhubarb, and, for comparison, wheat bran insoluble dietary fiber. Clean pear and kiwi lignin isolates allowed for substantive structural profiling, but it is suggested that the significance of lignin in wheat has been overestimated by reliance on nonspecific analytical methods. Volume integration of NMR contours in two-dimensional (13)C-(1)H correlation spectra shows that pear and wheat lignins have comparable guaiacyl and syringyl contributions and that kiwi lignins are particularly guaiacyl-rich (approximately 94% guaiacyl) and suggest that rhubarb lignins, which could not be isolated from contaminating materials, are as syringyl-rich (approximately 96% syringyl) as lignins from any known natural or transgenic fiber source. Typical lignin structures, including those newly NMR-validated (glycerols, spirodienones, and dibenzodioxocins), and resinols implicated as possible mammalian lignan precursors in the gut are demonstrated via their NMR correlation spectra in the fruit and vegetable samples. A novel putative benzodioxane structure appears to be associated with the kiwi lignin. It is concluded that the fruits and vegetables examined contain authentic lignins and that the detailed structural analysis exposes limitations of currently accepted analytical methods.

Metal Triflates for the Production of Aromatics from Lignin.

Science.gov (United States)

Deuss, Peter J; Lahive, Ciaran W; Lancefield, Christopher S; Westwood, Nicholas J; Kamer, Paul C J; Barta, Katalin; de Vries, Johannes G

2016-10-20

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 relies on the use of catalytic amounts of easy-to-handle metal triflates (M(OTf) x ). Initially, we evaluated the reactivity of a broad range of metal triflates using simple lignin model compounds. More advanced lignin model compounds were also used to study the reactivity of different lignin linkages. The product aromatic monomers were either phenolic C2-acetals obtained by stabilization of the aldehyde cleavage products by reaction with ethylene glycol or methyl aromatics obtained by catalytic decarbonylation. Notably, when the method was ultimately tested on lignin, especially Fe(OTf) 3 proved very effective and the phenolic C2-acetal products were obtained in an excellent, 19.3±3.2 wt % yield. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of paramagnetic polyconjugated clusters in lignin antioxidant activity (in vitro)

International Nuclear Information System (INIS)

Dizhbite, T; Ponomarenko, J; Andersone, A; Dobele, G; Lauberts, M; Krasilnikova, J; Telysheva, G; Mironova-Ulmane, N

2012-01-01

Using physico-chemical methods (EPR, SEC, Py-GC/MS and UV/VIS spectroscopy) and wet chemical analysis, the characteristics of 6 hardwood lignins in terms of functionality, molecular weight and composition of lignin substructures were determined and considered together with the results of DPPH., ABTS. + and O 2 . − antioxidant assays with the aim to understand the relationships governing antioxidant properties of lignin. The strong positive linear correlation between lignin antioxidant capacity in the three assays used and the extent of conjugation of paramagnetic polyconjugated clusters in lignin macromolecules was found. The biological activity of the most active alkaline lignins was assessed by in vitro experiment with human blood.

Animal bioavailability of defined xenobiotic lignin metabolites

International Nuclear Information System (INIS)

Sandermann, H. Jr.; Arjmand, M.; Gennity, I.; Winkler, R.; Struble, C.B.; Aschbacher, P.W.

1990-01-01

Lignin has been recognized as a major component of bound pesticide residues in plants and is thought to be undigestible in animals. Two defined ring-U- 14 C-labeled chloroaniline/lignin metabolites have now been fed to rats, where a release of ∼66% of the bound xenobiotic occurred in the form of simple chloroaniline derivatives. The observed high degree of bioavailability indicates that bound pesticidal residues may possess ecotoxicological significance. In parallel studies, the white-rot fungus Phanerochaete chrysosporium was more efficient, and a soil system was much less efficient, in the degradation of the [ring-U- 14 C]chloroaniline/lignin metabolites

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.

Modified Stieltjes Transform and Generalized Convolutions of Probability Distributions

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Lev B. Klebanov

2018-01-01

Full Text Available The classical Stieltjes transform is modified in such a way as to generalize both Stieltjes and Fourier transforms. This transform allows the introduction of new classes of commutative and non-commutative generalized convolutions. A particular case of such a convolution for degenerate distributions appears to be the Wigner semicircle distribution.

Characterisation and application of NovaFiber lignin

NARCIS (Netherlands)

Gosselink, R.J.A.; Snijder, M.H.B.; Kranenbarg, A.; Keijsers, E.R.P.; Jong, de E.; Stigsson, L.L.

2004-01-01

Sulphur-free lignin coming from a novel alkaline-pulping process called NovaFiber, which has been developed by KIRAM AB, has been characterised and evaluated for potential applications. A Kraft lignin has been used for comparison. Considering the characterisation results of a NovaFiber softwood and

Characterisation of Authentic Lignin Biorefinery Samples by Fourier Transform Infrared Spectroscopy and Determination of the Chemical Formula for Lignin

DEFF Research Database (Denmark)

Le, Duy Michael; Damgaard Nielsen, Anders; Sørensen, Hanne

2017-01-01

samples in situ with no prior purification and minimal sample preparation. Lignin chemical formulas and lignin Fourier transform infrared (FTIR) spectra were extracted from mixed spectra by filtering out signals from residual carbohydrates and minerals. From estimations of C, H and O and adjustment...

Size exclusion chromatography of lignin: The mechanistic aspects and elimination of undesired secondary interactions.

Science.gov (United States)

Andrianova, Anastasia A; Yeudakimenka, Natallia A; Lilak, Samuel L; Kozliak, Evguenii I; Ugrinov, Angel; Sibi, Mukund P; Kubátová, Alena

2018-01-26

Characterization of lignin and its degradation products, more specifically determination of their molecular weight (MW) distribution, is essential for assessment and applications of these potentially renewable phenolics. Several representative gel filtration and gel permeation systems were evaluated in this work focusing on understanding of undesired secondary non-SEC interactions while utilizing four sets of commercially available polymeric standards as well as low-MW lignin model compounds including diarene standards synthesized in-house. The gel permeation column with a nonpolar highly cross-linked porous polystyrene/divinylbenzene-based stationary phase provided the most effective separation by MW for both low and high MW model compounds. Notably, the column with a higher pore and lower particle size provided a better resolution towards polymeric standards, even though the particle size effect was downplayed in the earlier SEC studies of lignin. For two other evaluated gel filtration and gel permeation columns, the separation was strongly affected by functionalities of the analytes and correlated with the compounds' pK a rather than MW. We showed that the separation on the stationary phases featuring polar hydroxyl groups led to specific column-analyte secondary interactions, perhaps based on their hydrogen bonding with lignin. Further, the SEC column evaluation yielded similar results with two sets of chemically different standards. This setup may be used as a general approach to selecting an applicable column for lignin SEC analysis. We confirmed the obtained results with a different independent method implementing a novel approach for lignin number-average MW (M n ) calculation based on laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF-MS) data. The determined M n corroborated the SEC results. Copyright © 2017 Elsevier B.V. All rights reserved.

Alkaline and Organosolv Lignins from Furfural Residue: Structural Features and Antioxidant Activity

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Xue-Fei Cao

2013-12-01

Full Text Available Furfural residue (FR, composed mainly of cellulose and lignin, is an industrial waste produced during furfural manufacture. In this study, dioxane, alkali, ethanol, alkali-ethanol, and alkaline hydrogen peroxide (AHP were used to extract lignins from FR. The structural features of these lignins obtained were characterized by sugar analysis, GPC, UV, FT-IR, and HSQC spectra. As compared to dioxane lignin (DL, other lignins showed lower molecular weights (Mw owing to the partial cleavage of the linkages between lignin units. Results from HSQC spectra revealed that β-O-4' and β-5' were still the major linkages of the FR lignin. Moreover, p-coumaric and ferulic acids were released and co-precipitated in the lignin preparations extracted with alkali and AHP, whereas part of the esters in DL were preserved during the dioxane extraction. Antioxidant activity investigation indicated that the antioxidant property of the alkali and alkali-ethanol lignins was higher than that of the commercial antioxidant, butylated hydroxytoluene.

Environmental economics of lignin derived transport fuels.

Science.gov (United States)

Obydenkova, Svetlana V; Kouris, Panos D; Hensen, Emiel J M; Heeres, Hero J; Boot, Michael D

2017-11-01

This paper explores the environmental and economic aspects of fast pyrolytic conversion of lignin, obtained from 2G ethanol plants, to transport fuels for both the marine and automotive markets. Various scenarios are explored, pertaining to aggregation of lignin from several sites, alternative energy carries to replace lignin, transport modalities, and allocation methodology. The results highlight two critical factors that ultimately determine the economic and/or environmental fuel viability. The first factor, the logistics scheme, exhibited the disadvantage of the centralized approach, owing to prohibitively expensive transportation costs of the low energy-dense lignin. Life cycle analysis (LCA) displayed the second critical factor related to alternative energy carrier selection. Natural gas (NG) chosen over additional biomass boosts well-to-wheel greenhouse gas emissions (WTW GHG) to a level incompatible with the reduction targets set by the U.S. renewable fuel standard (RFS). Adversely, the process' economics revealed higher profits vs. fossil energy carrier. Copyright © 2017 The Author(s). Published by Elsevier Ltd.. All rights reserved.

Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

Science.gov (United States)

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.

A radioimmunoassay for lignin in plant cell walls

International Nuclear Information System (INIS)

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 β-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 ηg/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. 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 2 delignification. The RIA was found to be less sensitive than expected, so several avenues for improving the method are discussed

Signatures of cinnamyl alcohol dehydrogenase deficiency in poplar lignins.

Science.gov (United States)

Lapierre, Catherine; Pilate, Gilles; Pollet, Brigitte; Mila, Isabelle; Leplé, Jean-Charles; Jouanin, Lise; Kim, Hoon; Ralph, John

2004-02-01

A series of transgenic poplars down-regulated for cinnamyl alcohol dehydrogenase (CAD) was analyzed by thioacidolysis. Among the lignin-derived monomers, the indene compounds that were recently shown to originate from sinapaldehyde incorporated into lignins through 8-O-4-cross-coupling, were found to increase as a function of CAD deficiency level. While these syringyl markers were recovered in substantial amounts in the most severely depressed lines, the markers for coniferaldehyde incorporation were recovered in only low amounts. In conjunction with these additional sinapaldehyde units and relative to the control samples, lignins in CAD-deficient poplar lines had less conventional syringyl-units and beta-O-4-bonds and more free phenolic groups. We found that almost half of the polymers in the most deficient lines could be solubilized in alkali and at room temperature. This unusual behavior suggests that lignins in CAD-deficient poplars occur as small, alkali-leachable lignin domains. That mainly sinapaldehyde incorporates into the lignins of CAD-deficient poplars suggests that the recently identified sinapyl alcohol dehydrogenase (SAD), which is structurally distinct from the CAD enzyme targeted herein, does not play any substantial role in constitutive lignification in poplar.

Development of C-lignin with G/S-lignin and lipids in orchid seed coats – an unexpected diversity exposed by ATR-FT-IR spectroscopy

DEFF Research Database (Denmark)

Barsberg, Søren Talbro; Lee, Y.-I.; Rasmussen, Hanne Nina

2018-01-01

Cite this article: Barsberg ST, Lee Y-I, Rasmussen HN. Development of C-lignin with G/S-lignin and lipids in orchid seed coats – an unexpected diversity exposed by ATR-FT-IR spectroscopy. Seed Science Research https:// doi.org/10.1017/S0960258517000344......Cite this article: Barsberg ST, Lee Y-I, Rasmussen HN. Development of C-lignin with G/S-lignin and lipids in orchid seed coats – an unexpected diversity exposed by ATR-FT-IR spectroscopy. Seed Science Research https:// doi.org/10.1017/S0960258517000344...

Adsorption of cellulase on cellulolytic enzyme lignin from lodgepole pine.

Science.gov (United States)

Tu, Maobing; Pan, Xuejun; Saddler, Jack N

2009-09-09

Enzymatic hydrolysis of lignocellulosic materials is significantly affected by cellulase adsorption onto the lignocellulosic substrates and lignin. The presence of lignin plays an important role in lignocellulosic hydrolysis and enzyme recycling. Three cellulase preparations (Celluclast, Spezyme CP, and MSUBC) were evaluated to determine their adsorption onto cellulolytic enzyme lignin (CEL) from steam-exploded Lodgepole pine (SELP) and ethanol (organosolv)-pretreated Lodgepole pine (EPLP). The adsorption affinity of cellulase (Celluclast) onto isolated lignin (CEL-EPLP and CEL-SELP) was slightly higher than that from corresponding EPLP and SELP substrates on the basis of the Langmuir constants. Effects of temperature, ionic strength, and surfactant on cellulase adsorption onto isolated lignin were also explored in this study. Thermodynamic analysis of enzyme adsorption onto isolated lignin (Gibbs free energy change DeltaG(0) approximately -30 kJ/mol) indicated this adsorption was a spontaneous process. The addition of surfactant (0.2% w/v) could reduce the adsorption of cellulase onto CEL-SELP by 60%. Two types of adsorption isotherm were compared for cellulase adsorption onto isolated lignin. A Langmuir adsorption isotherm showed better fit for the experimental data than a Freundlich adsorption isotherm.

Process for conversion of lignin to reformulated hydrocarbon gasoline

Science.gov (United States)

Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

1999-09-28

A process for converting lignin into high-quality reformulated hydrocarbon gasoline compositions in high yields is disclosed. The process is a two-stage, catalytic reaction process that produces a reformulated hydrocarbon gasoline product with a controlled amount of aromatics. In the first stage, a lignin material is subjected to a base-catalyzed depolymerization reaction in the presence of a supercritical alcohol as a reaction medium, to thereby produce a depolymerized lignin product. In the second stage, the depolymerized lignin product is subjected to a sequential two-step hydroprocessing reaction to produce a reformulated hydrocarbon gasoline product. In the first hydroprocessing step, the depolymerized lignin is contacted with a hydrodeoxygenation catalyst to produce a hydrodeoxygenated intermediate product. In the second hydroprocessing step, the hydrodeoxygenated intermediate product is contacted with a hydrocracking/ring hydrogenation catalyst to produce the reformulated hydrocarbon gasoline product which includes various desirable naphthenic and paraffinic compounds.

Isolation and characterization of new lignin streams derived from extractive-ammonia (EA) pretreatment

Energy Technology Data Exchange (ETDEWEB)

da Costa Sousa, Leonardo [Michigan State Univ., East Lansing, MI (United States); Foston, Marcus [Washington Univ., St. Louis, MO (United States); Bokade, Vijay [National Chemical Lab., Pune (India); Azarpira, Ali [Univ. of Wisconsin, Madison, WI (United States); Lu, Fachuang [Univ. of Wisconsin, Madison, WI (United States); Ragauskas, Arthur J. [Univ. of Tennessee, Knoxville, TN (United States); Ralph, John [Univ. of Wisconsin, Madison, WI (United States); Dale, Bruce [Michigan State Univ., East Lansing, MI (United States); Balan, Venkatesh [Michigan State Univ., East Lansing, MI (United States)

2016-05-05

One of the key challenges facing lignin conversion to fuels and chemicals is related to the level of carbohydrate and ash impurities found in extracted lignin. Structural modifications of lignin may also occur as a result of biomass pretreatment and harsh lignin extraction protocols. Extractive-Ammonia (EA) is a new pretreatment technology that uses liquid ammonia to cleave lignin–carbohydrate complexes, decrystallize cellulose, solubilize lignin, and selectively extract lignin from lignocellulosic biomass, enabling better utilization of both lignin and carbohydrate components in a biorefinery. The EA-based biorefinery produces two different lignin-rich streams, with different properties, that could potentially be upgraded to fuels and chemicals using green processes. Here, a water/ethanol-based fractionation method was developed to enrich the ammonia-soluble extractives, resulting in a major product stream containing 92% lignin. Detailed characterization of the various streams resulting from EA treatment, including compositional analysis, structural characterization by nuclear magnetic resonance (NMR) spectrometry, elemental analysis, molecular weight analysis, and thermo-gravimetric analysis provides a broad evaluation of the EA-derived lignin product stream structures and properties, assessing their potential for commercial applications. In conclusion, EA-derived lignins preserve much of lignin's functionality, including the sensitive β-aryl ether units. Furthermore, we observed nitrogen incorporation in the lignin-rich streams, notably due to the presence of hydroxycinnamoyl amides formed during ammonia pretreatment.

Formation of a tyrosine adduct involved in lignin degradation by Trametopsis cervina lignin peroxidase: a novel peroxidase activation mechanism

Science.gov (United States)

Yuta Miki; Rebecca Pogni; Sandra Acebes; Fatima Lucas; Elena Fernandez-Fueyo; Maria Camilla Baratto; Maria I. Fernandez; Vivian De Los Rios; Francisco J. Ruiz-duenas; Adalgisa Sinicropi; Riccardo Basosi; Kenneth E. Hammel; Victor Guallar; Angel T. Martinez

2013-01-01

LiP (lignin peroxidase) from Trametopsis cervina has an exposed catalytic tyrosine residue (Tyr181) instead of the tryptophan conserved in other lignin-degrading peroxidases. Pristine LiP showed a lag period in VA (veratryl alcohol) oxidation. However, VA-LiP (LiP after treatment with H2O2...

Esterification and characterization of lignin aiming the synthesis of polymeric composite

International Nuclear Information System (INIS)

Victor, Priscilla A.; Machado, Fabricio

2015-01-01

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"-"1) and an increase of the characteristic ester band (1720 to 1740 cm"-"1). According to nuclear magnetic resonance ("1H NMR) analysis on esterified lignin, intense peaks were observed in the range from 1.7 to 2.05 ppm (-CH_3) and 5.4 ppm to 6.2 ppm (=CH_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)

Genetic loci simultaneously controlling lignin monomers and biomass digestibility of rice straw.

Science.gov (United States)

Hu, Zhen; Zhang, Guifen; Muhammad, Ali; Samad, Rana Abdul; Wang, Youmei; Walton, Jonathan D; He, Yuqing; Peng, Liangcai; Wang, Lingqiang

2018-02-26

Lignin content and composition are crucial factors affecting biomass digestibility. Exploring the genetic loci simultaneously affecting lignin-relevant traits and biomass digestibility is a precondition for lignin genetic manipulation towards energy crop breeding. In this study, a high-throughput platform was employed to assay the lignin content, lignin composition and biomass enzymatic digestibility of a rice recombinant inbred line population. Correlation analysis indicated that the absolute content of lignin monomers rather than lignin content had negative effects on biomass saccharification, whereas the relative content of p-hydroxyphenyl unit and the molar ratio of p-hydroxyphenyl unit to guaiacyl unit exhibited positive roles. Eight QTL clusters were identified and four of them affecting both lignin composition and biomass digestibility. The additive effects of clustered QTL revealed consistent relationships between lignin-relevant traits and biomass digestibility. Pyramiding rice lines containing the above four positive alleles for increasing biomass digestibility were selected and showed comparable lignin content, decreased syringyl or guaiacyl unit and increased molar percentage of p-hydroxyphenyl unit, the molar ratio of p-hydroxyphenyl unit to guaiacyl unit and sugar releases. More importantly, the lodging resistance and eating/cooking quality of pyramiding lines were not sacrificed, indicating the QTL information could be applied to select desirable energy rice lines.

Dissolved Vanillin as Tracer for Estuarine Lignin Conversion

Science.gov (United States)

Edelkraut, F.

1996-12-01

Lignin is produced only by vascular plants and therefore can be used as a tracer for terrestrial organic carbon input to the estuarine and marine environments. Lignin measurements have been done by analyses of the oxidation products such as vanillin or 4-hydroxybenzaldehyde. In the Elbe Estuary, free dissolved vanillin was analysed in order to test whether such measurements yield information on terrestrial carbon inputs into the Estuary and on the vanillin derived from lignin oxidation. In the period 1990-1992, concentrations of dissolved vanillin in the Elbe ranged from 0 to 60 μ g l -1(mean: 8 μg l -1). Higher values were found in areas of increased microbial activity such as the turbidity zone and the river mouth where the water chemistry is influenced by large tidal flats. No correlation was found between dissolved vanillin and suspended matter concentrations, although lignin is normally associated with suspended particulate matter, nor was a covariance seen between dissolved vanillin and the terrestrial carbon inputs into the Estuary. Apparently, biological conversion of lignin was faster than the transport processes, and local sources were more dominant for the vanillin concentration than riverine sources. The dissolved vanillin turnover was fast and, consequently, a significant amount of lignin may be converted within an estuary. In sediments from the Estuary, the concentrations of dissolved vanillin were similar to those found in the water phase and showed no clear vertical profile. The sediment is unlikely to be the source for vanillin.

Abundance and reactivity of dibenzodioxocins in softwood lignin.

Science.gov (United States)

Argyropoulos, Dimitris S; Jurasek, Lubo; Kristofová, Lívia; Xia, Zhicheng; Sun, Yujun; Palus, Ernest

2002-02-13

To define the abundance and comprehend the reactivity of dibenzodioxocins in lignin, model compound studies, specific degradation experiments on milled wood lignin, and molecular modeling calculations have been performed. Quantitative (31)P NMR measurements of the increase of biphenolic hydroxyl groups formed after a series of alkaline degradations in the presence of hydrosulfide anions (kraft conditions) showed the presence of 3.7 dibenzodioxocin rings/100 C9 units in milled wood lignin. The DFRC degradation protocol (Derivatization Followed by Reductive Cleavage) was chosen as an independent means to estimate their abundance. Initial experiments with a dibenzodioxocin model compound, trans-6,7-dihydro-7-(4-hydroxy-3-methoxyphenyl)-4,9-dimethoxy-2,11-dipropyldibenzo[e,g][1,4]dioxocin-6-ylmethanol, showed that it is not cleaved under DFRC conditions, but rather it isomerizes into a cyclic oxepine structure. Steric effects precluded this isomerization from occurring when DFRC was applied to milled wood lignin. Instead, monoacetylated biphenolic moieties were released and quantified by (31)P NMR, at 4.3 dibenzodioxocin rings/100 C9 units. The dibenzodioxocin content in residual lignins isolated from kraft pulps delignified to various degrees showed that during pulp delignification, the initial rate of dibenzodioxocin removal was considerably greater than the cleavage rate of arylglycerol-beta-aryl ether bonds. The activation energy for the degradation of dibenzodioxocins under kraft conditions in milled wood lignin was 96 +/- 9 kJ/mol, similar to that of arylglycerol-beta-aryl ether bond cleavage.

Lignin depletion enhances the digestibility of cellulose in cultured xylem cells.

Directory of Open Access Journals (Sweden)

Catherine I Lacayo

Full Text Available Plant lignocellulose constitutes an abundant and sustainable source of polysaccharides that can be converted into biofuels. However, the enzymatic digestion of native plant cell walls is inefficient, presenting a considerable barrier to cost-effective biofuel production. In addition to the insolubility of cellulose and hemicellulose, the tight association of lignin with these polysaccharides intensifies the problem of cell wall recalcitrance. To determine the extent to which lignin influences the enzymatic digestion of cellulose, specifically in secondary walls that contain the majority of cellulose and lignin in plants, we used a model system consisting of cultured xylem cells from Zinniaelegans. Rather than using purified cell wall substrates or plant tissue, we have applied this system to study cell wall degradation because it predominantly consists of homogeneous populations of single cells exhibiting large deposits of lignocellulose. We depleted lignin in these cells by treating with an oxidative chemical or by inhibiting lignin biosynthesis, and then examined the resulting cellulose digestibility and accessibility using a fluorescent cellulose-binding probe. Following cellulase digestion, we measured a significant decrease in relative cellulose content in lignin-depleted cells, whereas cells with intact lignin remained essentially unaltered. We also observed a significant increase in probe binding after lignin depletion, indicating that decreased lignin levels improve cellulose accessibility. These results indicate that lignin depletion considerably enhances the digestibility of cellulose in the cell wall by increasing the susceptibility of cellulose to enzymatic attack. Although other wall components are likely to contribute, our quantitative study exploits cultured Zinnia xylem cells to demonstrate the dominant influence of lignin on the enzymatic digestion of the cell wall. This system is simple enough for quantitative image analysis

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

OpenAIRE

Lin, Xiaona; Sui, Shujuan; Tan, Shun; Pittman, Charles; Sun, Jianping; Zhang, Zhijun

2015-01-01

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...

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...

Lignin-solubilizing ability of actinomycetes isolated from termite (Termitidae) gut

International Nuclear Information System (INIS)

Pasti, M.B.; Crawford, D.L.; Pometto, A.L. III; Nuti, M.P.

1990-01-01

The lignocellulose-degrading abilities of 11 novel actinomycete strains isolated from termite gut were determined and compared with that of the well-characterized actinomycete, Streptomyces viridosporus T7A. Lignocellulose bioconversion was followed by (i) monitoring the degradation of [ 14 C]lignin- and [ 14 C]cellulose-labeled phloem of Abies concolor to 14 CO 2 and 14 C-labeled water-soluble products, (ii) determining lignocellulose, lignin, and carbohydrate losses resulting from growth on a lignocellulose substrate prepared from corn stalks (Zea mays), and (iii) quantifying production of a water-soluble lignin degradation intermediate (acid-precipitable polymeric lignin). Of the assays used, total lignocellulose weight loss was most useful in determining overall bioconversion ability but not in identifying the best lignin-solubilizing strains. A screening procedure based on 14 CO 2 evolution from [ 14 C-lignin]lignocellulose combined with measurement of acid-precipitable polymeric lignin yield was the most effective in identifying lignin-solubilizing strains. For the termite gut strains, the pH of the medium showed no increase after 3 weeks of growth on lignocellulose. This is markedly different from the pattern observed with S. viridosporus T7A, which raises the medium pH considerably. Production of extracellular peroxidases by the 11 strains and S. viridosporus T7A was followed for 5 days in liquid cultures. On the basis of an increase of specific peroxidase activity in the presence of lignocellulose in the medium, the actinomycetes could be placed into the same three groups

The distribution of lignin in white birch wood as determined by bromination with TEM-EDXA

International Nuclear Information System (INIS)

Saka, S.; Goring, D.A.I.

1988-01-01

Ultraviolet absorbance and bromine uptake were measured on various morphological regions of birch wood. To facilitate precise comparison, observations were made on identical locations in successive cross sections. From the data, the concentration of lignin and the ratio of the guaiacyl to syringyl residues were determined. The results obtained were then compared with the previous findings from the use of UV microscopy alone

Lignin transformations and reactivity upon ozonation in aqueous media

Science.gov (United States)

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

2012-03-01

The reaction of ozone with lignin in aqueous acidic solutions is investigated. The Danckwerst model is used to describe the kinetics of gas/liquid processes occurring in a bubble reactor. The efficient ozonation rate of a soluble lignin analog, sodium lignosulfate, is determined. The main lines of the reaction between ozone and lignin are revealed on the basis of kinetic analysis results and IR and UV spectroscopy data.

Electron-beam mediated dry distillation of lignin

International Nuclear Information System (INIS)

Chulkov, V.N.; Bludenko, A.V.; Ponomarev, A.V.

2007-01-01

Radiation heating was studied for its application in dry distillation of lignin under high absorbed-dose irradiation with no supplementary heating device used. Commercial preparation Polyphepan containing lignin (90 wt.%) and cellulose (10 wt.%), dried at 102 deg C, was used. The test samples were exposed to 8 MeV electron beams on U-003 linear accelerator under atmospheric pressure, with dose rates of 3.6 and 4.8 kGy/s. It is demonstrated that an increased yield of liquid products of dry lignin distillation is observed under conditions studied with a two-fold decrease in energy consumption due to more favorable heating conditions and intensification of free-radical reactions [ru

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.

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

Structural Changes of Lignin from Wheat Straw by Steam Explosion and Ethanol Pretreatments

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Cheng Pan

2016-06-01

Full Text Available Effects of the pretreatment of wheat straw by steam explosion and ethanol were evaluated relative to the structural changes of lignin from the pretreated pulp. The lignin from steam explosion pulp (LS, lignin from steam blasting residual liquid (LL, lignin from ethanol pretreatment pulp (LE, lignin from black liquor (LB, and lignin from wheat straw (LW were separated, and the structural characteristics of the lignin fractions were compared based on analyses of Fourier transform-infrared, ultraviolet, thermogravimetric, and 1H and 13C nuclear magnetic resonance spectra. The proportions of the three structural units in all lignin fractions clearly changed during the pretreatment process because of inter-conversion reactions. The conjugated structure of lignin was destroyed in the pretreatment process and was also affected by the alkali extraction process. The alcoholic hydroxyl links on the aliphatic side chain were partly transformed into carbonyl groups during ethanol pretreatment. Demethoxylation occurred in all lignin fractions during the ethanol pretreatment and steam explosion process. The thermal stability of the LB fraction was relatively high because of the condensation reaction.

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.

Metallo-deuteroporphyrin as a biomimetic catalyst for the catalytic oxidation of lignin to aromatics.

Science.gov (United States)

Zhu, Chenjie; Ding, Weiwei; Shen, Tao; Tang, Chenglun; Sun, Chenguo; Xu, Shichao; Chen, Yong; Wu, Jinglan; Ying, Hanjie

2015-05-22

A series of metallo-deuteroporphyrins derived from hemin were prepared as models of the cytochrome P450 enzyme. With the aid of the highly active Co(II) deuteroporphyrin complex, the catalytic oxidation system was applied for the oxidation of several lignin model compounds, and high yields of monomeric products were obtained under mild reaction conditions. It was found that the modified cobalt deuteroporphyrin that has no substituents at the meso sites but does have the disulfide linkage in the propionate side chains at the β sites exhibited much higher activity and stability than the synthetic tetraphenylporphyrin. The changes in the propionate side chains can divert the reactivity of cobalt deuteroporphyrins from the typical CC bond cleavage to CO bond cleavage. Furthermore, this novel oxidative system can convert enzymolysis lignin into depolymerized products including a significant portion of well-defined aromatic monomers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Origin and processing of terrestrial organic carbon in the Amazon system: lignin phenols in river, shelf, and fan sediments

Science.gov (United States)

Sun, Shuwen; Schefuß, Enno; Mulitza, Stefan; Chiessi, Cristiano M.; Sawakuchi, André O.; Zabel, Matthias; Baker, Paul A.; Hefter, Jens; Mollenhauer, Gesine

2017-05-01

The Amazon River transports large amounts of terrestrial organic carbon (OCterr) from the Andean and Amazon neotropical forests to the Atlantic Ocean. In order to compare the biogeochemical characteristics of OCterr in the fluvial sediments from the Amazon drainage basin and in the adjacent marine sediments, we analysed riverbed sediments from the Amazon mainstream and its main tributaries as well as marine surface sediments from the Amazon shelf and fan for total organic carbon (TOC) content, organic carbon isotopic composition (δ13CTOC), and lignin phenol compositions. TOC and lignin content exhibit positive correlations with Al / Si ratios (indicative of the sediment grain size) implying that the grain size of sediment discharged by the Amazon River plays an important role in the preservation of TOC and leads to preferential preservation of lignin phenols in fine particles. Depleted δ13CTOC values (-26.1 to -29.9 ‰) in the main tributaries consistently correspond with the dominance of C3 vegetation. Ratios of syringyl to vanillyl (S / V) and cinnamyl to vanillyl (C / V) lignin phenols suggest that non-woody angiosperm tissues are the dominant source of lignin in the Amazon basin. Although the Amazon basin hosts a rich diversity of vascular plant types, distinct regional lignin compositions are not observed. In the marine sediments, the distribution of δ13CTOC and Λ8 (sum of eight lignin phenols in organic carbon (OC), expressed as mg/100 mg OC) values implies that OCterr discharged by the Amazon River is transported north-westward by the North Brazil Current and mostly deposited on the inner shelf. The lignin compositions in offshore sediments under the influence of the Amazon plume are consistent with the riverbed samples suggesting that processing of OCterr during offshore transport does not change the encoded source information. Therefore, the lignin compositions preserved in these offshore sediments can reliably reflect the vegetation in the Amazon

Lignin nanotubes as vehicles for gene delivery into human cells.

Science.gov (United States)

Ten, Elena; Ling, Chen; Wang, Yuan; Srivastava, Arun; Dempere, Luisa Amelia; Vermerris, Wilfred

2014-01-13

Lignin nanotubes (LNTs) synthesized from the aromatic plant cell wall polymer lignin in a sacrificial alumina membrane template have as useful features their flexibility, ease of functionalization due to the availability of many functional groups, label-free detection by autofluorescence, and customizable optical properties. In this report we show that the physicochemical properties of LNTs can be varied over a wide range to match requirements for specific applications by using lignin with different subunit composition, a function of plant species and genotype, and by choosing the lignin isolation method (thioglycolic acid, phosphoric acid, sulfuric acid (Klason), sodium hydroxide lignin), which influences the size and reactivity of the lignin fragments. Cytotoxicity studies with human HeLa cells showed that concentrations of up to 90 mg/mL are tolerated, which is a 10-fold higher concentration than observed for single- or multiwalled carbon nanotubes (CNTs). Confocal microscopy imaging revealed that all LNT formulations enter HeLa cells without auxiliary agents and that LNTs made from NaOH-lignin penetrate the cell nucleus. We further show that DNA can adsorb to LNTs. Consequently, exposure of HeLa cells to LNTs coated with DNA encoding the green fluorescent protein (GFP) leads to transfection and expression of GFP. The highest transfection efficiency was obtained with LNTs made from NaOH-lignin due to a combination of high DNA binding capacity and DNA delivery directly into the nucleus. These combined features of LNTs make LNTs attractive as smart delivery vehicles of DNA without the cytotoxicity associated with CNTs or the immunogenicity of viral vectors.

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

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

Science.gov (United States)

2012-01-01

Background For cellulosic biofuels processes, suitable characterization of the lignin remaining within the cell wall and correlation of quantified properties of lignin to cell wall polysaccharide enzymatic deconstruction is underrepresented in the literature. This is particularly true for grasses which represent a number of promising bioenergy feedstocks where quantification of grass lignins is particularly problematic due to the high fraction of p-hydroxycinnamates. The main focus of this work is to use grasses with a diverse range of lignin properties, and applying multiple lignin characterization platforms, attempt to correlate the differences in these lignin properties to the susceptibility to alkaline hydrogen peroxide (AHP) pretreatment and subsequent enzymatic deconstruction. Results We were able to determine that the enzymatic hydrolysis of cellulose to to glucose (i.e. digestibility) of four grasses with relatively diverse lignin phenotypes could be correlated to total lignin content and the content of p-hydroxycinnamates, while S/G ratios did not appear to contribute to the enzymatic digestibility or delignification. The lignins of the brown midrib corn stovers tested were significantly more condensed than a typical commercial corn stover and a significant finding was that pretreatment with alkaline hydrogen peroxide increases the fraction of lignins involved in condensed linkages from 88–95% to ~99% for all the corn stovers tested, which is much more than has been reported in the literature for other pretreatments. This indicates significant scission of β-O-4 bonds by pretreatment and/or induction of lignin condensation reactions. The S/G ratios in grasses determined by analytical pyrolysis are significantly lower than values obtained using either thioacidolysis or 2DHSQC NMR due to presumed interference by ferulates. Conclusions It was found that grass cell wall polysaccharide hydrolysis by cellulolytic enzymes for grasses exhibiting a diversity of

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

Directory of Open Access Journals (Sweden)

Li Muyang

2012-06-01

Full Text Available Abstract Background For cellulosic biofuels processes, suitable characterization of the lignin remaining within the cell wall and correlation of quantified properties of lignin to cell wall polysaccharide enzymatic deconstruction is underrepresented in the literature. This is particularly true for grasses which represent a number of promising bioenergy feedstocks where quantification of grass lignins is particularly problematic due to the high fraction of p-hydroxycinnamates. The main focus of this work is to use grasses with a diverse range of lignin properties, and applying multiple lignin characterization platforms, attempt to correlate the differences in these lignin properties to the susceptibility to alkaline hydrogen peroxide (AHP pretreatment and subsequent enzymatic deconstruction. Results We were able to determine that the enzymatic hydrolysis of cellulose to to glucose (i.e. digestibility of four grasses with relatively diverse lignin phenotypes could be correlated to total lignin content and the content of p-hydroxycinnamates, while S/G ratios did not appear to contribute to the enzymatic digestibility or delignification. The lignins of the brown midrib corn stovers tested were significantly more condensed than a typical commercial corn stover and a significant finding was that pretreatment with alkaline hydrogen peroxide increases the fraction of lignins involved in condensed linkages from 88–95% to ~99% for all the corn stovers tested, which is much more than has been reported in the literature for other pretreatments. This indicates significant scission of β-O-4 bonds by pretreatment and/or induction of lignin condensation reactions. The S/G ratios in grasses determined by analytical pyrolysis are significantly lower than values obtained using either thioacidolysis or 2DHSQC NMR due to presumed interference by ferulates. Conclusions It was found that grass cell wall polysaccharide hydrolysis by cellulolytic enzymes for grasses

Combinatorial pretreatment and fermentation optimization enabled a record yield on lignin bioconversion.

Science.gov (United States)

Liu, Zhi-Hua; Xie, Shangxian; Lin, Furong; Jin, Mingjie; Yuan, Joshua S

2018-01-01

Lignin valorization has recently been considered to be an essential process for sustainable and cost-effective biorefineries. Lignin represents a potential new feedstock for value-added products. Oleaginous bacteria such as Rhodococcus opacus can produce intracellular lipids from biodegradation of aromatic substrates. These lipids can be used for biofuel production, which can potentially replace petroleum-derived chemicals. However, the low reactivity of lignin produced from pretreatment and the underdeveloped fermentation technology hindered lignin bioconversion to lipids. In this study, combinatorial pretreatment with an optimized fermentation strategy was evaluated to improve lignin valorization into lipids using R. opacus PD630. As opposed to single pretreatment, combinatorial pretreatment produced a 12.8-75.6% higher lipid concentration in fermentation using lignin as the carbon source. Gas chromatography-mass spectrometry analysis showed that combinatorial pretreatment released more aromatic monomers, which could be more readily utilized by lignin-degrading strains. Three detoxification strategies were used to remove potential inhibitors produced from pretreatment. After heating detoxification of the lignin stream, the lipid concentration further increased by 2.9-9.7%. Different fermentation strategies were evaluated in scale-up lipid fermentation using a 2.0-l fermenter. With laccase treatment of the lignin stream produced from combinatorial pretreatment, the highest cell dry weight and lipid concentration were 10.1 and 1.83 g/l, respectively, in fed-batch fermentation, with a total soluble substrate concentration of 40 g/l. The improvement of the lipid fermentation performance may have resulted from lignin depolymerization by the combinatorial pretreatment and laccase treatment, reduced inhibition effects by fed-batch fermentation, adequate oxygen supply, and an accurate pH control in the fermenter. Overall, these results demonstrate that combinatorial

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, 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) including 4-hydroxy-2-methoxyphenol, p-hydroxybenzoic acid, vanillic acid, syringic acid, and 3,4-dihydroxybenzoic acid. The maximized MPC 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.

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.

Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading.

Science.gov (United States)

Schutyser, W; Renders, T; Van den Bosch, S; Koelewijn, S-F; Beckham, G T; Sels, B F

2018-02-05

In pursuit of more sustainable and competitive biorefineries, the effective valorisation of lignin is key. An alluring opportunity is the exploitation of lignin as a resource for chemicals. Three technological biorefinery aspects will determine the realisation of a successful lignin-to-chemicals valorisation chain, namely (i) lignocellulose fractionation, (ii) lignin depolymerisation, and (iii) upgrading towards targeted chemicals. This review provides a summary and perspective of the extensive research that has been devoted to each of these three interconnected biorefinery aspects, ranging from industrially well-established techniques to the latest cutting edge innovations. To navigate the reader through the overwhelming collection of literature on each topic, distinct strategies/topics were delineated and summarised in comprehensive overview figures. Upon closer inspection, conceptual principles arise that rationalise the success of certain methodologies, and more importantly, can guide future research to further expand the portfolio of promising technologies. When targeting chemicals, a key objective during the fractionation and depolymerisation stage is to minimise lignin condensation (i.e. formation of resistive carbon-carbon linkages). During fractionation, this can be achieved by either (i) preserving the (native) lignin structure or (ii) by tolerating depolymerisation of the lignin polymer but preventing condensation through chemical quenching or physical removal of reactive intermediates. The latter strategy is also commonly applied in the lignin depolymerisation stage, while an alternative approach is to augment the relative rate of depolymerisation vs. condensation by enhancing the reactivity of the lignin structure towards depolymerisation. Finally, because depolymerised lignins often consist of a complex mixture of various compounds, upgrading of the raw product mixture through convergent transformations embodies a promising approach to decrease the

Chemicals from Lignin: An Interplay of Lignocellulose Fractionation, Depolymerisation, and Upgrading

Energy Technology Data Exchange (ETDEWEB)

Beckham, Gregg T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Schutyser, Wouter [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Renders, Tom [KU Leuven; Van den Bosch, Sander [KU Leuven; Koelewijn, Steven-Friso [KU Leuven; Sels, Bert F. [KU Leuven

2018-01-01

In pursuit of more sustainable and competitive biorefineries, the effective valorisation of lignin is key. An alluring opportunity is the exploitation of lignin as a resource for chemicals. Three technological biorefinery aspects will determine the realisation of a successful lignin-to-chemicals valorisation chain, namely (i) lignocellulose fractionation, (ii) lignin depolymerisation, and (iii) upgrading towards targeted chemicals. This review provides a summary and perspective of the extensive research that has been devoted to each of these three interconnected biorefinery aspects, ranging from industrially well-established techniques to the latest cutting edge innovations. To navigate the reader through the overwhelming collection of literature on each topic, distinct strategies/topics were delineated and summarised in comprehensive overview figures. Upon closer inspection, conceptual principles arise that rationalise the success of certain methodologies, and more importantly, can guide future research to further expand the portfolio of promising technologies. When targeting chemicals, a key objective during the fractionation and depolymerisation stage is to minimise lignin condensation (i.e. formation of resistive carbon-carbon linkages). During fractionation, this can be achieved by either (i) preserving the (native) lignin structure or (ii) by tolerating depolymerisation of the lignin polymer but preventing condensation through chemical quenching or physical removal of reactive intermediates. The latter strategy is also commonly applied in the lignin depolymerisation stage, while an alternative approach is to augment the relative rate of depolymerisation vs. condensation by enhancing the reactivity of the lignin structure towards depolymerisation. Finally, because depolymerised lignins often consist of a complex mixture of various compounds, upgrading of the raw product mixture through convergent transformations embodies a promising approach to decrease the

Fractionation and characterization of saccharides and lignin components in wood prehydrolysis liquor from dissolving pulp production.

Science.gov (United States)

Wang, Zhaojiang; Wang, Xiaojun; Jiang, Jungang; Fu, Yingjuan; Qin, Menghua

2015-08-01

Saccharides and lignin components in prehydrolysis liquor (PHL) from kraft-based dissolving pulp production was characterized after being fractionated using membrane filtration. The results showed that the membrane filtration provided a method for organics fractionation with considerable recovery rate, but exhibited some disadvantages. Besides the limited ability in purifying oligosaccharides (OS) due to the overlaps of molecular weight distribution with lignin components, the membrane filtration could not improve the homogeneity of OS as indicated by the analysis of chemical compositions and the degree of polymerization (DP), which may be ascribed to the linear conformation of OS. The characterization of lignin components indicated a great potential for polymer industry because of the remarkable content of phenolic hydroxyl groups (PhOH), especially for low molecular weight (LMW) fraction. It was concluded the organics in PHL provided streams of value-added chemicals. However, the practical significance thereof can be realized and maximized only when they are successfully and completely fractionated. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dual role of lignin in plant litter decomposition in terrestrial ecosystems.

Science.gov (United States)

Austin, Amy T; Ballaré, Carlos L

2010-03-09

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

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.

Thermochemical Conversion of Lignin for Fuels and Chemicals: A Review Conversion thermochimique de la lignine en carburants et produits chimiques : une revue

Directory of Open Access Journals (Sweden)

Joffres B.

2013-10-01

Full Text Available Lignin is one of the biomass components potentially usable as renewable resource to produce fuels or chemicals. After separation from the lignocellulosic matrix, this macromolecule is nowadays essentially valorized by combustion in paper mills. If second generation ethanol is produced in the future from lignocellulosic biomass, some increasing reserves of lignin will be available in addition to the ones coming from the paper industry. The main thermochemical ways such as pyrolysis, solvolysis, hydrothermal conversion and hydroconversion considered for the valorization of the lignin are reviewed in this article. La lignine est une des composantes de la biomasse lignocellulosique potentiellement valorisable comme ressource renouvelable pour la production de carburants ou de produits chimiques. Après séparation de la matrice lignocellulosique, cette macromolécule est de nos jours essentiellement utilisée comme combustible dans l’industrie papetière. Outre cette filière papetière, la production d’éthanol de seconde génération à partir de la cellulose aura comme conséquence la mise à disponibilité d’encore plus grandes quantités de lignine. De nouvelles applications pourront donc être proposées pour l’utilisation de cette bio-ressource. Les différentes voies thermochimiques : pyrolyse, solvolyse, conversion hydrothermale et hydroconversion envisagées pour la valorisation de la lignine sont décrites dans cet article.

Chlorination of lignin by ubiquitous fungi has a likely role in global organochlorine production

Science.gov (United States)

Patricia Ortiz-Bermudez; Kolby C. Hirth; Ewald Srebotnik; Kenneth E. Hammel

2007-01-01

Soils and decayed plant litter contain significant quantities of chlorinated aromatic polymers that have a natural but largely unknown origin. We used cupric oxide ligninolysis coupled with gas chromatography/mass spectrometry to show that Curvularia inaequalis, a widely distributed litter ascomycete, chlorinated the aromatic rings of lignin in wood that it was...

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.

Comparative Analysis of Milled Wood Lignins (MWLs Isolated from Sugar Maple (SM and Hot-Water Extracted Sugar Maple (ESM

Directory of Open Access Journals (Sweden)

Mangesh J. Goundalkar

2014-03-01

Full Text Available To further elucidate the advantageous effects of hot-water extraction (HWE on delignification, milled wood lignin (MWL was isolated from sugar maple (SM and from hot-water extracted sugar maple (ESM. Ball-milled wood was analyzed for particle size distribution (PSD before and after dioxane:water (DW extraction. The MWL samples were analyzed by analytical and spectral methods. The results indicated that the MWL isolated from SM and ESM was mainly released from the middle lamella (ML and the secondary wall (SW, respectively. The cleavage of dibenzodioxocin (DB and spirodienone (SD lignin substructures during HWE is suggested. The removal of lignin during acetone:water (AW extraction of hot-water extracted wood indicates that including an additional operation in a hardwood HWE-based biorefinery would be beneficial for processing of wood.

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

Science.gov (United States)

Ma, Ruoshui; Guo, Mond; Lin, Kuan-Ting; Hebert, Vincent R; Zhang, Jinwen; Wolcott, Michael P; Quintero, Melissa; Ramasamy, Karthikeyan K; Chen, Xiaowen; Zhang, Xiao

2016-07-25

Lignin is the largest source of renewable material with an aromatic skeleton. However, due to the recalcitrant and heterogeneous nature of the lignin polymer, 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) including 4-hydroxy-2-methoxyphenol, p-hydroxybenzoic acid, vanillic acid, syringic acid, and 3,4-dihydroxybenzoic acid. The maximized MPC 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure variations of carbonizing lignin

International Nuclear Information System (INIS)

Otani, C.; Polidoro, H.A.; Otani, S.; Craievich, A.F.

1984-01-01

The studied lignin is a by-product of the process of ethanol production from eucaliptus. It was heat-treated under inert atmosphere conditions at increasing temperatures from 300C up to 2400C. The structural variations were studied by wide-angle X-ray diffraction, small-angle X-ray scattering and infrared absorption spectroscopy. The bulk and 'real' density of the compacted materials have also been determined as functions of the final temperature. These experimental results enabled us to establish a mechanism of structure variation based on the formation of a turbostratic graphite-like and porous structure within the initially amorphous lignin matrix. (Author) [pt

Effects of lignin and surfactant on adsorption and hydrolysis of cellulases on cellulose

OpenAIRE

Li, Yanfei; Sun, Zongping; Ge, Xiaoyan; Zhang, Junhua

2016-01-01

Background Considerable works have been reported concerning the obstruction of enzymatic hydrolysis efficiency by lignin. However, there is a lack of information about the influence of lignin on the adsorption of cellulases on cellulose, along with the hydrolytic activity of the cellulases adsorbed on lignin. In addition, limited discovery has been reported about the influence of additives on cellulase desorption from lignin and lignocellulosic materials. In this work, the effects of lignin o...

Unravelling Some of the Key Transformations in the Hydrothermal Liquefaction of Lignin.

Science.gov (United States)

Lui, Matthew Y; Chan, Bun; Yuen, Alexander K L; Masters, Anthony F; Montoya, Alejandro; Maschmeyer, Thomas

2017-05-22

Using both experimental and computational methods, focusing on intermediates and model compounds, some of the main features of the reaction mechanisms that operate during the hydrothermal processing of lignin were elucidated. Key reaction pathways and their connection to different structural features of lignin were proposed. Under neutral conditions, subcritical water was demonstrated to act as a bifunctional acid/base catalyst for the dissection of lignin structures. In a complex web of mutually dependent interactions, guaiacyl units within lignin were shown to significantly affect overall lignin reactivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of lignin for the production of new compounded materials.

Science.gov (United States)

Hüttermann, A; Mai, C; Kharazipour, A

2001-05-01

The cell walls of woody plants are compounded materials made by in situ polymerization of a polyphenolic matrix (lignin) into a web of fibers (cellulose), a process that is catalysed by polyphenoloxidases (laccases) or peroxidases. The first attempt to transform the basic strategy of this natural process for use in human craftsmanship was the ancient lacquer method. The sap of the lacquer tree (Rhus verniciflua) contains large amounts of a phenol (urushiol), a polysaccharide and the enzyme laccase. This oil-in-water emulsion solidifies in the presence of oxygen. The Chinese began using this phenomenon for the production of highly creative artwork more than 6,000 years ago. It was the first example of an isolated enzyme being used as a catalyst to create an artificial plastic compound. In order to apply this process to the production of products on an industrial scale, an inexpensive phenol must be used, which is transferred by an enzyme to active radicals that react with different components to form a compounded material. At present, the following approaches have been studied: (1) In situ polymerization of lignin for the production of particle boards. Adhesive cure is based on the oxidative polymerization of lignin using phenoloxidases (laccase) as radical donors. This lignin-based bio-adhesive can be applied under conventional pressing conditions. The resulting particle boards meet German performance standards. By this process, 80% of the petrochemical binders in the wood-composite industry can be replaced by materials from renewable resources. (2) Enzymatic copolymerization of lignin and alkenes. In the presence of organic hydroperoxides, laccase catalyses the reaction between lignin and olefins. Detailed studies on the reaction between lignin and acrylate monomers showed that chemo-enzymatic copolymerization offers the possibility to produce defined lignin-acrylate copolymers. The system allows control of the molecular weights of the products in a way that has

Aktivitas Ligninolitik Beberapa Jamur Aphyllophorales dan Kemampuannya Mendegradasi Lignin pada Lindi Hitam

Directory of Open Access Journals (Sweden)

Atria Martina

2016-03-01

Full Text Available Fourteen local isolate Aphyllophorales fungi were screened their ligninolytic activity. The isolate with highest ligninolytic activity was tested it capability to degrade kraft blackliquor lignin. The biodegradability of black liquor is low because the presence of lignin and lignin derivative in the wastewater. These fungal were screened for ligninolytic activity by decolorization on solid mediacontaining RBBR dye. The ability of the fungal strains to biodegrade kraft black liquor lignin was performed by submerged fermentation condition with agitation and incubation time as treatment. The solid culture result in 3 isolates had ligninolytic activity and Ganoderma sp.BTA1 gave the highest ligninolytic. Agitation and incubation time influenced ligninbiodegradation of blackliquor significantly. Optimum condition for lignin biodegradation was at 200 rpm during 25 days with lignin reduction was 45,786%.

Characterisation of lignins isolated from sugarcane bagasse pretreated with acidified ethylene glycol and ionic liquids

International Nuclear Information System (INIS)

Moghaddam, Lalehvash; Zhang, Zhanying; Wellard, R. Mark; Bartley, John P.; O'Hara, Ian M.; Doherty, William O.S.

2014-01-01

Sugarcane bagasse pretreatment processes using acidified aqueous ethylene glycol (EG) and ionic liquids (ILs) have been reported recently. In this study, recovery of lignins from these processes was conducted, as well as determination of their physico-chemical properties. The amount of lignins recovered from 1-butyl-3-methylimidazolium chloride ([bmim]Cl) with HCl as a catalyst and [bmim][CH 3 SO 3 ] was ∼42%, and ∼35%–36% by EG with HCl or H 2 SO 4 as a catalyst, respectively. The isolated lignins were characterised using wet chemistry, spectroscopy and thermogravimetry analysis (TGA), and the results compared to soda lignin from NaOH pretreatment of bagasse. The IL and EG lignins contained no or trace amounts of carbohydrates, slightly lower hydrogen content but slightly higher oxygen contents than soda lignin. The IL and EG lignins contained more C-3 and C-5 reactive sites for Mannich reaction and had more p-hydroxypheny propane unit structures than soda lignin. Two-dimensional heteronuclear single quantum coherence (2D HSQC) nuclear magnetic resonance (NMR) identified the major substructural units in the lignins, and allowed differences among them to be studied. As EG lignins were extracted in very reactive environment, intermediate enol ethers were formed and led to cleavage reactions which were not apparent in the other lignins. 31 P NMR and infra-red spectroscopy results showed that IL and EG lignins had lower total hydroxyl content than soda lignin, probably indicating that a higher degree of self-polymerisation occurred during bagasse pretreatment, despite the use of lower temperature and shorter reaction time. On the basis of the salient features of these lignins, potential applications were proposed. - Highlights: • Lignins were recovered from ethylene glycol (EG) and ionic liquid (IL) processes. • IL and EG lignins contained no or trace amounts of carbohydrates. • IL and EG lignin had more C-3 and C-5 sites for Mannich reaction than soda

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia.

Science.gov (United States)

Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

2016-10-20

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.

Ultra violet resonance Raman spectroscopy in lignin analysis: determination of characteristic vibrations of p-hydroxyphenyl, guaiacyl, and syringyl lignin structures.

Science.gov (United States)

Saariaho, Anna-Maija; Jääskeläinen, Anna-Stiina; Nuopponen, Mari; Vuorinen, Tapani

2003-01-01

Raman spectroscopy of wood and lignin samples is preferably carried out in the near-infrared region because lignin produces an intense laser-induced fluorescence background at visible excitation wavelengths. However, excitation of aromatic and conjugated lignin structures with deep ultra violet (UV) light gives resonance-enhanced Raman signals while the overlapping fluorescence is eliminated. In this study, ultra violet resonance Raman (UVRR) spectroscopy was used to define characteristic vibration bands of model compounds of p-hydroxyphenyl, guaiacyl, and syringyl lignin structures at three excitation wavelengths (229, 244, and 257 nm). The intensities of each band, relative to the intensity of the aromatic vibration band at 1600 cm-1, were defined and the most suitable excitation wavelength was suggested for each structure. p-Hydroxyphenyl structures showed intensive characteristic bands at 1217-1214 and 1179-1167 cm-1 with excitation at 244 nm, whereas the bands of guaiacyl structures were more intensive with 257 nm excitation. Most intensive characteristic bands of guaiacyl structures were found at 1289-1279, 1187-1185, 1158-1155, and 791-704 cm-1. Syringyl structures had almost identical spectra with 244 and 257 nm excitations with characteristic bands at 1514-1506, 1333-1330, and 981-962 cm-1. The characteristic bands of the three structural units were also found from the compression wood, softwood, and hardwood samples, indicating that UVRR spectroscopy can be applied for the determination of chemical structures of lignin.

Fiber and lignin analysis in concentrate, forage, and feces

DEFF Research Database (Denmark)

Hindrichsen, I.K.; Kreuzer, M.; Madsen, Jørgen

2006-01-01

Hemicelluloses, cellulose, and lignin contents of contrasting feeds, with emphasis on concentrate ingredients and complete concentrates, were analyzed using the Van Soest detergent procedure (analyzing neutral detergent fiber, acid detergent fiber, and acid detergent lignin) and the enzymatic...

Lignin-solubilizing ability of actinomycetes isolated from termite (Termitidae) gut.

Science.gov (United States)

Pasti, M B; Pometto, A L; Nuti, M P; Crawford, D L

1990-01-01

The lignocellulose-degrading abilities of 11 novel actinomycete strains isolated from termite gut were determined and compared with that of the well-characterized actinomycete, Streptomyces viridosporus T7A. Lignocellulose bioconversion was followed by (i) monitoring the degradation of [14C]lignin- and [14C]cellulose-labeled phloem of Abies concolor to 14CO2 and 14C-labeled water-soluble products, (ii) determining lignocellulose, lignin, and carbohydrate losses resulting from growth on a lignocellulose substrate prepared from corn stalks (Zea mays), and (iii) quantifying production of a water-soluble lignin degradation intermediate (acid-precipitable polymeric lignin). The actinomycetes were all Streptomyces strains and could be placed into three groups, including a group of five strains that appear superior to S. viridosporus T7A in lignocellulose-degrading ability, three strains of approximately equal ability, and three strains of lesser ability. Strain A2 was clearly the superior and most effective lignocellulose decomposer of those tested. Of the assays used, total lignocellulose weight loss was most useful in determining overall bioconversion ability but not in identifying the best lignin-solubilizing strains. A screening procedure based on 14CO2 evolution from [14C-lignin]lignocellulose combined with measurement of acid-precipitable polymeric lignin yield was the most effective in identifying lignin-solubilizing strains. For the termite gut strains, the pH of the medium showed no increase after 3 weeks of growth on lignocellulose. This is markedly different from the pattern observed with S. viridosporus T7A, which raises the medium pH considerably. Production of extracellular peroxidases by the 11 strains and S. viridosporus T7A was followed for 5 days in liquid cultures.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2167628

Physical vapor deposited thin films of lignins extracted from sugar cane bagasse: morphology, electrical properties, and sensing applications.

Science.gov (United States)

Volpati, Diogo; Machado, Aislan D; Olivati, Clarissa A; Alves, Neri; Curvelo, Antonio A S; Pasquini, Daniel; Constantino, Carlos J L

2011-09-12

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 × 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan δ of 3.9 × 10(-3), and conductivity of 1.75 × 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being

Sulfur-free lignins from alkaline pulping tested in mortar for use as mortar additives.

Science.gov (United States)

Nadif, A; Hunkeler, D; Käuper, P

2002-08-01

Sulfur-free lignin, obtained through the acid precipitation of black liquor from the soda pulping process, has been tested as water reducer in mortar. It has also been compared to existing commercial additives such as naphthalene sulfonates and lignosulfonates. The ash content and sugar content of these lignins are low in comparison to lignosulfonates, conferring on them higher purity. A procedure for small scale testing derived from the industrial norms SN-EN196 and ASTM (Designation C230-90) is presented. Specifically, all the sulfur-free lignins tested improved the flow of the mortar. Selected flax lignins performed better than lignosulfonates though still less than naphthalene sulfonates. Furthermore, certain hemp lignins gave comparable results to the lignosulfonates. Overall, the straw lignin prepared herein is comparable in performance to commercially available lignins, such as Organocell, Alcell and Curan 100. The plant from which the lignin was isolated, and the process of the pulp mill are the primary influences on the performance of the lignin.

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...

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-...

Survey of Lignin-Structure Changes and Depolymerization during Ionic Liquid Pretreatment

Energy Technology Data Exchange (ETDEWEB)

Dutta, Tanmoy; Isern, Nancy G.; Sun, Jian; Wang, Eileen; Hull, Sarah; Cort, John R.; Simmons, Blake A.; Singh, Seema

2017-09-26

A detailed study of chemical changes in lignin structure during the ionic liquid (IL) pretreatment process is not only pivotal for understanding and overcoming biomass recalcitrance during IL pretreatment, but also is necessary for designing new routes for lignin valorization. Chemical changes in lignin were systematically studied as a function of pretreatment temperature, time and type of IL used. Kraft lignin was used as the lignin source and common pretreatment conditions were employed using three different ILs of varying chemical structure in terms of acidic or basic character. The chemical changes in the lignin structure due to IL pretreatment processes were monitored using 1H-13C HSQC NMR, 31P NMR, elemental analysis, GPC, FT-IR, and the depolymerized products were analyzed using GC-MS. Although pretreatment in acidic IL, triethylammonium hydrogensulfate ([TEA][HSO4]) results in maximum decrease in β-aryl ether bond, maximum dehydration and recondensation pathways were also evident, with the net process showing a minimum decrease in the molecular weight of regenerated lignin. However, 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) pretreatment yields a smaller decrease in the β-aryl ether content along with minimum evidence of recondensation, resulting in the maximum decrease in the molecular weight. Cholinium lysinate ([Ch][Lys]) pretreatment shows an intermediate result, with moderate depolymerization, dehydration and recondensation observed. The depolymerization products after IL pretreatment are found to be a function of the pretreatment temperature and the specific chemical nature of the IL used. At higher pretreatment temperature, [Ch][Lys] pretreatment yields guaiacol, [TEA][HSO4] yields guaiacylacetone, and [C2C1Im][OAc] yields both guaiacol and guaiacylacetone as major products. These results clearly indicate that the changes in lignin structure as well as the depolymerized product profile depend on the pretreatment conditions and the nature

Synthesis of novel ionic liquids from lignin-derived compounds

Science.gov (United States)

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.

Syringyl lignin is unaltered by severe sinapyl alcohol dehydrogenase suppression in tobacco.

Science.gov (United States)

Barakate, Abdellah; Stephens, Jennifer; Goldie, Alison; Hunter, William N; Marshall, David; Hancock, Robert D; Lapierre, Catherine; Morreel, Kris; Boerjan, Wout; Halpin, Claire

2011-12-01

The manipulation of lignin could, in principle, facilitate efficient biofuel production from plant biomass. Despite intensive study of the lignin pathway, uncertainty exists about the enzyme catalyzing the last step in syringyl (S) monolignol biosynthesis, the reduction of sinapaldehyde to sinapyl alcohol. Traditional schemes of the pathway suggested that both guaiacyl (G) and S monolignols are produced by a single substrate-versatile enzyme, cinnamyl alcohol dehydrogenase (CAD). This was challenged by the discovery of a novel sinapyl alcohol dehydrogenase (SAD) that preferentially uses sinapaldehyde as a substrate and that was claimed to regulate S lignin biosynthesis in angiosperms. Consequently, most pathway schemes now show SAD (or SAD and CAD) at the sinapaldehyde reduction step, although functional evidence is lacking. We cloned SAD from tobacco (Nicotiana tabacum) and suppressed it in transgenic plants using RNA interference-inducing vectors. Characterization of lignin in the woody stems shows no change to content, composition, or structure, and S lignin is normal. By contrast, plants additionally suppressed in CAD have changes to lignin structure and S:G ratio and have increased sinapaldehyde in lignin, similar to plants suppressed in CAD alone. These data demonstrate that CAD, not SAD, is the enzyme responsible for S lignin biosynthesis in woody angiosperm xylem.

Understanding the chemical and structural transformations of lignin macromolecule during torrefaction

International Nuclear Information System (INIS)

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

2014-01-01

Highlights: • The terrified bamboo has a high energy yield of 85.7% and a HHV of 20.13 MJ/kg. • The structural changes of hemicelluloses, cellulose, and lignin were investigated. • First study on the structural transformations of lignin during torrefaction. • The mechanism of structural changes of lignin has been proposed. - Abstract: Torrefaction is an efficient method to recover energy from biomass. Herein, the characteristics (mass yield, energy yield, physical, and chemical characteristics) of torrefied bamboo at diverse temperatures (200–300 °C) were firstly evaluated by elemental analysis, XRD, and CP–MAS 13 C NMR methodologies. Under an optimal condition the terrified bamboo has a relative high energy yield of 85.7% and a HHV of 20.13 MJ/kg. The chemical and structural transformations of lignin induced by thermal treatment were thoroughly investigated by FT-IR and solution-state NMR techniques (quantitative 13 C NMR, 2D-HSQC, and 31 P-NMR methodologies). The results highlighted the chemical reactions of the native bamboo lignins towards severe torrefaction treatments occurred, such as depolymerization, demethoxylation, bond cleavage, and condensation reactions. NMR results indicated that aryl-ether bonds (β-O-4) and p-coumaric ester in lignin were cleaved during the torrefaction process at mild conditions. The severe treatments of bamboo (275 °C and 300 °C) induced a dramatic enrichment in lignin content together with the almost complete disappearance of β-O-4, β-β, and β-5 linkages. Further analysis of the molecular weight of milled wood lignin (MWL) indicated that the average molecular weights of “torrefied MWL” were lower than those of control MWL. It is believed that understanding of the reactivity and chemical transformations of lignin during torrefaction will contribute to the integrated torrefaction mechanism

Lignin conversion to high-octane fuel additives

Energy Technology Data Exchange (ETDEWEB)

Shabtai, J.; Zmierczak, W.; Kadangode, S. [University of Utah, Salt Lake City (United States); Chornet, E.; Johnson, D.K. [National Renewable Energy Laboratory, Golden, CO (United States)

1999-07-01

Continuing previous studies on the conversion of lignin to reformulated gasoline compositions, new lignin upgrading processes were developed that allow preferential production of specific high-octane fuel additives of two distinct types: (1) C{sub 7}-C{sub 10} alkylbenzenes; and (2) aryl methyl ethers, where aryl mostly = phenyl, 2-methylphenyl, 4-methylphenyl, and dimethylphenyl. Process (1) comprises base-catalyzed depolymerization (BCD) and simultaneous partial ({approx} 50%) deoxygenation of lignin at 270 - 290{sup o}C, in the presence of supercritical methanol as reaction medium, followed by exhaustive hydrodeoxygenation and attendant mild hydrocracking of the BCD product with sulfided catalysts to yield C{sub 8}-C{sub 10} alkylbenzenes as main products. Process (2) involves mild BCD at 250 - 270{sup o}C with preservation of the lignin oxygen, followed by selective C-C hydrocracking with solid superacid catalysts. This method preferentially yields a mixture of alkylated phenols, which upon acid-catalyzed etherification with methanol are converted into corresponding aryl methyl ethers (see above) possessing blending octane numbers in the range of 142-166. In a recent extension of this work, a greatly advantageous procedure for performing the BCD stage of processes (1) and (2) in water as reaction medium was developed. (author)

PREPARATION AND CHARACTERIZATION OF COMPOSITES COMPRISING MODIFIED HARDWOOD AND WOOD POLYMERS/POLY(VINYL CHLORIDE

Directory of Open Access Journals (Sweden)

Ruxanda Bodîrlău

Full Text Available Chemical modification of hardwood sawdust from ash-tree species was carried out with a solution of maleic anhydride in acetone. Wood polymers, lignin, and cellulose were isolated from the wood sawdust and modified by the same method. Samples were characterized by Fourier transform infrared spectroscopy (FTIR, providing evidence that maleic anhydride esterifies the free hydroxyl groups of the wood polymer components. Composites comprising chemically modified wood sawdust and wood polymers (cellulose, lignin-as variable weight percentages-, and poly (vinyl chloride were obtained and further characterized by using FTIR spectroscopy and scanning electron microscopy (SEM. The thermal behavior of composites was investigated by using the thermogravimetric analysis (TGA. In all cases, thermal properties were affected by fillers addition.

Influence of lignin on biochemical methane potential of biomass for biogas production

DEFF Research Database (Denmark)

Triolo, Jin Mi; Sommer, Sven G.; Møller, Henrik Bjarne

2011-01-01

model for these two biomass groups. Validation of the combined model was carried out using datasets from the literature. This study showed that lignin was not degraded during anaerobic digestion. Furthermore, lignin concentration in organic materials was the strongest predictor of BMP for all...... the biomass groups. The square of the sample correlation coefficient (R2) from the BMP versus lignin was 0.908 (P lignin concentration could be used to predict...

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.

Lignin: an adhesive raw material of the future or waste of research energy?

OpenAIRE

Hemmilä, Venla; Trischler, Johann; Sandberg, Dick

2013-01-01

Lignin has been studied as an adhesive for more than 100 years, but there are only a few industrial applications. The reason for the current interest is the high availability and low price of lignin. Lignin is the main by-product of paper pulping processes and is typically burned as fuel. Being the natural glue in plants and having a phenolic nature makes lignins an attractive replacement for wood adhesives.An adhesive system for wood composites consisting mainly of lignin has yet to be devel...

Disruption of Mediator rescues the stunted growth of a lignin-deficient Arabidopsis mutant.

Science.gov (United States)

Bonawitz, Nicholas D; Kim, Jeong Im; Tobimatsu, Yuki; Ciesielski, Peter N; Anderson, Nickolas A; Ximenes, Eduardo; Maeda, Junko; Ralph, John; Donohoe, Bryon S; Ladisch, Michael; Chapple, Clint

2014-05-15

Lignin is a phenylpropanoid-derived heteropolymer important for the strength and rigidity of the plant secondary cell wall. Genetic disruption of lignin biosynthesis has been proposed as a means to improve forage and bioenergy crops, but frequently results in stunted growth and developmental abnormalities, the mechanisms of which are poorly understood. Here we show that the phenotype of a lignin-deficient Arabidopsis mutant is dependent on the transcriptional co-regulatory complex, Mediator. Disruption of the Mediator complex subunits MED5a (also known as REF4) and MED5b (also known as RFR1) rescues the stunted growth, lignin deficiency and widespread changes in gene expression seen in the phenylpropanoid pathway mutant ref8, without restoring the synthesis of guaiacyl and syringyl lignin subunits. Cell walls of rescued med5a/5b ref8 plants instead contain a novel lignin consisting almost exclusively of p-hydroxyphenyl lignin subunits, and moreover exhibit substantially facilitated polysaccharide saccharification. These results demonstrate that guaiacyl and syringyl lignin subunits are largely dispensable for normal growth and development, implicate Mediator in an active transcriptional process responsible for dwarfing and inhibition of lignin biosynthesis, and suggest that the transcription machinery and signalling pathways responding to cell wall defects may be important targets to include in efforts to reduce biomass recalcitrance.

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

Efficient, environmentally-friendly and specific valorization of lignin: promising role of non-radical lignolytic enzymes.

Science.gov (United States)

Wang, Wenya; Zhang, Chao; Sun, Xinxiao; Su, Sisi; Li, Qiang; Linhardt, Robert J

2017-06-01

Lignin is the second most abundant bio-resource in nature. It is increasingly important to convert lignin into high value-added chemicals to accelerate the development of the lignocellulose biorefinery. Over the past several decades, physical and chemical methods have been widely explored to degrade lignin and convert it into valuable chemicals. Unfortunately, these developments have lagged because of several difficulties, of which high energy consumption and non-specific cleavage of chemical bonds in lignin remain the greatest challenges. A large number of enzymes have been discovered for lignin degradation and these are classified as radical lignolytic enzymes and non-radical lignolytic enzymes. Radical lignolytic enzymes, including laccases, lignin peroxidases, manganese peroxidases and versatile peroxidases, are radical-based bio-catalysts, which degrade lignins through non-specific cleavage of chemical bonds but can also catalyze the radical-based re-polymerization of lignin fragments. In contrast, non-radical lignolytic enzymes selectively cleave chemical bonds in lignin and lignin model compounds and, thus, show promise for use in the preparation of high value-added chemicals. In this mini-review, recent developments on non-radical lignolytic enzymes are discussed. These include recently discovered non-radical lignolytic enzymes, their metabolic pathways for lignin conversion, their recent application in the lignin biorefinery, and the combination of bio-catalysts with physical/chemical methods for industrial development of the lignin refinery.

[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.

Nano-lignin filled natural rubber composites: Preparation and characterization

Directory of Open Access Journals (Sweden)

C. Jiang

2013-05-01

Full Text Available This paper presents a novel strategy to prepare nano-lignin and its composites with natural rubber. The nanolignin was ontained by fabricating colloidal lignin-Poly (diallyldimethylammonium chloride (PDADMAC complexes (LPCs via self-assembly technology. The characteristics of LPCs were investigated by zeta potential, dynamic light scattering (DLS, transmission electron microscopy (TEM, Fourier transform infrared spectroscopy (FTIR and ultraviolet – visible (UV-vis absorption measurements. The results indicated that PDADMAC intensively interacted with lignin by cation-π and π-π interactions, and lignin particles were stable in aqueous solution with an average particle size less than 100 nm. LPCs accelerated the vulcanization of NR/LPCs nanocomposites. Morphological studies and Dynamic mechanical analysis (DMA showed the homogeneous dispersion of LPCs in the NR matrix and the strong interfacial adhesion between them. The nanoscale dispersion of LPCs significantly enhanced the thermal stability and mechanical properties of NR/LPCs nanocomposites.

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

A structured understanding of cellobiohydrolase I binding to poplar lignin fractions after dilute acid pretreatment.

Science.gov (United States)

Yao, Lan; Yoo, Chang Geun; Meng, Xianzhi; Li, Mi; Pu, Yunqiao; Ragauskas, Arthur J; Yang, Haitao

2018-01-01

Cellulase adsorption to lignin is considered a cost barrier for bioethanol production; however, its detailed association mechanism is still not fully understood. In this study, two natural poplar variants with high and low sugar release performance were selected as the low and high recalcitrant raw materials (named L and H , respectively). Three different lignin fractions were extracted using ethanol, followed by p -dioxane and then cellulase treatment from the dilute acid pretreated poplar solids (fraction 1, 2, and 3, respectively). Each lignin fraction had different physicochemical properties. Ethanol-extracted lignin had the lowest weight average molecular weight, while the molecular weights for the other two lignin fractions were similar. 31 P NMR analysis revealed that lignin fraction with higher molecular weight contained more aliphatic hydroxyl groups and less phenolic hydroxyl groups. Semi-quantitative analysis by 2D HSQC NMR indicated that the lignin fractions isolated from the natural variants had different contents of syringyl (S), guaiacyl (G) and interunit linkages. Lignin extracted by ethanol contained the largest amount of S units, the smallest amounts of G and p -hydroxybenzoate (PB) subunits, while the contents of these lignin subunits in the other two lignin fractions were similar. The lignin fraction obtained after cellulase treatment was primarily comprised of β- O -4 linkages with small amounts of β-5 and β-β linkages. The binding strength of these three lignin fractions obtained by Langmuir equations were in the order of L 1  >  L 3  >  L 2 for the low recalcitrance poplar and H 1  >  H 2  >  H 3 for the high recalcitrance poplar. Overall, adsorption ability of lignin was correlated with the sugar release of poplar. Structural features of lignin were associated with its binding to CBH. For natural poplar variants, lignin fractions with lower molecular weight and polydispersity index (PDI) exhibited more CBH adsorption

Bio-oil from fast pyrolysis of lignin: Effects of process and upgrading parameters.

Science.gov (United States)

Fan, Liangliang; Zhang, Yaning; Liu, Shiyu; Zhou, Nan; Chen, Paul; Cheng, Yanling; Addy, Min; Lu, Qian; Omar, Muhammad Mubashar; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Anderson, Erik; Peng, Peng; Lei, Hanwu; Ruan, Roger

2017-10-01

Effects of process parameters on the yield and chemical profile of bio-oil from fast pyrolysis of lignin and the processes for lignin-derived bio-oil upgrading were reviewed. Various process parameters including pyrolysis temperature, reactor types, lignin characteristics, residence time, and feeding rate were discussed and the optimal parameter conditions for improved bio-oil yield and quality were concluded. In terms of lignin-derived bio-oil upgrading, three routes including pretreatment of lignin, catalytic upgrading, and co-pyrolysis of hydrogen-rich materials have been investigated. Zeolite cracking and hydrodeoxygenation (HDO) treatment are two main methods for catalytic upgrading of lignin-derived bio-oil. Factors affecting zeolite activity and the main zeolite catalytic mechanisms for lignin conversion were analyzed. Noble metal-based catalysts and metal sulfide catalysts are normally used as the HDO catalysts and the conversion mechanisms associated with a series of reactions have been proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structure of Thermobifida fusca DyP-type peroxidase and activity towards Kraft lignin and lignin model compounds.

Science.gov (United States)

Rahmanpour, Rahman; Rea, Dean; Jamshidi, Shirin; Fülöp, Vilmos; Bugg, Timothy D H

2016-03-15

A Dyp-type peroxidase enzyme from thermophilic cellulose degrader Thermobifida fusca (TfuDyP) was investigated for catalytic ability towards lignin oxidation. TfuDyP was characterised kinetically against a range of phenolic substrates, and a compound I reaction intermediate was observed via pre-steady state kinetic analysis at λmax 404 nm. TfuDyP showed reactivity towards Kraft lignin, and was found to oxidise a β-aryl ether lignin model compound, forming an oxidised dimer. A crystal structure of TfuDyP was determined, to 1.8 Å resolution, which was found to contain a diatomic oxygen ligand bound to the heme centre, positioned close to active site residues Asp-203 and Arg-315. The structure contains two channels providing access to the heme cofactor for organic substrates and hydrogen peroxide. Site-directed mutant D203A showed no activity towards phenolic substrates, but reduced activity towards ABTS, while mutant R315Q showed no activity towards phenolic substrates, nor ABTS. Copyright © 2016 Elsevier Inc. All rights reserved.

Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol : Influence of Reaction Temperature and Feedstock

NARCIS (Netherlands)

Huang, Xiaoming; Atay, Ceylanpinar; Zhu, Jiadong; Palstra, Sanne W L; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

2017-01-01

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while

Bio-inspired MOF-based Catalysts for Lignin Valorization.

Energy Technology Data Exchange (ETDEWEB)

Allendorf, Mark D.; Stavila, Vitalie; Ramakrishnan, Parthasarathi; Davis, Ryan Wesley

2014-09-01

Lignin is a potentially plentiful source of renewable organics, with %7E50Mtons/yr produced by the pulp/paper industry and 200-300 Mtons/yr projected production by a US biofuels industry. This industry must process approximately 1 billion tons of biomass to meet the US Renewable Fuel goals. However, there are currently no efficient processes for converting lignin to value-added chemicals and drop-in fuels. Lignin is therefore an opportunity for production of valuable renewable chemicals, but presents staggering technical and economic challenges due to the quantities of material involved and the strong chemical bonds comprising this polymer. Aggressive chemistries and high temperatures are required to degrade lignin without catalysts. Moreover, chemical non-uniformity among lignins leads to complex product mixtures that tend to repolymerize. Conventional petrochemical approaches (pyrolysis, catalytic cracking, gasification) are energy intensive (400-800 degC), require complicated separations, and remove valuable chemical functionality. Low-temperature (25-200 degC) alternatives are clearly desirable, but enzymes are thermally fragile and incompatible with liquid organic compounds, making them impractical for large-scale biorefining. Alternatively, homogeneous catalysts, such as recently developed vanadium complexes, must be separated from product mixtures, while many heterogenous catalysts involve costly noble metals. The objective of this project is to demonstrate proof of concept that an entirely new class of biomimetic, efficient, and industrially robust synthetic catalysts based on nanoporous Metal- Organic Frameworks (MOFs) can be developed. Although catalytic MOFs are known, catalysis of bond cleavage reactions needed for lignin degradation is completely unexplored. Thus, fundamental research is required that industry and most sponsoring agencies are currently unwilling to undertake. We introduce MOFs infiltrated with titanium and nickel species as catalysts

Effect of Lignin-Containing Media on Growth of Medicinal Mushroom Lentinula Edodes

Directory of Open Access Journals (Sweden)

Matjuškova Nataļja

2017-04-01

Full Text Available The effect of lignocellulose and lignin on growth of mycelium of mushroom Lentinula edodes and laccase activity in cultivation medium was studied. It was shown that cultivation of L. edodes mycelium in liquid nutrient medium with addition of 0.25-0.5% of kraft lignin increased mycelium biomass yield approximately two times compared with reference conditions without addition of lignin. Similar results were obtained in experiments in which 0.5% lignocellulose that remained after obtaining furfural, and 0.5% lignin that remained after obtaining furfural and glucose from wheat straw, were added to the nutrient medium. This effect was greater in the conditions of cultivation with good aeration, compared with static culture. Laccase activity in medium increased after addition of wheat straw lignocellulose or lignin only in the case of mycelium cultivation with aeration. In the case of mushroom cultivation on solid nutrient medium, addition of wheat straw lignocellulose and lignin promoted growth of mycelium only during the first 7 days of cultivation.

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.

Developing lignin-based bio-nanofibers by centrifugal spinning technique.

Science.gov (United States)

Stojanovska, Elena; Kurtulus, Mustafa; Abdelgawad, Abdelrahman; Candan, Zeki; Kilic, Ali

2018-07-01

Lignin-based nanofibers were produced via centrifugal spinning from lignin-thermoplastic polyurethane polymer blends. The most suitable process parameters were chosen by optimization of the rotational speed, nozzle diameter and spinneret-to-collector distance using different blend ratios of the two polymers at different total polymer concentrations. The basic characteristics of polymer solutions were enlightened by their viscosity and surface tension. The morphology of the fibers produced was characterized by SEM, while their thermal properties by DSC and TG analysis. Multiply regression was used to determine the parameters that have higher impact on the fiber diameter. It was possible to obtain thermally stable lignin/polyurethane nanofibers with diameters below 500nm. From the aspect of spinnability, 1:1 lignin/TPU contents were shown to be more feasible. On the other side, the most suitable processing parameters were found to be angular velocity of 8500rpm for nozzles of 0.5mm diameter and working distance of 30cm. Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis of syringyl and guaiacyl (S/G) ratio in lignin

CSIR Research Space (South Africa)

Spark, A

2006-12-01

Full Text Available the acidolysis products – Validate the new S/G ratio method Why are S/G ratios important? Gives a good indication of the reactivity of the lignin Experimental design Literature Review Establishing Acidolysis conditions Permanganate oxidation Lignin...-method is quick • Permanganate oxidation-method is slow but it is the standard method used at present • Nitrobenzene Oxidation, Pyrolysis, Cupric Oxidation and Thioacidolysis Lignin can be broken down to syringyl and guaiacyl subunits: OCH3 OH OCH3 OH...

Laccase catalyzed grafting of-N-OH type mediators to lignin via radical-radical coupling

DEFF Research Database (Denmark)

Munk, Line; Punt, A. M.; Kabel, M. A.

2017-01-01

Lignin is an underexploited resource in biomass refining. Laccases (EC 1.10.3.2) catalyze oxidation of phenolic hydroxyls using O2 as electron acceptor and may facilitate lignin modification in the presence of mediators. This study assessed the reactivity of four different synthetic mediators...... better than HBT (1-hydroxybenzotriazole). Three different mechanisms are suggested to explain the grafting of HPI and HBT, all involving radical-radical coupling to produce covalent bonding to lignin. Lignin from exhaustive cellulase treatment of wheat straw was more susceptible to grafting than beech...... organosolv lignin with the relative abundance of grafting being 35% vs. 11% for HPI and 5% vs. 1% for HBT on these lignin substrates. The data imply that lignin can be functionalized via laccase catalysis with-N-OH type mediators....

THE FUNGAL ABILITY FOR BIOBLEACHING/BIOPULPING/BIOREMEDIATION OF LIGNIN-LIKE COMPOUNDS OF AGRO-INDUSTRIAL RAW MATERIAL

Directory of Open Access Journals (Sweden)

Ana Maria Queijeiro López

Full Text Available Lignin is present in plant cell secondary wall, associated to carbohydrates preventing their efficient hydrolysis, and cellulose pulp manufacture basically consists in breaking down the middle lamella of plant cells, individualizing fibers such as cellulose from the other biopolymers. Different levels of lignocellulose are found in plant residues and they can be decomposed by extracellular fungal lignin modifying enzymes, used as a tool to reduce waste materials in contaminated soils and effluents. In the paper mill industries, for instance, they are a suitable or complementary alternative to the traditional methods of pulping/bleaching, contributing to improve paper strength as well as to reduce the pitch content, the quantity of chemicals and the consume of electrical energy. The aim of this review was to describe the fungal degradation of lignocellulosic like-material, the non-specific enzymatic aspects of the attack of wood and agricultural wastes, the fungal ability for biosorption and bioconversion, and its applications in the pulp/paper industry and bioremediation.

Methylene blue as a lignin surrogate in manganese peroxidase reaction systems.

Science.gov (United States)

Goby, Jeffrey D; Penner, Michael H; Lajoie, Curtis A; Kelly, Christine J

2017-11-15

Manganese peroxidase (MnP) is associated with lignin degradation and is thus relevant to lignocellulosic-utilization technologies. Technological applications require reaction mixture optimization. A surrogate substrate can facilitate this if its susceptibility to degradation is easily monitored and mirrors that of lignin. The dye methylene blue (MB) was evaluated in these respects as a surrogate substrate by testing its reactivity in reaction mixtures containing relevant redox mediators (dicarboxylic acids, fatty acids). Relative rates of MB degradation were compared to available literature reports of lignin degradation under similar conditions, and suggest that MB can be a useful lignin surrogate in MnP systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Thermoplastic Starch with Improved Properties by Blending with Lignins and Radiation Processing

International Nuclear Information System (INIS)

Zheng, D.; Baumberger, S.; Mikus, P.-Y.; Dole, P.; Soulestin, J.; Lacrampe, M.F.; Bliard, C.; Coqueret, X.

2010-01-01

The biorefinery of lignocellulosics generates lignin-rich fractions, which are potential source of phenolic molecules for chemistry and polymeric materials. The LignoStarch project aims at using such fractions to functionalize a renewable material, starch, by a clean physical grafting process, without any synthetic chemical additive and without any by-products generation. Previous works suggested that the low-molar-mass phenolic compounds in technical lignin could be responsible for the reactivity of starch-lignin system under electron-beam irradiation and improvement of starch water resistance. A particular aspect of the current studies is focused on the role of lignin phenolic extractables and to investigate the different chemical and physical parameters likely to impact the surface properties of starch-lignin materials. (author)

High Shear Homogenization of Lignin to Nanolignin and Thermal Stability of Nanolignin-Polyvinyl Alcohol Blends

Science.gov (United States)

Sandeep S. Nair; Sudhir Sharma; Yunqiao Pu; Qining Sun; Shaobo Pan; J.Y. Zhu; Yulin Deng; Art J. Ragauskas

2014-01-01

A new method to prepare nanolignin using a simple high shear homogenizer is presented. The kraft lignin particles with a broad distribution ranging from large micron- to nano-sized particles were completely homogenized to nanolignin particles with sizes less than 100 nm after 4 h of mechanical shearing. The 13C nuclear magnetic resonance (NMR)...

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.

Production of lignin peroxidase by Ganoderma leucidum using solid ...

African Journals Online (AJOL)

The main objectives of this study were to optimize the culture conditions for the production of lignin peroxidase by Ganoderma leucidum, economic utilization of waste corn cobs as inducers substrate by pollution free fermentation technology and to optimize the solid state fermentation (SSF) process for lignin peroxidase ...

Effect of periodate on lignin for wood adhesive application

NARCIS (Netherlands)

Gosselink, R.J.A.; Dam, van J.E.G.; Jong, de E.; Gellerstedt, G.; Scott, E.L.; Sanders, J.P.M.

2011-01-01

Development of eco-friendly binders with no harmful emission during its complete life cycle is of high interest for the wood-based industry. In this paper, a fully renewable binder based on activated lignin and poly-furfuryl alcohol and a partly renewable lignin based phenol-formaldehyde (PF) binder

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

Enhancement of Lignin Biopolymer Isolation from Hybrid Poplar by Organosolv Pretreatments

Directory of Open Access Journals (Sweden)

Miao Wu

2014-01-01

Full Text Available Lignocellulosic biomass is an abundant renewable resource that has the potential to displace petroleum in the production of biomaterials and biofuels. In the present study, the fractionation of different lignin biopolymers from hybrid poplar based on organosolv pretreatments using 80% aqueous methanol, ethanol, 1-propanol, and 1-butanol at 220°C for 30 min was investigated. The isolated lignin fractions were characterized by Fourier transform infrared spectroscopy (FT-IR, high-performance anion exchange chromatography (HPAEC, 2D nuclear magnetic resonance (2D NMR, and thermogravimetric analysis (TGA. The results showed that the lignin fraction obtained with aqueous ethanol (EOL possessed the highest yield and the strongest thermal stability compared with other lignin fractions. In addition, other lignin fractions were almost absent of neutral sugars (1.16–1.46% though lignin preparation extracted with 1-butanol (BOL was incongruent (7.53%. 2D HSQC spectra analysis revealed that the four lignin fractions mainly consisted of β-O-4′ linkages combined with small amounts of β-β′ and β-5′ linkages. Furthermore, substitution of Cα in β-O-4′ substructures had occurred due to the effects of dissolvent during the autocatalyzed alcohol organosolv pretreatments. Therefore, aqueous ethanol was found to be the most promising alcoholic organic solvent compared with other alcohols to be used in noncatalyzed processes for the pretreatment of lignocellulosic biomass in biorefinery.

Lignin-enriched Fermentation Residues from Bioethanol Production of Fast-growing Poplar and Forage Sorghum

Directory of Open Access Journals (Sweden)

José I Santos

2015-07-01

Full Text Available The current challenges in developing a cost-effective bioethanol industry include the production of not only high-volume, low cost biofuels but also high-value products with minimal downstream waste. The up-grading of side-stream lignins from bioethanol production plants to novel high-value products will improve the profitability of the bioethanol industry; to do that, a precise understanding of lignin is required. In the present study, lignin-enriched fermentation residues from bioethanol production (steam explosion pretreatment, saccharification, and fermentation of fast-growing poplar and forage sorghum were characterized. In addition to the purity and composition, lignin structure (syringyl/guaiacyl (S/G ratio, inter-unit linkages was also analyzed with spectroscopy techniques such as Fourier transform infrared and two-dimensional nuclear magnetic resonance. Bioethanol processing and feedstock origins seemed to be the main factors determining the purity, composition, and structure of lignins. Residual lignins from poplar and forage sorghum contained significant amounts of sugar and protein impurities. Poplar lignin showed a very high S/G ratio associated with p-hydroxybenzoate. A lower S/G ratio together with H lignin units and p-hydroxycinnamates (p-coumarate and ferulate was observed for forage sorghum lignin. The main inter-unit linkages present in both lignins were β-O-4´ aryl ether followed by resinols and phenylcoumarans.

Fast Curing Bio-Based Phenolic Resins via Lignin Demethylated under Mild Reaction Condition

OpenAIRE

Jiongjiong Li; Jizhi Zhang; Shifeng Zhang; Qiang Gao; Jianzhang Li; Wei Zhang

2017-01-01

Demethylation technique has been used to enhance lignin reactivity for preparation of phenolic resins. However, the demethylation efficiency and the demethylated lignin (DL) reactivity were still unsatisfactory. To improve the demethylation efficiency, alkali lignin was demethylated under different mild conditions using sodium sulfite as a catalyst. Lignin and DL were characterized by 1H-NMR (nuclear magnetic resonance) and Fourier transform infrared (FT-IR) spectroscopy to determine the deme...

Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer

DEFF Research Database (Denmark)

Westereng, Bjorge; Cannella, David; Wittrup Agger, Jane

2015-01-01

in biological systems are only partly understood. We show here that insoluble high molecular weight lignin functions as a reservoir of electrons facilitating LPMO activity. The electrons are donated to the enzyme by long-range electron transfer involving soluble low molecular weight lignins present in plant...... cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...

Catalytic hydrotreating of lignin with water-soluble molybdenum catalyst

Energy Technology Data Exchange (ETDEWEB)

Osmaa, A.; Johansson, A. (Technical Research Centre of Finland, Espoo (Finland). Lab. of Fuel and Process Technology)

High yields (61% of the original lignin) of low molecular weight oil (84% of the oil eluted through GC) have been obtained by hydrotreating kraft pine lignin with a water-soluble molybdenum catalyst at 430[degree]C for 60 min. The main compounds in the product oil were phenols (8.7% of the original lignin), cyclohexanes (5.0%), benzenes (3.8%), naphthalenes (4.0%), and phenanthrenes (1.2%). The degree of hydrodeoxygenation was 98%. The quality (measured by GPC and GC) of the product was as good as when using more expensive solid NiMo-CR[sub 2]O[sub 3] catalysts. 30 refs., 6 tabs.

Radiolysis of lignin: Prospective mechanism of high-temperature decomposition

Science.gov (United States)

Ponomarev, A. V.

2017-12-01

The range of the radiation-thermal processes resulting in conversion of lignin into monomeric phenols is considered. Statistically the most probable places of macromolecule ionization are aromatic units. Release of phenolic products from a lignin macromolecule is the multistage process beginning via fragmentation of primary cation-radicals. Reactions of electrons and small radicals with macromolecules, also as degradation of cation-radicals, result in formation of phenoxyl radicals. Macroradicals possess lower heat stability in comparison with macromolecules. Thermal decomposition of macroradicals leads to release of monohydric and dihydric phenols. The probability of benzenediols formation increases in the presence of alkanes. As noted, partial transformation of lignin into charcoal is inevitable.

Structural Changes of Lignin after Liquid Hot Water Pretreatment and Its Effect on the Enzymatic Hydrolysis

Directory of Open Access Journals (Sweden)

Wen Wang

2016-01-01

Full Text Available During liquid hot water (LHW pretreatment, lignin is mostly retained in the pretreated biomass, and the changes in the chemical and structural characteristics of lignin should probably refer to re-/depolymerization, solubilization, or glass transition. The residual lignin could influence the effective enzymatic hydrolysis of cellulose. The pure lignin was used to evaluate the effect of LHW process on its structural and chemical features. The surface morphology of LHW-treated lignin observed with the scanning electron microscopy (SEM was more porous and irregular than that of untreated lignin. Compared to the untreated lignin, the surface area, total pore volume, and average pore size of LHW-treated lignin tested with the Brunner-Emmet-Teller (BET measurement were increased. FTIR analysis showed that the chemical structure of lignin was broken down in the LHW process. Additionally, the impact of untreated and treated lignin on the enzymatic hydrolysis of cellulose was also explored. The LHW-treated lignin had little impact on the cellulase adsorption and enzyme activities and somehow could improve the enzymatic hydrolysis of cellulose.

Biobased alkylphenols from lignins via a two-step pyrolysis - Hydrodeoxygenation approach.

Science.gov (United States)

de Wild, P J; Huijgen, W J J; Kloekhorst, A; Chowdari, R K; Heeres, H J

2017-04-01

Five technical lignins (three organosolv, Kraft and soda lignin) were depolymerised to produce monomeric biobased aromatics, particularly alkylphenols, by a new two-stage thermochemical approach consisting of dedicated pyrolysis followed by catalytic hydrodeoxygenation (HDO) of the resulting pyrolysis oils. Pyrolysis yielded a mixture of guaiacols, catechols and, optionally, syringols in addition to alkylphenols. HDO with heterogeneous catalysts (Ru/C, CoMo/alumina, phosphided NiMO/C) effectively directed the product mixture towards alkylphenols by, among others, demethoxylation. Up to 15wt% monomeric aromatics of which 11wt% alkylphenols was obtained (on the lignin intake) with limited solid formation (<3wt% on lignin oil intake). For comparison, solid Kraft lignin was also directly hydrotreated for simultaneous depolymerisation and deoxygenation resulting in two times more alkylphenols. However, the alkylphenols concentration in the product oil is higher for the two-stage approach. Future research should compare direct hydrotreatment and the two-stage approach in more detail by techno-economic assessments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of common lignin methods and modifications on forage and lignocellulosic biomass materials.

Science.gov (United States)

Goff, Ben M; Murphy, Patrick T; Moore, Kenneth J

2012-03-15

A variety of methods have been developed for estimating lignin concentration within plant materials. The objective of this study was to compare the lignin concentrations produced by six methods on a diverse population of forage and biomass materials and to examine the relationship between these concentrations and the portions of these materials that are available for utilisation by livestock or for ethanol conversion. Several methods produced lignin concentrations that were highly correlated with the digestibility of the forages, but there were few relationships between these methods and the available carbohydrate of the biomass materials. The use of Na₂SO₃ during preparation of residues for hydrolysis resulted in reduced lignin concentrations and decreased correlation with digestibility of forage materials, particularly the warm-season grasses. There were several methods that were well suited for predicting the digestible portion of forage materials, with the acid detergent lignin and Klason lignin method giving the highest correlation across the three types of forage. The continued use of Na₂SO₃ during preparation of Van Soest fibres needs to be evaluated owing to its ability to reduce lignin concentrations and effectiveness in predicting the utilisation of feedstuffs and feedstocks. Because there was little correlation between the lignin concentration and the biomass materials, there is a need to examine alternative or develop new methods to estimate lignin concentrations that may be used to predict the availability of carbohydrates for ethanol conversion. Copyright © 2011 Society of Chemical Industry.

Syringyl Lignin Is Unaltered by Severe Sinapyl Alcohol Dehydrogenase Suppression in Tobacco[W

Science.gov (United States)

Barakate, Abdellah; Stephens, Jennifer; Goldie, Alison; Hunter, William N.; Marshall, David; Hancock, Robert D.; Lapierre, Catherine; Morreel, Kris; Boerjan, Wout; Halpin, Claire

2011-01-01

The manipulation of lignin could, in principle, facilitate efficient biofuel production from plant biomass. Despite intensive study of the lignin pathway, uncertainty exists about the enzyme catalyzing the last step in syringyl (S) monolignol biosynthesis, the reduction of sinapaldehyde to sinapyl alcohol. Traditional schemes of the pathway suggested that both guaiacyl (G) and S monolignols are produced by a single substrate-versatile enzyme, cinnamyl alcohol dehydrogenase (CAD). This was challenged by the discovery of a novel sinapyl alcohol dehydrogenase (SAD) that preferentially uses sinapaldehyde as a substrate and that was claimed to regulate S lignin biosynthesis in angiosperms. Consequently, most pathway schemes now show SAD (or SAD and CAD) at the sinapaldehyde reduction step, although functional evidence is lacking. We cloned SAD from tobacco (Nicotiana tabacum) and suppressed it in transgenic plants using RNA interference–inducing vectors. Characterization of lignin in the woody stems shows no change to content, composition, or structure, and S lignin is normal. By contrast, plants additionally suppressed in CAD have changes to lignin structure and S:G ratio and have increased sinapaldehyde in lignin, similar to plants suppressed in CAD alone. These data demonstrate that CAD, not SAD, is the enzyme responsible for S lignin biosynthesis in woody angiosperm xylem. PMID:22158465

Microwave-assisted acid pretreatment of alkali lignin: Effect on characteristics and pyrolysis behavior.

Science.gov (United States)

Duan, Dengle; Ruan, Roger; Wang, Yunpu; Liu, Yuhuan; Dai, Leilei; Zhao, Yunfeng; Zhou, Yue; Wu, Qiuhao

2018-03-01

This study performed microwave-assisted acid pretreatment on pure lignin. The effects of microwave temperature, microwave time, and hydrochloric acid concentration on characteristics and pyrolysis behavior of lignin were examined. Results of ultimate analysis revealed better properties of all pretreated samples than those of raw lignin. Fourier transform infrared spectroscopy analysis showed breakage of βO4 bond and aliphatic side chain, decrease in OH groups, and formation of CO groups in pretreatment. Microwave temperature exerted more significant influence on lignin structure. Thermal stability of treated lignin was improved and insensitive to short microwave time and acid concentration under mild conditions. Resulting from improved alkyl-phenols and decreased alkoxy-phenols, microwave-assisted acid pretreatment of lignin yielded bio-oil with excellent quality. Total yield of phenols in pyrolysis vapors (200 °C) improved to 14.15%, whereas that of guaiacols decreased to 22.36%. This study shows that microwave-assisted acid pretreatment is a promising technology for lignin conversion. Copyright © 2017 Elsevier Ltd. All rights reserved.

Production of Micro- and Nanoscale Lignin from Wheat Straw Using Different Precipitation Setups.

Science.gov (United States)

Beisl, Stefan; Loidolt, Petra; Miltner, Angela; Harasek, Michael; Friedl, Anton

2018-03-11

Micro- and nanosize lignin has recently gained interest due to its improved properties compared to standard lignin available today. As the second most abundant biopolymer after cellulose, lignin is readily available but used for rather low-value applications. Applications for lignin in micro- to nanoscale however, ranging from improvement of mechanical properties of polymer nanocomposites, have bactericidal and antioxidant properties and impregnations to hollow lignin drug carriers for hydrophobic and hydrophilic substances. This research represents a whole biorefinery process chain and compares different precipitation setups to produce submicron lignin particles from lignin containing an organosolv pretreatment extract from wheat straw. A batch precipitation in a stirred vessel was compared with continuous mixing of extract and antisolvent in a T-fitting and mixing in a T-fitting followed by a static mixer. The precipitation in the combination of T-fitting and static mixer with improved precipitation parameters yields the smallest particle size of around 100 nm. Furthermore, drying of particles did not influence the particle sizes negatively by showing decreased particle diameters after the separation process.

Enzymes in Commercial Cellulase Preparations Bind Differently to Dioxane Extracted Lignins

Energy Technology Data Exchange (ETDEWEB)

Yarbrough, John M.; Mittal, Ashutosh; Katahira, Rui; Mansfield, Elisabeth; Taylor, Larry E.; Decker, Stephen R.; Himmel, Michael E.; Vinzant, Todd

2017-04-24

Commercial fungal cellulases used in biomass-to-biofuels processes can be grouped into three general classes: native, augmented, and engineered. To evaluate lignin binding affinities of different enzyme activities in various commercial cellulase formulations in order to determine if enzyme losses due to lignin binding can be modulated by using different enzymes of the same activity We used water:dioxane (1:9) to extract lignin from pretreated corn stover. Commercial cellulases were incubated with lignin and the unbound supernatants were evaluated for individual enzyme loss by SDS=PAGE and these were correlated with activity loss using various pNP-sugar substrates. Colorimetric assays for general glycosyl hydrolase activities showed distinct differences in enzyme binding to lignin for each enzyme activity. Native systems demonstrated low binding of endo- and exo-cellulases, high binding of xylanase, and moderate ..beta..-glucosidase binding. Engineered cellulase mixtures exhibited low binding of exo-cellulases, very strong binding of endocellulases and ..beta..- glucosidase, and mixed binding of xylanase activity. The augmented cellulase had low binding of exocellulase, high binding of endocellulase and xylanase, and moderate binding of ..beta..-glucosidase activities. Bound and unbound activities were correlated with general molecular weight ranges of proteins as measured by loss of proteins bands in bound fractions on SDS-PAGE gels. Lignin-bound high molecular weight bands correlated with binding of ..beta..-glucosidase activity. While ..beta..-glucosidases demonstrated high binding in many cases, they have been shown to remain active. Bound low molecular weight bands correlated with xylanase activity binding. Contrary to other literature, exocellulase activity did not show strong lignin binding. The variation in enzyme activity binding between the three classes of cellulases preparations indicate that it is certainly possible to alter the binding of specific

Exploring the antioxidant potential of lignin isolated from black liquor of oil palm waste.

Science.gov (United States)

Bhat, Rajeev; Khalil, H P S A; Karim, A A

2009-09-01

This study was conducted to evaluate the potential antioxidant activity of lignin obtained from black liquor, a hazardous waste product generated during the extraction of palm oil. Antioxidant potential of the extracted lignin was evaluated by dissolving the extracted samples in 2 different solvent systems, namely, 2-methoxy ethanol and DMSO. Results revealed high percent inhibition of the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical in the lignin sample dissolved in 2-methoxy ethanol over DMSO (concentration range of 1-100 microg/ml). Lignin extracted in 2-methoxy ethanol exhibited higher inhibition percentage (at 50 microg/ml, 84.2%), whereas a concentration of 100 microg/ml was found to be effective in the case of the DMSO solvent (69.8%). Fourier transform infrared (FTIR) spectrometry revealed that the functional groups from the extracted lignin and commercial lignin were highly similar, indicating the purity of the lignin extracted from black liquor. These results provide a strong basis for further applications of lignin in the food industry and also illustrate an eco-friendly approach to utilize oil palm black liquor.

Conversion of kraft lignin over hierarchical MFI zeolite.

Science.gov (United States)

Kim, Seong-Soo; Lee, Hyung Won; Ryoo, Ryong; Kim, Wookdong; Park, Sung Hoon; Jeon, Jong-Ki; Park, Young-Kwon

2014-03-01

Catalytic pyrolysis of kraft lignin was carried out using pyrolysis gas chromatography/mass spectrometry. Hierarchical mesoporous MFI was used as the catalyst and another mesoporous material Al-SBA-15 was also used for comparison. The characteristics of mesoporous MFI were analyzed by X-ray diffraction patterns, N2 adsorption-desorption isotherms, and temperature programmed desorption of NH3. Two catalyst/lignin mass ratios were tested: 5/1 and 10/1. Aromatics and alkyl phenolics were the main products of the catalytic pyrolysis of lignin over mesoporous MFI. In particular, the yields of mono-aromatics such as benzene, toluene, ethylbenzene, and xylene were increased substantially by catalytic upgrading. Increase in the catalyst dose enhanced the production of aromatics further, which is attributed to decarboxylation, decarbonlyation, and aromatization reactions occurring over the acid sites of mesoporous MFI.

Properties and Possible Applications for Lignin Streams Obtained from Rice Straw Processing

DEFF Research Database (Denmark)

Mussatto, Solange I.

This study aimed to evaluate the chemical and physical properties of lignin streams recovered from rice straw processing and to study the extraction of antioxidant phenolic compounds from these materials. The evaluated samples included two different cellulignin fermentation residues (FR’s) and an......This study aimed to evaluate the chemical and physical properties of lignin streams recovered from rice straw processing and to study the extraction of antioxidant phenolic compounds from these materials. The evaluated samples included two different cellulignin fermentation residues (FR......’s) and an acid-precipitated lignin from alkaline-deacetylated black liquor (DBLL). For comparison, a standard lignin sample (Kraft lignin, from Sigma-Aldrich) was also assayed. Besides providing a better understanding about such materials, the obtained results made also possible to propose some potential...

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.

Aromatic chemicals by iron-catalyzed hydrotreatment of lignin pyrolysis vapor.

Science.gov (United States)

Olcese, Roberto Nicolas; Lardier, George; Bettahar, Mohammed; Ghanbaja, Jaafar; Fontana, Sébastien; Carré, Vincent; Aubriet, Frédéric; Petitjean, Dominique; Dufour, Anthony

2013-08-01

Lignin is a potential renewable material for the production of bio-sourced aromatic chemicals. We present the first hydrotreatment of lignin pyrolysis vapors, before any condensation, using inexpensive and sustainable iron-silica (Fe/SiO2 ) and iron-activated carbon (Fe/AC) catalysts. Lignin pyrolysis was conducted in a tubular reactor and vapors were injected in a fixed bed of catalysts (673 K, 1 bar) with stacks to investigate the profile of coke deposit. More than 170 GC-analyzable compounds were identified by GCxGC (heart cutting)/flame ionization detector mass spectrometry. Lignin oligomers were analyzed by very high resolution mass spectrometry, called the "petroleomic" method. They are trapped by the catalytic fixed bed and, in particular, by the AC. The catalysts showed a good selectivity for the hydrodeoxygenation of real lignin vapors to benzene, toluene, xylenes, phenol, cresols, and alkyl phenols. The spent catalysts were characterized by temperature-programmed oxidation, transmission electron microscopy (TEM), and N2 sorption. Micropores in the Fe/AC catalyst are completely plugged by coke deposits, whereas the mesoporous structure of Fe/SiO2 is unaffected. TEM images reveal two different types of coke deposit: 1) catalytic coke deposited in the vicinity of iron particles and 2) thermal coke (carbonaceous particles ≈1 μm in diameter) formed from the gas-phase growth of lignin oligomers. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Styrene-spaced copolymers including anthraquinone and β-O-4 lignin model units: synthesis, characterization and reactivity under alkaline pulping conditions.

Science.gov (United States)

Megiatto, Jackson D; Cazeils, Emmanuel; Ham-Pichavant, Frédérique; Grelier, Stéphane; Gardrat, Christian; Castellan, Alain

2012-05-14

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

Oxidative degradation of lignin by photochemical and chemical radical generating systems

International Nuclear Information System (INIS)

Gold, M.H.; Kutsuki, H.; Morgan, M.A.

1983-01-01

Oxidation of specifically radiolabeled 14 C-lignins by UV/H 2 O 2 , Fenton's reagent, photosensitizing riboflavin, UV- and γ-irradiation was examined. In the presence of UV/H 2 O 2 , a hydroxyl radical (radicalOH) generating system, 14 C-methoxy, 2-[ 14 C-sidechain] and 14 C-ring labeled lignin were rapidly and extensively degraded as measured by gel filtration of the reaction products on Sephadex LH-20. This suggested that exposure to radicalOH leads to rapid, nonspecific lignin degradation. Rapid degradation of 14 C-methoxy, 2-[ 14 C-sidechain] and 14 C-ring labeled lignin also occurred in the presence of the radicalOH generating system, Fenton's reagent, confirming the primary role of radicalOH in these reactions. Photosensitizing riboflavin, also capable of effecting transformation of organic compounds via Type I hydrogen radical abstractions, caused extensive oxidative degradation of 14 C-methoxy labeled lignin and significant degradation of 2-[ 14 C-sidechain] and 14 C-ring labeled lignin. In addition, UV- and γ-irradiation caused slower but extensive degradation of the polymers, probably via radical type mechanisms. All of these results indicate that radicalOH as well as organic radical generating systems are effective agents for the purpose of degrading this heterogeneous, optically inactive and random biopolymer. (author)

Improved Lignin Polyurethane Properties with Lewis Acid Treatment

OpenAIRE

Chung, Hoyong; Washburn, Newell R.

2012-01-01

Chemical modification strategies to improve the mechanical properties of lignin-based polyurethanes are presented. We hypothesized that treatment of lignin with Lewis acids would increase the concentration of hydroxyl groups available to react with diisocyanate monomers. Under the conditions used, hydrogen bromide-catalyzed modification resulted in a 28% increase in hydroxyl group content. Associated increases in hydrophilicity of solvent-cast thin films were also recorded as evidenced by ...

Valorisation of lignin – Achievements of the LignoValue project

NARCIS (Netherlands)

Gosselink, R.J.A.; Dam, van J.E.G.; Wild, de P.; Huijgen, W.; Bridgwater, T.; Heeres, H.J.; Kloekhorst, A.; Scott, E.L.; Sanders, J.P.M.

2011-01-01

Lignocellulosic biorefinery for production of biofuels, materials and chemicals requires valorization of all fractions including lignin. As a consequence of its poly-aromatic structure, lignin potentially serves as a source for aromatic chemicals. The developed biorefinery concept of the LignoValue

Experimental and Kinetic Study on Lignin Depolymerization in Water/Formic Acid System

Directory of Open Access Journals (Sweden)

Qi Wang

2017-10-01

Full Text Available Microwave-assisted depolymerization of black-liquor lignin in formic acid was studied, concentrating on the yield of liquid fractions as bio-oil 1 (mainly aromatic monomers and bio-oil 2 (mainly aromatic oligomers and the distribution of the specific compositions. Bio-oil 1 (9.69% and bio-oil 2 (54.39% achieved their maximum yields under 160 °C with the reaction time of 30 min. The chemical compositions of bio-oil 1 and bio-oil 2 were respectively identified by means of Gas Chromatography-Mass Spectrometer (GC-MS and Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS. Ethanone, 1-(4-hydroxy-3-methoxyphenyl and Ethanone, 1-(4-hydrox-3,5-dimethoxyphenyl were evidenced to be the two prominent compounds in bio-oil 1. Production of aromatic oligomers with the molecular weight of 328, 342, 358, 378, 394, 424 and 454 identified by MALDI-TOF MS was substantially tuned with the reaction temperature. A two-separate-stage kinetic model was proposed to describe the acidic solvolysis of lignin assisted by microwave heating, where the first stage is dominated by the depolyerization of lignin to monomers and oligomers with the activation energy of 40.27 kJ·mol−1, and the second stage with the activation energy of 49.18 kJ·mol−1 is mainly ascribed to the repolymerization of first-stage produced compounds.

A NEW PROCESS DEVELOPED FOR SEPARATION OF LIGNIN FROM AMMONIUM HYDROXIDE PRETREATMENT SOLUTIONS

Energy Technology Data Exchange (ETDEWEB)

Sherman, S.; Gorensek, M.; Milliken, C.

2010-12-14

A method is described for separating lignin from liquid solutions resulting from the pretreatment of lignocellulosic materials such as switchgrass with ammonium hydroxide. The method involves a sequence of steps including acidification, evaporation, and precipitation or centrifugation that are performed under defined conditions, and results in a relatively pure, solid lignin product. The method is tested on ammonium hydroxide solutions containing lignin extracted from switchgrass. Experimental results show that the method is capable of recovering between 66-95% of dissolved lignin as a precipitated solid. Cost estimates of pilot-scale and industrial-scale expressions of the process indicate that breakeven lignin prices of $2.36/kg and $0.78/kg, respectively, may be obtainable with this recovery method.

Paving the Way for Lignin Valorisation : Recent Advances in Bioengineering, Biorefining and Catalysis

NARCIS (Netherlands)

Rinaldi, Roberto; Jastrzebski, Robin|info:eu-repo/dai/nl/338017747; Clough, Matthew T; Ralph, John; Kennema, Marco; Bruijnincx, Pieter C A|info:eu-repo/dai/nl/33799529X; Weckhuysen, Bert M|info:eu-repo/dai/nl/285484397

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

Fast Curing Bio-Based Phenolic Resins via Lignin Demethylated under Mild Reaction Condition

Directory of Open Access Journals (Sweden)

Jiongjiong Li

2017-09-01

Full Text Available Demethylation technique has been used to enhance lignin reactivity for preparation of phenolic resins. However, the demethylation efficiency and the demethylated lignin (DL reactivity were still unsatisfactory. To improve the demethylation efficiency, alkali lignin was demethylated under different mild conditions using sodium sulfite as a catalyst. Lignin and DL were characterized by 1H-NMR (nuclear magnetic resonance and Fourier transform infrared (FT-IR spectroscopy to determine the demethylation mechanism. With the demethylation of lignin, the methoxyl group content decreased from 1.93 m mol/g to 1.09 m mol/g, and the phenolic hydroxyl group content increased from 0.56 m mol/g to 0.82 m mol/g. These results revealed that methoxyl groups were attacked by SO32−, and some methoxyl groups were converted to phenolic hydroxyl groups by a nucleophilic substitution reaction, generating DL with high reactivity. The chemical properties of lignin-based phenolic resins were studied by 13C-NMR and FT-IR spectroscopy, and their physical properties were also investigated. The results indicated that lignin-based phenolic resins exhibited faster curing rate and shorter gel time. In addition, the bonding strength increased from 0.92 MPa to 1.07 MPa, and the formaldehyde emission decreased from 0.58 mg/L to 0.22 mg/L after lignin demethylated at the optimum condition.

Structural changes in lignin during organosolv pretreatment of Liriodendron tulipifera and the effect on enzymatic hydrolysis

International Nuclear Information System (INIS)

Koo, Bon-Wook; Min, Byeong-Cheol; Gwak, Ki-Seob; Lee, Soo-Min; Choi, Joon-Weon; Yeo, Hwanmyeong; Choi, In-Gyu

2012-01-01

Although organosolv pretreatment removed substantial amounts of lignin and xylan, the yield of glucan which is a major sugar source for fermentation to ethanol is more than 90% in most conditions of the organosolv pretreatment. Relative lignin contents of all pretreated biomass were more than 200 g kg −1 , however enzymatic conversions were increased dramatically comparing to untreated biomass. Therefore the correlation between lignin and enzymatic hydrolysis could not be explained just by lignin content, and other changes resulting from lignin removal affected enzymatic hydrolysis. Results on enzymatic conversion and sugar recovery suggested that the critical temperature improving enzymatic hydrolysis significantly was between 120 °C and 130 °C. Microscopic analysis using Field emission scanning electron microscopy (FE-SEM) showed that structural lignin changes happened through organosolv pretreatment. Lignins were isolated from lignin carbohydrate complex (LCC) at the initial stage and then migrated to the surface of biomass. The isolated and migrated lignins were finally redistributed onto surface. These structural changes formed droplets on surface and increased pore volume in pretreated biomass. The increase in pore volume also increased available surface area and enzyme adsorption at initial stage, and thus enzymatic conversion increased significantly through organosolv pretreatment. It was verified that the droplets were mainly composed of lignin and the lignin droplets inhibited enzymatic hydrolysis through adsorption with cellulase. -- Highlights: ► Just lignin contents cannot explain a correlation with enzymatic hydrolysis. ► Several changes resulted from lignin removal must affect enzymatic hydrolysis. ► Droplets are formed by structural changes in lignin during organosolv pretreatment. ► Formation of the lignin droplet increases the pore volume in biomass. ► The increase in pore volume enhances the enzymatic hydrolysis.

Probing the interactions between lignin and inorganic oxides using atomic force microscopy

Energy Technology Data Exchange (ETDEWEB)

Wang, Jingyu; Qian, Yong, E-mail: qianyong86@163.com; Deng, Yonghong; Liu, Di; Li, Hao; Qiu, Xueqing, E-mail: xueqingqiu66@163.com

2016-12-30

Graphical abstract: The interactions between lignin and inorganic oxides are quantitatively probed by atomic force microscopy, which is fundamental but beneficial for understanding and optimizing the absorption-dispersion and catalytic degradation processes of lignin. - Highlights: • The interactions between lignin and inorganic oxides are measured using AFM. • The adhesion forces between lignin and metal oxides are larger than that in nonmetal systems. • Hydrogen bond plays an important role in lignin-inorganic oxides system. - Abstract: Understanding the interactions between lignin and inorganic oxides has both fundamental and practical importance in industrial and energy fields. In this work, the specific interactions between alkali lignin (AL) and three inorganic oxide substrates in aqueous environment are quantitatively measured using atomic force microscopy (AFM). The results show that the average adhesion force between AL and metal oxide such as Al{sub 2}O{sub 3} or MgO is nearly two times bigger than that between AL and nonmetal oxide such as SiO{sub 2} due to the electrostatic difference and cation-π interaction. When 83% hydroxyl groups of AL is blocked by acetylation, the adhesion forces between AL and Al{sub 2}O{sub 3}, MgO and SiO{sub 2} decrease 43, 35 and 75% respectively, which indicate hydrogen bonds play an important role between AL and inorganic oxides, especially in AL-silica system.

Improved lignin pyrolysis for phenolics production in a bubbling bed reactor--Effect of bed materials.

Science.gov (United States)

Li, Dongbing; Briens, Cedric; Berruti, Franco

2015-01-01

Lignin pyrolysis was studied in a bubbling fluidized bed reactor equipped with a fractional condensation train, using nitrogen as the fluidization gas. The effect of different bed materials (silica sand, lignin char, activated lignin char, birch bark char, and foamed glass beads) on bio-oil yield and quality was investigated for a pyrolysis temperature of 550 °C. Results how that a bed of activated lignin char is preferable to the commonly used silica sand: pyrolysis of Kraft lignin with a bed of activated lignin char not only provides a pure char product, but also a higher dry bio-oil yield (with a relative increase of 43%), lower pyrolytic water production, and better bio-oil quality. The bio-oil obtained from Kraft lignin pyrolysis with a bed of activated lignin char has a lower average molecular weight, less tar, more phenolics, and less acidity than when sand is used as bed material. Copyright © 2015 Elsevier Ltd. All rights reserved.

Connecting tropical river DOM and POM to the landscape with lignin

Science.gov (United States)

Hernes, Peter J.; Dyda, Rachael Y.; McDowell, William H.

2017-12-01

Tropical rivers account for two thirds of global fluxes of terrigenous organic matter to the oceans, yet because of their remote locations relative to most industrialized countries, they are poorly studied compared to temperate and even Arctic rivers. Further, most tropical river research has focused on large rivers like the Amazon or Congo, yet more than half of organic matter fluxes from tropical rivers comes from much smaller rivers. This study focuses on two such rivers in the Luquillo Experimental Forest of Puerto Rico, namely the Rio Mameyes and Rio Icacos, and uses time-series measurements of lignin biomarkers to put them in context with much bigger tropical rivers in the literature. Although lignin concentrations and carbon-normalized yields offer some distinction between mountainous vs. floodplain tropical river reaches, compositional differences appear to offer greater potential, including S:V vs. C:V plots that may capture the poorly-studied influence of palm trees, and (Ad:Al)s vs. (Ad:Al)v plots that may reflect differences in underlying mineralogy and degradation in soils. Even though dissolved and particulate lignin ultimately come from the same vegetation sources, comparison of dissolved and particulate lignin parameters within the two Puerto Rican rivers indicate that the pathways by which they end up in the same parcel of river water are largely decoupled. Across several particulate lignin studies in tropical rivers, mineral composition and concentration appears to exert a strong control on particulate lignin compositions and concentrations. Finally, the time-series nature of this study allows for new ways of analyzing dissolved lignin endmember compositions and degradation within the catchment. Plots of dissolved lignin parameters vs. lignin concentration reveal both the composition of "fresh" DOM that is likely mobilized from organic-rich soil surface layers along with the extent and trajectory of degradation of that signature that is possible

Analysis of Structural Units and Their Influence on Thermal Degradation of Alkali Lignins

Directory of Open Access Journals (Sweden)

Wen Hua

2016-01-01

Full Text Available The chemical structures of four alkali lignins isolated from poplar, fir, straw, and bagasse were investigated. To explore the relationship between the structural units and the thermal decomposition behavior, the system was tested by elemental analysis, Fourier transform infrared spectrometry, thermogravimetric analysis (TGA, and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS. The results indicated that the carbon content of poplar lignin (PL was higher than that of others. Fir lignin (FL exhibited the highest guaiacol units, while the other three lignins were abundant in syringol units. The thermal decomposition characteristics and pyrolysis products of the four lignins were influenced by the material structural and composition. The DTG curves showed that the initial temperatures and major degradation temperatures of woody lignins（FL and PL） with complex inherent structures were shifted to the high temperature zoom compared with that of non-woody （BL and SL）lignins. Py-GC/MS analysis showed that guaiacol-type phenolic compounds were predominant pyrolysis products derived from the four lignins. The yield of guaiacol-type phenols could reach 82.87%. Moreover, the BL had selectively on phenol-type compounds with yield of 27.89%.

Removal of oil palm trunk lignin in ammonium hydroxide pretreatment

Science.gov (United States)

Az-Zahraa, Balqis; Zakaria, Sarani; Daud, Muhammad F. B.; Jaafar, Sharifah Nabihah Syed

2018-04-01

Alkaline pretreatment using ammonium hydroxide, NH4OH serves as one of a process to remove lignin from lignocellulosic biomass such as oil palm trunk fiber. In this study, the effect of NH4OH pretreatment on removal of oil palm trunk lignin was investigated. The oil palm trunk fiber was dissolved in NH4OH with different concentrations (6, 8 and 10 %), different duration (3, 5 and 7 h) and temperatures (60, 80 and 100 °C). The samples were analyzed by using UV-Vis to estimate the concentration of extracted lignin. The result indicates that the optimum conditions to gain maximum extracted lignin were 8% NH4OH, 100 °C and 5 h with concentration of 64 mgL-1 while the lowest was at 6% NH4OH, 100 °C and 5 h with concentration of 62.5 mgL-1.

Structural variations and physical properties of lignin coke

International Nuclear Information System (INIS)

Otani, C.

1986-01-01

The studied lignin is a by-product of the process of ethanol production from eucaliptus. It was heat-treated under inert atmosphere conditions at increasing temperatures from 300 0 C up to 2600 0 C. This material has about 35 weight % of carbon yield and low ash content (0.70 w %). The structural variations were studied by wide-angle X-ray diffraction, small-angle X-ray scattering and infra-red spectroscopy. The bulk and the ''real'' density of the samples have also been determined as a function of the heat treatment temperatures. These experimental results enabled us to establish a mechanism of structure variation based on the formation of a graphite-like and porous structure within the initially amorphous lignin matrix. It has been possible to specify the adequate heat treatment temperature based upon the lignin coke applications. (author) [pt

Reactivity of lignin and problems of its oxidative destruction with peroxy reagents

International Nuclear Information System (INIS)

Demin, Valerii A; Shereshovets, Valerii V; Monakov, Yurii B

1999-01-01

Published data on reactivity and oxidation of lignin and model compounds with hydrogen peroxide, ozone and chlorine dioxide as well as on oxidative destruction of the sulfate pulp lignin with various reagents during bleaching are systematised and generalised. Concepts of lignin activation towards its selective oxidation and kinetic features of sulfate pulp oxidative delignification are considered. The bibliography includes 157 references.

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)...

Catalytic constructive deoxygenation of lignin-derived phenols: new C-C bond formation processes from imidazole-sulfonates and ether cleavage reactions.

Science.gov (United States)

Leckie, Stuart M; Harkness, Gavin J; Clarke, Matthew L

2014-10-09

As part of a programme aimed at exploiting lignin as a chemical feedstock for less oxygenated fine chemicals, several catalytic C-C bond forming reactions utilising guaiacol imidazole sulfonate are demonstrated. These include the cross-coupling of a Grignard, a non-toxic cyanide source, a benzoxazole, and nitromethane. A modified Meyers reaction is used to accomplish a second constructive deoxygenation on a benzoxazole functionalised anisole.

Lignin properties in topsoils of a beech/oak forest after 8 years of manipulated litter fall: relevance of altered input and oxidation of lignin

NARCIS (Netherlands)

Klotzbücher, T.; Strohmeier, S.; Kaiser, K.; Bowden, R.D.; Lajtha, K.; Ohm, H.; Kalbitz, K.

2013-01-01

Background and aims We studied the response of lignin oxidation in soils of a beech/oak forest to changes in litter fall. Additionally we considered possible factors in lignin oxidation, including altered (i) input of fresh organic matter and (ii) fungi-to-bacteria ratios. Methods The field-based

Influence of alkaline hydrothermal pretreatment on shrub wood Tamarix ramosissima: Characteristics of degraded lignin

International Nuclear Information System (INIS)

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

2014-01-01

The objective of this work was to evaluate the influence of alkaline hydrothermal (AH) pretreatment on the physicochemical properties of the degraded lignins, attempt to upgrade the potential of lignin for value-added chemicals and fuel production. For this purpose, shrub wood Tamarix ramosissima lignin was fractionated using a two-stage process based on an AH pretreatment followed by an alkaline ethanol post-treatment. The recovered lignin fractions were investigated by comparison with milled wood lignin (MWL) in terms of fractionation yield, carbohydrate composition, gel permeation chromatography, Fourier transform infrared spectroscopy, 13 C and 2D heteronuclear single quantum correlation nuclear magnetic resonance, as well as pyrolysis-gas chromatography/mass spectrometry. The result showed that AH pretreatment led to the degradation of β-O-4 linkages and consequently the increased severity caused a release of more S-units lignin fractions with molecular weights between 1300 and 2500 g/mol in the liquid but higher molecular weights (3000–4400 g/mol) in the residues. Moreover, it was found that the lignin syringyl-to-guaiacyl (S/G) ratios from analytical pyrolysis slightly changed after AH pretreatment (S/G, 1.8–2.3) but higher than those of MWL (S/G, 1.7). Overall, the present study demonstrates that these lignins dissolved during AH pretreatment and those recovered from the solid residues isolated with alkaline ethanol post-treatment could be profitably exploited as feedstock in integrated forest biorefineries, rather than traditional use as low-value energy sources.- Highlights: • Alkaline hydrothermal pretreatment and alkaline ethanol post-treatment were proposed. • The influence of AH pretreatment on the lignin structural changes was characterized. • Aryl-O-ether linkages of lignin were extensively cleaved. • Lignin recovered from solid residue is a potential resource for the production of value-added chemicals

Selective production of arenes via direct lignin upgrading over a niobium-based catalyst

Science.gov (United States)

Shao, Yi; Xia, Qineng; Dong, Lin; Liu, Xiaohui; Han, Xue; Parker, Stewart F.; Cheng, Yongqiang; Daemen, Luke L.; Ramirez-Cuesta, Anibal J.; Yang, Sihai; Wang, Yanqin

2017-07-01

Lignin is the only large-volume renewable source of aromatic chemicals. Efficient depolymerization and deoxygenation of lignin while retaining the aromatic functionality are attractive but extremely challenging. Here we report the selective production of arenes via direct hydrodeoxygenation of organosolv lignin over a porous Ru/Nb2O5 catalyst that enabled the complete removal of the oxygen content from lignin. The conversion of birch lignin to monomer C7-C9 hydrocarbons is nearly quantitative based on its monomer content, with a total mass yield of 35.5 wt% and an exceptional arene selectivity of 71 wt%. Inelastic neutron scattering and DFT calculations confirm that the Nb2O5 support is catalytically unique compared with other traditional oxide supports, and the disassociation energy of Caromatic-OH bonds in phenolics is significantly reduced upon adsorption on Nb2O5, resulting in its distinct selectivity to arenes. This one-pot process provides a promising approach for improved lignin valorization with general applicability.

A process for producing lignin and volatile compounds from hydrolysis liquor.

Science.gov (United States)

Khazraie, Tooran; Zhang, Yiqian; Tarasov, Dmitry; Gao, Weijue; Price, Jacquelyn; DeMartini, Nikolai; Hupa, Leena; Fatehi, Pedram

2017-01-01

Hot water hydrolysis process is commercially applied for treating wood chips prior to pulping or wood pellet production, while it produces hydrolysis liquor as a by-product. Since the hydrolysis liquor is dilute, the production of value-added materials from it would be challenging. In this study, acidification was proposed as a viable method to extract (1) furfural and acetic acid from hot water hydrolysis liquor and (2) lignin compounds from the liquor. The thermal properties of the precipitates made from the acidification of hydrolysis liquor confirmed the volatile characteristics of precipitates. Membrane dialysis was effective in removing inorganic salts associated with lignin compounds. The purified lignin compounds had a glass transition temperature (Tg) of 180-190 °C, and were thermally stable. The results confirmed that lignin compounds present in hot water hydrolysis liquor had different characteristics. The acidification of hydrolysis liquor primarily removed the volatile compounds from hydrolysis liquor. Based on these results, a process for producing purified lignin and precipitates of volatile compounds was proposed.

Purification and characterization of lignin peroxidases from Penicillium decumbens P6

Energy Technology Data Exchange (ETDEWEB)

Yang, J.S.; Yuan, H.L.; Wang, H.X.; Chen, W.X. [China Agricultural University, Beijing (China). College of Biological Science

2005-06-01

Peroxidases are essential enzymes in biodegradation of lignin and lignite which have been investigated intensively in the white-rot fungi. This is the first report of purification and characterization of lignin peroxidase from Penicillium sp. P6 as lignite degradation fungus. The results indicated that the lignin peroxidase of Penicillium decumbens P6 had physical and chemical properties and a N-terminal amino acid sequence different from the lignin peroxidases of white-rot fungi. The lignin peroxidase was isolated from a liquid culture of P. decumbens P6. This enzyme had a molecular weight of 46.3 KDa in SDS-PAGE and exhibited greater activity, temperature stability and wider pH range than those previously reported. The isolation procedure involved (NH{sub 4}){sub 2}SO{sub 4} precipitation, ion-exchange chromatography on DEAE-cellulose and CM-cellulose, gel filtration on Sephadex G-100, and non-denaturing, discontinuous polyacrylamide gel electrophoresis. The K{sub m} and V{sub max} values of this enzyme using veratryl alcohol as substrate were 0.565 mmol L{sup -1} and 0.088 mmol (mg protein){sup -1} min{sup -1} respectively. The optimum pH of P6 lignin peroxidase was 4.0, and 70.6% of the relative activity was remained at pH 9.0. The optimum temperature of the enzyme was 45{sup o}C.

Kraft lignin chain extension chemistry via propargylation, oxidative coupling, and Claisen rearrangement.

Science.gov (United States)

Sen, Sanghamitra; Sadeghifar, Hasan; Argyropoulos, Dimitris S

2013-10-14

Despite its aromatic and polymeric nature, the heterogeneous, stochastic, and reactive characteristics of softwood kraft lignin seriously limit its potential for thermoplastic applications. Our continuing efforts toward creating thermoplastic lignin polymers are now focused at exploring propargylation derivatization chemistry and its potential as a versatile novel route for the eventual utilization of technical lignins with a significant amount of molecular control. To do this, we initially report the systematic propargylation of softwood kraft lignin. The synthesized derivatives were extensively characterized with thermal methods (DSC, TGA), (1)H, (13)C, and quantitative (31)P NMR and IR spectroscopies. Further on, we explore the versatile nature of the lignin pendant propargyl groups by demonstrating two distinct chain extension chemistries; the solution-based, copper-mediated, oxidative coupling and the thermally induced, solid-state, Claissen rearrangement polymerization chemistries. Overall, we show that it is possible to modulate the reactivity of softwood kraft lignin via a combination of methylation and chain extension providing a rational means for the creation of higher molecular weight polymers with the potential for thermoplastic materials and carbon fibers with the desired control of structure-property relations.

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.

Catalytic Reforming of Lignin-Derived Bio-Oil Over a Nanoporous Molecular Sieve Silicoaluminophosphate-11.

Science.gov (United States)

Park, Y K; Kang, Hyeon Koo; Jang, Hansaem; Suh, Dong Jin; Park, Sung Hoon

2016-05-01

Catalytic pyrolysis of lignin, a major constituent of biomass, was performed. A nanoporous molecular sieve silicoaluminophosphate-11 (SAPO-11) was selected as catalyst. Thermogravimetric analysis showed that 500 degrees C was the optimal pyrolysis temperature. Pyrolyzer-gas chromatography/mass spectroscopy was used to investigate the pyrolysis product distribution. Production of phenolics, the dominant product from the pyrolysis of lignin, was promoted by the increase in the catalyst dose. In particular, low-molecular-mass phenolics were produced more over SAPO-11, while high-molecular-mass phenolics and double-bond-containing phenolics were produced less. The fraction of aromatic compounds, including benzene, toluene, xylene, and ethylbenzene, was also increased by catalytic reforming. The catalytic effects were more pronounced when the catalyst/biomass ratio was increased. The enhanced production of aromatic compounds by an acidic catalyst obtained in this study is in good agreement with the results of previous studies.

The investigation of wood hydrolysis lignin ability for uranium sorption

International Nuclear Information System (INIS)

Rachkova, N.G.; Shuktomova, I.I.; Taskaev, A.I.

2001-01-01

The uranium are sorbed in wood hydrolysis lignin efficacious and very strong both in uranyl nitrate solutions and in podsolic soil. It may well be that formation of complexes are possible mechanism of irreversible sorption. The static capacity of lignin are 2.7 mg/g. (author)

Lignin decomposition is sustained under fluctuating redox conditions in humid tropical forest soils

Science.gov (United States)

Steven J. Hall; Whendee L. Silver; Vitaliy I. Timokhin; Kenneth E. Hammel

2015-01-01

Lignin mineralization represents a critical flux in the terrestrial carbon (C) cycle, yet little is known about mechanisms and environmental factors controlling lignin breakdown in mineral soils. Hypoxia is thought to suppress lignin decomposition, yet potential effects of oxygen (O2) variability in surface soils have not been explored. Here, we...

Genes encoding enzymes of the lignin biosynthesis pathway in Eucalyptus

Directory of Open Access Journals (Sweden)

Ricardo Harakava

2005-01-01

Full Text Available Eucalyptus ESTs libraries were screened for genes involved in lignin biosynthesis. This search was performed under the perspective of recent revisions on the monolignols biosynthetic pathway. Eucalyptus orthologues of all genes of the phenylpropanoid pathway leading to lignin biosynthesis reported in other plant species were identified. A library made with mRNAs extracted from wood was enriched for genes involved in lignin biosynthesis and allowed to infer the isoforms of each gene family that play a major role in wood lignin formation. Analysis of the wood library suggests that, besides the enzymes of the phenylpropanoids pathway, chitinases, laccases, and dirigent proteins are also important for lignification. Colocalization of several enzymes on the endoplasmic reticulum membrane, as predicted by amino acid sequence analysis, supports the existence of metabolic channeling in the phenylpropanoid pathway. This study establishes a framework for future investigations on gene expression level, protein expression and enzymatic assays, sequence polymorphisms, and genetic engineering.

Porous core-shell carbon fibers derived from lignin and cellulose nanofibrils

KAUST Repository

Xu, Xuezhu

2013-10-01

This letter reports a method to produce lignin and cellulose nanofibrils (CNFs) based porous core-shell carbon fibers via co-electrospinning followed by controlled carbonization. Lignin formed the shell of the fiber while CNF network formed the porous core. Polyacrylonitrile (PAN) was added to the lignin solution to increase its electrospinability. CNFs were surface acetylated and dispersed in silicon oil to obtain a homogenous dispersion for electrospinning the porous core. Hollow lignin fibers were also electrospun using glycerin as the core material. FT-IR measurements confirmed the CNF acetylation. SEM micrographs showed the core-shell and hollow fiber nanostructures before and after carbonization. The novel carbon fibers synthesized in this study exhibited increased surface area and porosity that are promising for many advanced applications. © 2013 Elsevier B.V.

Porous core-shell carbon fibers derived from lignin and cellulose nanofibrils

KAUST Repository

Xu, Xuezhu; Zhou, Jian; Jiang, Long; Lubineau, Gilles; Chen, Ye; Wu, Xiangfa; Piere, Robert

2013-01-01

This letter reports a method to produce lignin and cellulose nanofibrils (CNFs) based porous core-shell carbon fibers via co-electrospinning followed by controlled carbonization. Lignin formed the shell of the fiber while CNF network formed the porous core. Polyacrylonitrile (PAN) was added to the lignin solution to increase its electrospinability. CNFs were surface acetylated and dispersed in silicon oil to obtain a homogenous dispersion for electrospinning the porous core. Hollow lignin fibers were also electrospun using glycerin as the core material. FT-IR measurements confirmed the CNF acetylation. SEM micrographs showed the core-shell and hollow fiber nanostructures before and after carbonization. The novel carbon fibers synthesized in this study exhibited increased surface area and porosity that are promising for many advanced applications. © 2013 Elsevier B.V.

Evidence supporting dissimilatory and assimilatory lignin degradation in Enterobacter lignolyticus SCF1

Energy Technology Data Exchange (ETDEWEB)

DeAngelis, Kristen M.; Sharma, Deepak; Varney, Rebecca; Simmons, Blake A.; Isern, Nancy G.; Markillie, Lye Meng; Nicora, Carrie D.; Norbeck, Angela D.; Taylor, Ronald C.; Aldrich, Joshua T.; Robinson, Errol W.

2013-08-29

The anaerobic isolate Enterobacter lignolyticus SCF1 was initially cultivated based on anaerobic growth on lignin as sole carbon source. The source of the isolated bacteria was from tropical forest soils that decompose litter rapidly with low and fluctuating redox potentials, making it likely that bacteria using oxygen-independent enzymes play an important role in decomposition. We have examined differential expression of the anaerobic isolate Enterobacter lignolyticus SCF1 during growth on lignin. After 48 hours of growth, we used transcriptomics and proteomics to define the enzymes and other regulatory machinery that these organisms use to degrade lignin, as well as metabolomics to measure lignin degradation and monitor the use of lignin and iron as terminal electron acceptors that facilitate more efficient use of carbon. Proteomics revealed accelerated xylose uptake and metabolism under lignin-amended growth, and lignin degradation via the 4-hydroxyphenylacetate degradation pathway, catalase/peroxidase enzymes, and the glutathione biosynthesis and glutathione S-transferase proteins. We also observed increased production of NADH-quinone oxidoreductase, other electron transport chain proteins, and ATP synthase and ATP-binding cassette (ABC) transporters. Our data shows the advantages of a multi-omics approach, where incomplete pathways identified by genomics were completed, and new observations made on coping with poor carbon availability. The fast growth, high efficiency and specificity of enzymes employed in bacterial anaerobic litter deconstruction makes these soils useful templates for improving biofuel production.

Preparation of Silk Sericin/Lignin Blend Beads for the Removal of Hexavalent Chromium Ions

Science.gov (United States)

Kwak, Hyo Won; Shin, Munju; Yun, Haesung; Lee, Ki Hoon

2016-01-01

In the present study, novel adsorbents having high adsorption capability and reusability were prepared using agricultural by-products: silk sericin and lignin. Silk sericin and lignin blend beads were successfully prepared using simple coagulation methods for the removal of hexavalent chromium (Cr(VI)) from aqueous solution. A 1 M lithium chloride (LiCl)/dimethyl sulfoxide (DMSO) solvent system successfully dissolved both sericin and lignin and had sufficient viscosity for bead preparation. Compared to the conventional sericin bead adsorbent, sericin/lignin blend beads showed higher Cr(VI) adsorption capacity. The amount of lignin added to the adsorbent greatly affected the adsorption capacity of the beads, and a 50:50 sericin/lignin blend ratio was optimal. Adsorption behavior followed the Freundlich isotherm, which means the adsorption of Cr(VI) occurred on the heterogeneous surface. Cr(VI) adsorption capability increased with temperature because of thermodynamic-kinetic effects. In addition, over 90% of Cr(VI) ions were recovered from the Cr(VI) adsorbed sericin/lignin beads in a 1 M NaOH solution. The adsorption-desorption recycling process was stable for more than seven cycles, and the recycling efficiency was 82%. It is expected that the sericin/lignin beads could be successfully applied in wastewater remediation especially for hazardous Cr(VI) ions in industrial wastewater. PMID:27598142

Preparation of Silk Sericin/Lignin Blend Beads for the Removal of Hexavalent Chromium Ions

Directory of Open Access Journals (Sweden)

Hyo Won Kwak

2016-09-01

Full Text Available In the present study, novel adsorbents having high adsorption capability and reusability were prepared using agricultural by-products: silk sericin and lignin. Silk sericin and lignin blend beads were successfully prepared using simple coagulation methods for the removal of hexavalent chromium (Cr(VI from aqueous solution. A 1 M lithium chloride (LiCl/dimethyl sulfoxide (DMSO solvent system successfully dissolved both sericin and lignin and had sufficient viscosity for bead preparation. Compared to the conventional sericin bead adsorbent, sericin/lignin blend beads showed higher Cr(VI adsorption capacity. The amount of lignin added to the adsorbent greatly affected the adsorption capacity of the beads, and a 50:50 sericin/lignin blend ratio was optimal. Adsorption behavior followed the Freundlich isotherm, which means the adsorption of Cr(VI occurred on the heterogeneous surface. Cr(VI adsorption capability increased with temperature because of thermodynamic-kinetic effects. In addition, over 90% of Cr(VI ions were recovered from the Cr(VI adsorbed sericin/lignin beads in a 1 M NaOH solution. The adsorption-desorption recycling process was stable for more than seven cycles, and the recycling efficiency was 82%. It is expected that the sericin/lignin beads could be successfully applied in wastewater remediation especially for hazardous Cr(VI ions in industrial wastewater.

Comparative studies on anthraquinone retention following the soda/anthraquinone process using 14C-labelled anthraquinone, and mode of action of anthraquinone on lignins and lignin model components

International Nuclear Information System (INIS)

Pfuetze, E.

1982-01-01

This dissertation contributes to the clarification of the following questions: how much of the additive is retained in cellulose following soda/anthraquinone-wood pulping; how much anthraquinone can be detected after extraction studies and after a conventional CEHD-bleaching treatment; can differences be detected between soda lignins and soda/anthraquinone lignins with respect to analytical data, spectroscopie characteristics and macromolecular properties; and how do dimeric lignin models with #betta#-arylether structure behave in decomposition studies using the soda/anthraquinone process. (orig./MG) [de

Anti-HCV effect of Lentinula edodes mycelia solid culture extracts and low-molecular-weight lignin.

Science.gov (United States)

Matsuhisa, Koji; Yamane, Seiji; Okamoto, Toru; Watari, Akihiro; Kondoh, Masuo; Matsuura, Yoshiharu; Yagi, Kiyohito

2015-06-19

Lentinula edodes mycelia solid culture extract (MSCE) contains several bioactive molecules, including some polyphenolic compounds, which exert immunomodulatory, antitumor, and hepatoprotective effects. In this study, we examined the anti-hepatitis C virus (HCV) activity of MSCE and low-molecular-weight lignin (LM-lignin), which is the active component responsible for the hepatoprotective effect of MSCE. Both MSCE and LM-lignin inhibited the entry of two HCV pseudovirus (HCVpv) types into Huh7.5.1 cells. LM-lignin inhibited HCVpv entry at a lower concentration than MSCE and inhibited the entry of HCV particles in cell culture (HCVcc). MSCE also inhibited HCV subgenome replication. LM-lignin had no effect on HCV replication, suggesting that MSCE contains additional active substances. We demonstrate here for the first time the anti-HCV effects of plant-derived LM-lignin and MSCE. The hepatoprotective effect of LM-lignin suggests that lignin derivatives, which can be produced in abundance from existing plant resources, may be effective in the treatment of HCV-related diseases. Copyright © 2015 Elsevier Inc. All rights reserved.

Selective lignin downregulation leads to constitutive defense response expression in alfalfa (Medicago sativa L.).

Science.gov (United States)

Gallego-Giraldo, Lina; Jikumaru, Yusuke; Kamiya, Yuji; Tang, Yuhong; Dixon, Richard A

2011-05-01

• Downregulation of hydroxycinnamoyl CoA: shikimate hydroxycinnamoyl transferase (HCT) in alfalfa (Medicago sativa) reduces lignin levels and improves forage quality and saccharification efficiency for bioethanol production. However, the plants have reduced stature. It was previously reported that HCT-down-regulated Arabidopsis have impaired auxin transport, but this has recently been disproved. • To address the basis for the phenotypes of lignin-modified alfalfa, we measured auxin transport, profiled a range of metabolites including flavonoids and hormones, and performed in depth transcriptome analyses. • Auxin transport is unaffected in HCT antisense alfalfa despite increased flavonoid biosynthesis. The plants show increased cytokinin and reduced auxin levels, and gibberellin levels and sensitivity are both reduced. Levels of salicylic, jasmonic and abscisic acids are elevated, associated with massive upregulation of pathogenesis and abiotic stress-related genes and enhanced tolerance to fungal infection and drought. • We suggest that HCT downregulated alfalfa plants exhibit constitutive activation of defense responses, triggered by release of bioactive cell wall fragments and production of hydrogen peroxide as a result of impaired secondary cell wall integrity. © 2011 The Authors. New Phytologist © 2011 New Phytologist Trust.

Thermochemical properties of cellulose acetate blends with acetosolv and sawdust lignin: A comparative study.

Science.gov (United States)

Peredo, Karol; Escobar, Danilo; Vega-Lara, Johana; Berg, Alex; Pereira, Miguel

2016-02-01

Sawdust (SD) and cotton-lignin blends (CLB) were acetylated and the effect of lignin type and content on thermoplastic properties of the acetate produced was studied. The lignin in samples did not significantly affect the degree of acetylation. An increase in acetyl groups of 1-3% was observed in acetylated SD (ASD) unlike acetylated CLB (ACLB). Thermogravimetric analysis showed two thermal degradation zones; one at 190-200°C and the other at 330-370°C. The early degradation in ASD corresponds to galactoglucomannans while that in ACLB corresponds to the low-molecular-weight lignin. The second degradation is due to decomposition of cellulose acetate and high-molecular-weight lignin. DSC analysis showed homogeneous behaviour in ASD with only one glass transition temperature (Tg) at 170-180°C, unlike ACLB that showed two Tgs at 170-180°C. Sawdust acetylation, taking advantage of its residual lignin, showed higher reactivity and miscibility as compared to the same material produced by adding previously extracted lignin on cotton. Copyright © 2015 Elsevier B.V. All rights reserved.

Inhibition of lignin-derived phenolic compounds to cellulase.

Science.gov (United States)

Qin, Lei; Li, Wen-Chao; Liu, Li; Zhu, Jia-Qing; Li, Xia; Li, Bing-Zhi; Yuan, Ying-Jin

2016-01-01

Lignin-derived phenolic compounds are universal in the hydrolysate of pretreated lignocellulosic biomass. The phenolics reduce the efficiency of enzymatic hydrolysis and increase the cost of ethanol production. We investigated inhibition of phenolics on cellulase during enzymatic hydrolysis using vanillin as one of the typical lignin-derived phenolics and Avicel as cellulose substrate. As vanillin concentration increased from 0 to 10 mg/mL, cellulose conversion after 72-h enzymatic hydrolysis decreased from 53 to 26 %. Enzyme deactivation and precipitation were detected with the vanillin addition. The enzyme concentration and activity consecutively decreased during hydrolysis, but the inhibition degree, expressed as the ratio of the cellulose conversion without vanillin to the conversion with vanillin (A 0 /A), was almost independent on hydrolysis time. Inhibition can be mitigated by increasing cellulose loading or cellulase concentration. The inhibition degree showed linear relationship with the vanillin concentration and exponential relationship with the cellulose loading and the cellulase concentration. The addition of calcium chloride, BSA, and Tween 80 did not release the inhibition of vanillin significantly. pH and temperature for hydrolysis also showed no significant impact on inhibition degree. The presence of hydroxyl group, carbonyl group, and methoxy group in phenolics affected the inhibition degree. Besides phenolics concentration, other factors such as cellulose loading, enzyme concentration, and phenolic structure also affect the inhibition of cellulose conversion. Lignin-blocking agents have little effect on the inhibition effect of soluble phenolics, indicating that the inhibition mechanism of phenolics to enzyme is likely different from insoluble lignin. The inhibition of soluble phenolics can hardly be entirely removed by increasing enzyme concentration or adding blocking proteins due to the dispersity and multiple binding sites of phenolics

The impact of alterations in lignin deposition on cellulose organization of the plant cell wall

Energy Technology Data Exchange (ETDEWEB)

Liu, Jiliang; Kim, Jeong Im; Cusumano, Joanne C.; Chapple, Clint; 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

Acid-catalysed xylose dehydration into furfural in the presence of kraft lignin.

Science.gov (United States)

Lamminpää, Kaisa; Ahola, Juha; Tanskanen, Juha

2015-02-01

In this study, the effects of kraft lignin (Indulin AT) on acid-catalysed xylose dehydration into furfural were studied in formic and sulphuric acids. The study was done using D-optimal design. Three variables in both acids were included in the design: time (20-80 min), temperature (160-180°C) and initial lignin concentration (0-20 g/l). The dependent variables were xylose conversion, furfural yield, furfural selectivity and pH change. The results showed that the xylose conversion and furfural yield decreased in sulphuric acid, while in formic acid the changes were minor. Additionally, it was showed that lignin has an acid-neutralising capacity, and the added lignin increased the pH of reactant solutions in both acids. The pH rise was considerably lower in formic acid than in sulphuric acid. However, the higher pH did not explain all the changes in conversion and yield, and thus lignin evidently inhibits the formation of furfural. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sugarcane expressed sequences tags (ESTs encoding enzymes involved in lignin biosynthesis pathways

Directory of Open Access Journals (Sweden)

Ramos Rose Lucia Braz

2001-01-01

Full Text Available Lignins are phenolic polymers found in the secondary wall of plant conductive systems where they play an important role by reducing the permeability of the cell wall to water. Lignins are also responsible for the rigidity of the cell wall and are involved in mechanisms of resistance to pathogens. The metabolic routes and enzymes involved in synthesis of lignins have been largely characterized and representative genes that encode enzymes involved in these processes have been cloned from several plant species. The synthesis of lignins is liked to the general metabolism of the phenylpropanoids in plants, having enzymes (e.g. phenylalanine ammonia-lyase (PAL, cinnamate 4-hydroxylase (C4H and caffeic acid O-methyltransferase (COMT common to other processes as well as specific enzymes such as cinnamoyl-CoA reductase (CCR and cinnamyl alcohol dehydrogenase (CAD. Some maize and sorghum mutants, shown to have defective in CAD and/or COMT activity, are easier to digest because they have a reduced lignin content, something which has motivated different research groups to alter the lignin content and composition of model plants by genetic engineering try to improve, for example, the efficiency of paper pulping and digestibility. In the work reported in this paper, we have made an inventory of the sugarcane expressed sequence tag (EST coding for enzymes involved in lignin metabolism which are present in the sugarcane EST genome project (SUCEST database. Our analysis focused on the key enzymes ferulate-5-hydroxylase (F5H, caffeic acid O-methyltransferase (COMT, caffeoyl CoA O-methyltransferase (CCoAOMT, hydroxycinnamate CoA ligase (4CL, cinnamoyl-CoA reductase (CCR and cinnamyl alcohol dehydrogenase (CAD. The comparative analysis of these genes with those described in other species could be used as molecular markers for breeding as well as for the manipulation of lignin metabolism in sugarcane.

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

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 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

Imidazolium-Based Ionic Liquids as Efficient Reagents for the C-O Bond Cleavage of Lignin.

Science.gov (United States)

Thierry, Marina; Majira, Amel; Pégot, Bruce; Cezard, Laurent; Bourdreux, Flavien; Clément, Gilles; Perreau, François; Boutet-Mercey, Stéphanie; Diter, Patrick; Vo-Thanh, Giang; Lapierre, Catherine; Ducrot, Paul-Henri; Magnier, Emmanuel; Baumberger, Stéphanie; Cottyn, Betty

2018-01-23

The demethylation of lignin in ionic liquids (ILs) was investigated by using pure lignin model monomers and dimers together with dioxane-isolated lignins from poplar, miscanthus, and maize. Different methylimidazolium ILs were compared and the samples were treated with two different heating processes: microwave irradiation and conventional heating in a sealed tube. The conversion yield and influence of the treatment on the lignin structure were assessed by 31 P NMR spectroscopy, size-exclusion chromatography, and thioacidolysis. The acidic methylimidazolium IL [HMIM]Br was shown to be an effective combination of solvent and reagent for the demethylation and depolymerization of lignin. The relatively mild reaction conditions, the clean work-up, and the ability to reuse the IL makes the described procedure an attractive and new green method for the conversion of lignin to produce phenol-rich lignin oligomers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lignin phenols used to infer organic matter sources to Sepetiba Bay - RJ, Brasil

Science.gov (United States)

Rezende, C. E.; Pfeiffer, W. C.; Martinelli, L. A.; Tsamakis, E.; Hedges, J. I.; Keil, R. G.

2010-04-01

Lignin phenols were measured in the sediments of Sepitiba Bay, Rio de Janeiro, Brazil and in bedload sediments and suspended sediments of the four major fluvial inputs to the bay; São Francisco and Guandu Channels and the Guarda and Cação Rivers. Fluvial suspended lignin yields (Σ8 3.5-14.6 mgC 10 g dw -1) vary little between the wet and dry seasons and are poorly correlated with fluvial chlorophyll concentrations (0.8-50.2 μgC L -1). Despite current land use practices that favor grassland agriculture or industrial uses, fluvial lignin compositions are dominated by a degraded leaf-sourced material. The exception is the Guarda River, which has a slight influence from grasses. The Lignin Phenol Vegetation Index, coupled with acid/aldehyde and 3.5 Db/V ratios, indicate that degraded leaf-derived phenols are also the primary preserved lignin component in the bay. The presence of fringe Typha sp. and Spartina sp. grass beds surrounding portions of the Bay are not reflected in the lignin signature. Instead, lignin entering the bay appears to reflect the erosion of soils containing a degraded signature from the former Atlantic rain forest that once dominated the watershed, instead of containing a significant signature derived from current agricultural uses. A three-component mixing model using the LPVI, atomic N:C ratios, and stable carbon isotopes (which range between -26.8 and -21.8‰) supports the hypothesis that fluvial inputs to the bay are dominated by planktonic matter (78% of the input), with lignin dominated by leaf (14% of the input) over grass (6%). Sediments are composed of a roughly 50-50 mixture of autochthonous material and terrigenous material, with lignin being primarily sourced from leaf.

Drivers of lignin composition in boreal forest organic soils across a climate gradient

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Myers-Pigg, A.; Kaiser, K.; Benner, R. H.; Ziegler, S. E.

2017-12-01

Lignin diagenesis in soils, including the cumulative effects of degradation and leaching, increases with experimental warming, signifying a potentially important change relevant to soil organic matter accumulation and fate. However, decadal to centennial climatic effects including changes in precipitation, litterfall inputs, and understory sources, on lignin composition are poorly constrained. We examined the lignin content and composition, via cupric oxide oxidation (CuO), within the organic layers of podzolic soils under similar balsam fir forests across a latitudinal climate gradient in Atlantic Canada. By exploring variation in lignin by both soil depth and climate region, this study informs on the climate drivers of lignin stability within boreal forest soil. A two-way analysis of variance (ANOVA) revealed significant variations in common signatures of CuO by-products with depth and/or site, indicating source and/or diagenetic controllers. Importantly, none of these signatures, with the exception of p-hydroxyphenols, exhibited a site by depth interaction indicating a similar degree of diagenetic alternation with depth across climates. The site by depth interaction for p-hydroxyphenols is a result of greater moss input in the northernmost site. To better elucidate this climate-induced source variation on our interpretation of lignin diagenesis, a principle component (PCA) model was built using signatures varying by site (pforest soils. A lignin diagenesis PCA model was built using (1) all non-moss related signatures identified in the first PCA model, and (2) scores for additional sites within each region, calculated from modeled lignin composition based on 13C-NMR spectra. The combined results indicate that the lignin diagenetic states among soils is similar, despite the large increase in soil C turnover with climate warming across this transect. Thus our results indicate that shifts in moss contribution, and not increased diagenesis, controls CuO by

INVESTIGATION OF AQUEOUS BIPHASIC SYSTEMS FOR THE SEPARATIONS OF LIGNINS FROM CELLULOSE IN THE PAPER PULPING PROCESS. (R826732)

Science.gov (United States)

In efforts to apply a polymer-based aqueous biphasic system (ABS) extraction to the paper pulping process, the study of the distribution of various lignin and cellulosic fractions in ABS and the effects of temperature on system composition and solute partitioning have been inv...

Lignin-Based Materials Through Thiol-Maleimide "Click" Polymerization.

Science.gov (United States)

Buono, Pietro; Duval, Antoine; Averous, Luc; Habibi, Youssef

2017-03-09

In the present report an environmentally friendly approach to transforming renewable feedstocks into value-added materials is proposed. This transformation pathway was conducted under green conditions, without the use of solvents or catalyst. First, controlled modification of lignin, a major biopolymer present in wood and plants, was achieved by esterification with 11-maleimidoundecylenic acid (11-MUA), a derivative from castor oil that contains maleimide groups, following its transformation into 11-maleimidoundecanoyl chloride (11-MUC). Different degrees of substitution were achieved by using various amounts of the 11-MUC, leading to an efficient conversion of lignin hydroxy groups, as demonstrated by 1 H and 31 P NMR analyses. These fully biobased maleimide-lignin derivatives were subjected to an extremely fast (ca. 1 min) thiol-ene "click" polymerization with thiol-containing linkers. Aliphatic and aromatic thiol linkers bearing two to four thiol groups were used to tune the reactivity and crosslink density. The properties of the resulting materials were evaluated by swelling tests and thermal and mechanical analyses, which showed that varying the degree of functionality of the linker and the linker structure allowed accurate tailoring of the thermal and mechanical properties of the final materials, thus providing interesting perspectives for lignin in functional aromatic polymers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biobased alkylphenols from lignins via a two-step pyrolysis - Hydrodeoxygenation approach

NARCIS (Netherlands)

de Wild, P. J.; Huijgen, W.J.J.; Kloekhorst, A.; Chowdari, R. K.; Heeres, H. J.

Five technical lignins (three organosolv, Kraft and soda lignin) were depolymerised to produce monomeric biobased aromatics, particularly alkylphenols, by a new two-stage thermochemical approach consisting of dedicated pyrolysis followed by catalytic hydrodeoxygenation (HDO) of the resulting

Structural characterization of guaiacyl-rich lignins in flax (Linum usitatissimum) fibers and shives.

Science.gov (United States)

del Río, José C; Rencoret, Jorge; Gutiérrez, Ana; Nieto, Lidia; Jiménez-Barbero, Jesús; Martínez, Ángel T

2011-10-26

The structural characteristics of the lignins from flax (Linum usitatissimum) fibers and shives were studied. Significant differences in the content and composition of the lignin from both parts were observed. The lignin contents were 3.8% in the fibers and 29.0% in the shives. Analysis by Py-GC/MS indicated a H:G:S molar ratio of 13:72:15 in the milled wood lignin (MWL) isolated from flax fibers and a molar ratio of 5:87:8 in the MWL isolated from flax shives. In addition, 2D-NMR showed a predominance of β-O-4' aryl ether linkages, followed by β-5' phenylcoumaran and β-β' resinol-type linkages in both MWLs, with a higher content of condensed linkages in flax shives. Thioacidolysis (followed by Raney nickel desulfurization) gave further information on the lignin units involved in the different linkages and confirmed the enrichment of G units. The thioacidolysis dimers released were similar from both lignins, with a predominance of the β-5' followed by β-1' and 5-5' structures.

From gene to biorefinery: microbial β-etherases as promising biocatalysts for lignin valorization

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Pere ePicart

2015-09-01

Full Text Available The set-up of biorefineries for the valorization of lignocellulosic biomass will be core in the future to reach sustainability targets. In this area, biomass-degrading enzymes are attracting significant research interest for their potential in the production of chemicals and biofuels from renewable feedstock. Gluthatione-dependent β-etherases are emerging enzymes for the biocatalytic depolymerization of lignin, a heterogeneous aromatic polymer abundant in Nature. They selectively catalyze the reductive cleavage of β-O-4 aryl-ether bonds which account for 45-60% of linkages present in lignin. Hence, application of β-etherases in lignin depolymerization would enable a specific lignin breakdown, selectively yielding (valuable low-molecular-mass aromatics. Albeit β-etherases have been biochemically known for decades, only very recently novel β-etherases have been identified and thoroughly characterized for lignin valorization, expanding the enzyme toolbox for efficient β-O-4 aryl-ether bond cleavage. Given their emerging importance and potential, this mini-review discusses recent developments in the field of β-etherase biocatalysis covering all aspects from enzyme identification to biocatalytic applications with real lignin samples.

From gene to biorefinery: microbial β-etherases as promising biocatalysts for lignin valorization.

Science.gov (United States)

Picart, Pere; de María, Pablo Domínguez; Schallmey, Anett

2015-01-01

The set-up of biorefineries for the valorization of lignocellulosic biomass will be core in the future to reach sustainability targets. In this area, biomass-degrading enzymes are attracting significant research interest for their potential in the production of chemicals and biofuels from renewable feedstock. Glutathione-dependent β-etherases are emerging enzymes for the biocatalytic depolymerization of lignin, a heterogeneous aromatic polymer abundant in nature. They selectively catalyze the reductive cleavage of β-O-4 aryl-ether bonds which account for 45-60% of linkages present in lignin. Hence, application of β-etherases in lignin depolymerization would enable a specific lignin breakdown, selectively yielding (valuable) low-molecular-mass aromatics. Albeit β-etherases have been biochemically known for decades, only very recently novel β-etherases have been identified and thoroughly characterized for lignin valorization, expanding the enzyme toolbox for efficient β-O-4 aryl-ether bond cleavage. Given their emerging importance and potential, this mini-review discusses recent developments in the field of β-etherase biocatalysis covering all aspects from enzyme identification to biocatalytic applications with real lignin samples.

Lignin valorization through integrated biological funneling and chemical catalysis

Science.gov (United States)

Linger, Jeffrey G.; Vardon, Derek R.; Guarnieri, Michael T.; Karp, Eric M.; Hunsinger, Glendon B.; Franden, Mary Ann; Johnson, Christopher W.; Chupka, Gina; Strathmann, Timothy J.; Pienkos, Philip T.; Beckham, Gregg T.

2014-01-01

Lignin is an energy-dense, heterogeneous polymer comprised of phenylpropanoid monomers used by plants for structure, water transport, and defense, and it is the second most abundant biopolymer on Earth after cellulose. In production of fuels and chemicals from biomass, lignin is typically underused as a feedstock and burned for process heat because its inherent heterogeneity and recalcitrance make it difficult to selectively valorize. In nature, however, some organisms have evolved metabolic pathways that enable the utilization of lignin-derived aromatic molecules as carbon sources. Aromatic catabolism typically occurs via upper pathways that act as a “biological funnel” to convert heterogeneous substrates to central intermediates, such as protocatechuate or catechol. These intermediates undergo ring cleavage and are further converted via the β-ketoadipate pathway to central carbon metabolism. Here, we use a natural aromatic-catabolizing organism, Pseudomonas putida KT2440, to demonstrate that these aromatic metabolic pathways can be used to convert both aromatic model compounds and heterogeneous, lignin-enriched streams derived from pilot-scale biomass pretreatment into medium chain-length polyhydroxyalkanoates (mcl-PHAs). mcl-PHAs were then isolated from the cells and demonstrated to be similar in physicochemical properties to conventional carbohydrate-derived mcl-PHAs, which have applications as bioplastics. In a further demonstration of their utility, mcl-PHAs were catalytically converted to both chemical precursors and fuel-range hydrocarbons. Overall, this work demonstrates that the use of aromatic catabolic pathways enables an approach to valorize lignin by overcoming its inherent heterogeneity to produce fuels, chemicals, and materials. PMID:25092344

The chemical oxidation of lignin found in Sappi Saiccor dissolving ...

African Journals Online (AJOL)

Sappi Saiccor (situated in Durban, South Africa) dissolving pulp mill effluent, produced from an acid bisulphite pulping process, uses acacia and eucalyptus hardwoods to produce a unique and different blend of lignin that has not been previously studied. The chemical oxidation of lignin found in Sappi Saiccor's effluent has ...

The Paleozoic origin of enzymatic mechanisms for lignin degradation reconstructed using 31 fungal genomes

OpenAIRE

Floudas, Dimitrios; Binder, Manfred; Riley, Robert; Barry, Kerrie; Blanchette, Robert A; Henrissat, Bernard; Martinez, Angel T.; Otillar, Robert; Spatafora, Joseph W.; Yadav, Jagit S.; Aerts, Andrea; Benoit, Isabelle; Boyd, Alex; Carlson, Alexis; Copeland, Alex

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) suggest that lignin-degrading peroxidases expanded in the lineage leading to the ancestor of the Agaricomycetes, which is reconstruc...

Conditions for selective degradation of lignin by the fungus Ganoderma australis

Energy Technology Data Exchange (ETDEWEB)

Rios, S.; Eyzaguirre, J. (Universidad Catolica de Chile, Santiago (Chile). Lab. de Bioquimica)

1992-08-01

The white-rot fungus Ganoderma australis selectively degrades lignin in the ecosystem 'palo podrido'. Using conditions that simulate those of 'palo podrido' in the laboratory, it was found that low nitrogen content and low O{sub 2} tension stimulate the production of manganese peroxidase and lignin degradation, and depress cellulose degradation and cellulase production. The inverse is found at high nitrogen concentration and high O{sub 2} tension. This agrees with previous results indicating that low O{sub 2} tension and low nitrogen stimulate selective lignin degradation by this fungus. (orig.).

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

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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.

Temperature and pH influence adsorption of cellobiohydrolase onto lignin by changing the protein properties.

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Lu, Xianqin; Wang, Can; Li, Xuezhi; Zhao, Jian

2017-12-01

Non-productive adsorption of cellulase onto lignin restricted the movement of cellulase and also hindered the cellulase recycling in bioconversion of lignocellulose. In this study, effect of temperature and pH on adsorption and desorption of cellobiohydrolase (CBH) on lignin and its possible mechanism were discussed. It found that pH value and temperature influenced the adsorption and desorption behaviors of CBH on lignin. Different thermodynamic models suggested that the action between lignin and CBH was physical action. More CBH was adsorbed onto lignin, but lower initial adsorption velocity was detected at 50°C comparing with 4°C. Elevating pH value could improve desorption of cellulase from lignin. The changes of hydrophobicity and electric potential on protein surface may partially explain the impact of environmental conditions on the adsorption and desorption behaviors of CBH on lignin, and comparing to electrical interaction, the hydrophobicity may be the dominating factor influencing the behaviors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interactive forces between lignin and cellulase as determined by atomic force microscopy

OpenAIRE

Qin, Chengrong; Clarke, Kimberley; Li, Kecheng

2014-01-01

Background Lignin is a complex polymer which inhibits the enzymatic conversion of cellulose to glucose in lignocellulose biomass for biofuel production. Cellulase enzymes irreversibly bind to lignin, deactivating the enzyme and lowering the overall activity of the hydrolyzing reaction solution. Within this study, atomic force microscopy (AFM) is used to compare the adhesion forces between cellulase and lignin with the forces between cellulase and cellulose, and to study the moiety groups invo...

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

OpenAIRE

Hulin, Lise; Husson, Eric; Bonnet, Jean-Pierre; Stevanovic, Tatjana; Sarazin, Catherine

2015-01-01

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 f...

Use of Agave tequilana-lignin and zinc oxide nanoparticles for skin photoprotection.

Science.gov (United States)

Gutiérrez-Hernández, José Manuel; Escalante, Alfredo; Murillo-Vázquez, Raquel Nalleli; Delgado, Ezequiel; González, Francisco Javier; Toríz, Guillermo

2016-10-01

The use of sunscreens is essential for preventing skin damage and the potential appearance of skin cancer in humans. Inorganic active components such as zinc oxide (ZnO) have been used commonly in sunscreens due to their ability to block UVA radiation. This ultraviolet (UV) protection might be enhanced to cover the UVB and UVC bands when combined with other components such as titanium dioxide (TiO2). In this work we evaluate the photoprotection properties of organic nanoparticles made from lignin in combination with ZnO nanoparticles as active ingredients for sunscreens. Lignin nanoparticles were synthesized from Agave tequilana lignin. Two different pulping methods were used for dissolving lignin from agave bagasse. ZnO nanoparticles were synthesized by the precipitation method. All nanoparticles were characterized by SEM, UV-Vis and FT-IR spectroscopy. Nanoparticles were mixed with a neutral vehicle in different concentrations and in-vitro sun protection factor (SPF) values were calculated. Different sizes of spherical lignin nanoparticles were obtained from the spent liquors of two different pulping methods. ZnO nanoparticles resulted with a flake shape. The mixture of all components gave SPF values in a range between 4 and 13. Lignin nanoparticles showed absorption in the UVB and UVC regions which can enhance the SPF value of sunscreens composed only of zinc oxide nanoparticles. Lignin nanoparticles have the added advantage of being of organic nature and its brown color can be used to match the skin tone of the person using it. Copyright © 2016 Elsevier B.V. All rights reserved.

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

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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.

Application of bioethanol derived lignin for improving physico-mechanical properties of thermoset biocomposites.

Science.gov (United States)

Bajwa, Dilpreet S; Wang, Xinnan; Sitz, Evan; Loll, Tyler; Bhattacharjee, Sujal

2016-08-01

Lignin is the most abundant of renewable polymers next to cellulose with a global annual production of 70million tons, largely produced from pulping and second generation biofuel industries. Low value of industrial lignin makes it an attractive biomaterial for wide range of applications. The study investigated the application of wheat straw and corn stover based lignin derived from ethanol production for use in thermoset biocomposites. The biocomposite matrix constituted a two component low viscosity Araldite(®)LY 8601/Aradur(®) 8602 epoxy resin system and the lignin content varied from 0 to 25% by weight fraction. The analysis of the physical and mechanical properties of the biocomposites show bioethanol derived lignin can improve selective properties such as impact strength, and thermal stability without compromising the modulus and strength attributes. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Properties of Lignin from Oil Palm Empty Fruit Bunch and Its Application for Plywood Adhesive

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Lucky Risanto

2014-10-01

Full Text Available Lignin from lignocellulosic biomass is a potential biopolymer for wood adhesive. The aims of this study were to characterize lignin isolated from the black liquor of oil palm empty fruit bunch fiber pretreated with steam explosion in alkaline conditions and to examine the bond quality of aqueous polymer isocyanate (API adhesive prepared from lignin, natural rubber latex (NRL, and polyvinyl alcohol (PVA as base polymers with isocyanate crosslinkers. Lignin was precipitated from the black liquor by adding hydrochloric acid; then the precipitate was separated by filtration, thoroughly washed with water up to pH 2 and pH 5, and dried. The isolated lignin was characterized by ultimate analysis, UV spectroscopy, FT-IR spectroscopy, and thermal analysis. Three-layer plywood samples were prepared, and the bond strengths of the plywood samples were determined in dry conditions and after cyclic boiling. The lignin isolates with different pH values did not have significantly different chemical and thermal properties. Both lignin isolates had similar C, H, and O contents, identical functional groups in the FTIR spectra, similar absorption in the UV spectra, and high decomposition temperatures. The base polymers composition that could produce API adhesive for exterior applications was NRL/PVA/lignin (4/4/2. The use of more lignin in the adhesive formulation decreased the bond strength of the plywood.

Preparation of Lignin/Sodium Dodecyl Sulfate Composite Nanoparticles and Their Application in Pickering Emulsion Template-Based Microencapsulation.

Science.gov (United States)

Pang, Yuxia; Wang, Shengwen; Qiu, Xueqing; Luo, Yanling; Lou, Hongming; Huang, Jinhao

2017-12-20

Lignin is a vastly underutilized biomass resource. The preparation of water-dispersed lignin nanoparticles is an effective way to realize the high-value utilization of lignin. However, the currently reported preparation methods of lignin nanoparticles still have some drawbacks, such as the requirement for toxic organic solvent or chemical modification, complicated operation process, and poor dispersibility. Here, lignin/sodium dodecyl sulfate (SDS) composite nanoparticles (LSNPs) with outstanding water dispersibility and a size range of 70-200 nm were facilely prepared via acidifying the mixed basic solution of alkaline lignin and SDS. No harsh chemical was needed. The formation mechanism was systematically studied. Results indicated that the LSNPs were obtained by acid precipitation of the mixed micelles formed by the self-assembly of lignin and SDS. In addition, on the basis of the LSNP-stabilized Pickering emulsions, lignin/polyurea composite microcapsules combining the excellent chemical stability of a synthetic polyurea shell with the fantastic antiphotolysis and antioxidant properties of lignin were successfully prepared.

Characteristics of Lignin Fractions from Dilute Acid Pretreated Switchgrass and Their Effect on Cellobiohydrolase from Trichoderma longibrachiatum

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Lan Yao

2018-02-01

Full Text Available To investigate the interactions between acid pretreated switchgrass lignin and cellobiohydrolase (CBH, three different lignin fractions were isolated from dilute acid pretreated switchgrass by (i ethanol extraction, followed by (ii dioxane/H2O extraction, and (iii cellulase treatment, respectively. Structural properties of each lignin fraction were elucidated by GPC, 13C-NMR, and 2D-HSQC NMR analyses. The adsorptions of CBH to the isolated lignin fractions were also studied by Langmuir adsorption isotherms. Ethanol-extractable lignin fraction, mainly composed of syringyl (S and guaiacyl (G units, had the lowest molecular weight, while dioxane/H2O-extracted lignin fraction had the lowest S/G ratio with higher content of p-coumaric acid (pCA unit. The residual lignin fraction after enzymatic treatment had the highest S/G ratio without hydroxyphenyl (H unit. Strong associations were found between lignin properties such as lignin composition and S/G ratio and its non-productive enzyme adsorption factors including the maximum adsorption capacity and binding strength.

Structural elucidation and antioxidant activity of lignin isolated from rice straw and alkali‑oxygen black liquor.

Science.gov (United States)

Jiang, Bo; Zhang, Yu; Gu, Lihui; Wu, Wenjuan; Zhao, Huifang; Jin, Yongcan

2018-05-17

Alkali‑oxygen cooking of lignocellulose offers lignin many structural properties and bioactivities for biorefinery. In this work, milled wood lignin (MWL) and alkali‑oxygen lignin (AOL) were isolated from rice straw and alkali‑oxygen black liquor, respectively. The lignin structure was characterized by spectroscopy and wet chemistry. Antioxidant activity of lignins was assessed by DPPH·and ABTS scavenging ability assay. Results showed the oxidization and condensation of lignin occurred during alkali‑oxygen cooking. The p-hydroxyphenyl was more easily removed from rice straw than guaiacyl and syringyl units. The ester or ether linkages derived from hydroxycynnamic acids, and the main interunit linkages, i.e. β-O-4' bonds, were mostly cleaved. Lignin-xylan complex had high reactivity under alkali‑oxygen condition. Tricin, incorporated into lignin, was detected in MWL but was absent in AOL. Nitrobenzene oxidation showed MWL can well represent the protolignin of rice straw, and the products yield decreased dramatically after alkali‑oxygen cooking. AOL had higher radical scavenging ability than MWL indicating alkali‑oxygen cooking was an effective pathway for the enhancement of antioxidant activity of lignin. Copyright © 2018 Elsevier B.V. All rights reserved.

Chemical composition and enzymatic digestibility of sugarcane clones selected for varied lignin content

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Masarin Fernando

2011-12-01

Full Text Available Abstract Background The recalcitrance of lignocellulosic materials is a major limitation for their conversion into fermentable sugars. Lignin depletion in new cultivars or transgenic plants has been identified as a way to diminish this recalcitrance. In this study, we assessed the success of a sugarcane breeding program in selecting sugarcane plants with low lignin content, and report the chemical composition and agronomic characteristics of eleven experimental hybrids and two reference samples. The enzymatic digestion of untreated and chemically delignified samples was evaluated to advance the performance of the sugarcane residue (bagasse in cellulosic-ethanol production processes. Results The ranges for the percentages of glucan, hemicellulose, lignin, and extractive (based on oven-dry biomass of the experimental hybrids and reference samples were 38% to 43%, 25% to 32%, 17% to 24%, and 1.6% to 7.5%, respectively. The samples with the smallest amounts of lignin did not produce the largest amounts of total polysaccharides. Instead, a variable increase in the mass of a number of components, including extractives, seemed to compensate for the reduction in lignin content. Hydroxycinnamic acids accounted for a significant part of the aromatic compounds in the samples, with p-coumaric acid predominating, whereas ferulic acid was present only in low amounts. Hydroxycinnamic acids with ester linkage to the hemicelluloses varied from 2.3% to 3.6%. The percentage of total hydroxycinnamic acids (including the fraction linked to lignin through ether linkages varied from 5.0% to 9.2%, and correlated to some extent with the lignin content. These clones released up to 31% of glucose after 72 hours of digestion with commercial cellulases, whereas chemically delignified samples led to cellulose conversion values of more than 80%. However, plants with lower lignin content required less delignification to reach higher efficiencies of cellulose conversion during

SbCOMT (Bmr12) is involved in the biosynthesis of tricin-lignin in sorghum

Science.gov (United States)

Lignin in plant biomass represents a target for engineering strategies towards the development of a sustainable bioeconomy. In addition to the conventional lignin monomers, namely p-coumaryl, coniferyl and sinapyl alcohols, tricin has been shown to be part of the native lignin polymer in certain mon...

New Insights Toward Quantitative Relationships between Lignin Reactivity to Monomers and Their Structural Characteristics.

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Ma, Ruoshui; Zhang, Xiumei; Wang, Yi; Zhang, Xiao

2018-04-27

The heterogeneous and complex structural characteristics of lignin present a significant challenge to predict its processability (e.g. depolymerization, modifications etc) to valuable products. This study provides a detailed characterization and comparison of structural properties of seven representative biorefinery lignin samples derived from forest and agricultural residues, which were subjected to representative pretreatment methods. A range of wet chemistry and spectroscopy methods were applied to determine specific lignin structural characteristics such as functional groups, inter-unit linkages and peak molecular weight. In parallel, oxidative depolymerization of these lignin samples to either monomeric phenolic compounds or dicarboxylic acids were conducted, and the product yields were quantified. Based on these results (lignin structural characteristics and monomer yields), we demonstrated for the first time to apply multiple-variable linear estimations (MVLE) approach using R statistics to gain insight toward a quantitative correlation between lignin structural properties and their conversion reactivity toward oxidative depolymerization to monomers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relationship between lignin structure and delignification degree in Pinus pinaster kraft pulps.

Science.gov (United States)

Baptista, C; Robert, D; Duarte, A P

2008-05-01

This study examines the structure of residual and dissolved lignins from Pinus pinaster pulps obtained at different degrees of delignification by laboratory conventional kraft pulping. The cooking H factor was varied from 85 to 8049. The residual and dissolved lignin samples were characterised by elemental analysis, residual carbohydrate content, permanganate oxidation and 13C NMR spectroscopy. The reflectance factor of the pulps was also determined in order to tentatively correlate the delignification degree and residual lignin structure with the pulp colour. The obtained results confirmed that the delignification degree increases the condensation of the lignin structure, which might have an influence upon the observed increased pulp colour. The lack of selectivity of kraft pulping process in the case of more delignified pulps was also shown.

EFFECT OF LIGNIN CONTENT OF Eucalyptus globulus WOOD IN KRAFT PULPING PERFORMANCE

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Gabriel Valim Cardoso

2011-03-01

Full Text Available In this research, it was analyzed the lignin content effect of Eucalyptus globulus wood in kraft pulping optimization. Seventy-two laboratory cooking were made with wood chips obtained from six Eucalyptus globulus trees selected from a group of 50 trees. The wood chips from three trees with the lowest lignin content, with average 20,53%, were mixed proportionally based on the tree weights, obtaining the sample of low lignin content wood. The same was made to obtain the sample for wood chips with the highest lignin content, with average 23,02%. The two lignin levels were statistically different. The two wood samples had basic densities statistically not different. Using three maximum temperatures levels (160, 165 and 170ºC, and three active alkali charged (17, 18,5 and 20%, the wood chips were converted to kraft pulps. The pulps were then characterized to analyze the influence of the distinct treatments employed in the cooking on their properties. The effect of the cooking conditions was expressed by mathematical models in order to determine the optimum points for each of the evaluated properties. The optimization process indicated maximum temperature of 168ºC, and active alkali of 19%, for maximum kraft pulping yield to achieve kappa number 18; this result was for woods with low lignin content. For woods containing the high lignin content, the optimization showed maximum cooking temperature of 169ºC and active alkali of 19% for kappa number of 18. The average reduction of 2,49% in wood lignin content resulted a correspondent gain of 2,2% in the kraft yield (o.d. basis and a reduction on the active alkali charge of 1,2% (o.d. basis to achieve kappa numbers from 16 to 19, preserving pulp properties. If the option is to work with kappa number 19 instead of 16, the gain in kraft yield is approximately 2%. Therefore, when working with low lignin content wood and kappa number 19 instead of 16, a substantial gain of approximately 4,2% is obtained

Density functional theory study of spirodienone stereoisomers in lignin

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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...

Retention of lignin in seagrasses: angiosperms that returned to the sea

NARCIS (Netherlands)

Klap, V.A.; Hemminga, M.A.; Boon, J.J.

2000-01-01

Using Curie-point Pyrolysis Gas Chromatography Mass Spectrometry (Py-GCMS) and Direct Temperature-resolved Mass Spectrometry (DT-MS), lignin was detected in highly purified preparations (Milled Wood Lignin = MWL) of various tissues of the seagrasses Zostera marina and Posidonia oceanica. The results

Enrichment of Bacteria From Eastern Mediterranean Sea Involved in Lignin Degradation via the Phenylacetyl-CoA Pathway

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Hannah L. Woo

2018-05-01

Full Text Available The degradation of allochthonous terrestrial organic matter, such as recalcitrant lignin and hemicellulose from plants, occurs in the ocean. We hypothesize that bacteria instead of white-rot fungi, the model organisms of aerobic lignin degradation within terrestrial environments, are responsible for lignin degradation in the ocean due to the ocean’s oligotrophy and hypersalinity. Warm oxic seawater from the Eastern Mediterranean Sea was enriched on lignin in laboratory microcosms. Lignin mineralization rates by the lignin-adapted consortia improved after two sequential incubations. Shotgun metagenomic sequencing detected a higher abundance of aromatic compound degradation genes in response to lignin, particularly phenylacetyl-CoA, which may be an effective strategy for marine microbes in fluctuating oxygen concentrations. 16S rRNA gene amplicon sequencing detected a higher abundance of Gammaproteobacteria and Alphaproteobacteria bacteria such as taxonomic families Idiomarinaceae, Alcanivoraceae, and Alteromonadaceae in response to lignin. Meanwhile, fungal Ascomycetes and Basidiomycetes remained at very low abundance. Our findings demonstrate the significant potential of bacteria and microbes utilizing the phenylacetyl-CoA pathway to contribute to lignin degradation in the Eastern Mediterranean where environmental conditions are unfavorable for fungi. Exploring the diversity of bacterial lignin degraders may provide important enzymes for lignin conversion in industry. Enzymes may be key in breaking down high molecular weight lignin and enabling industry to use it as a low-cost and sustainable feedstock for biofuels or other higher-value products.

Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen

NARCIS (Netherlands)

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

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

Control of lignin solubility and particle formation modulates its antioxidant efficiency in lipid medium

DEFF Research Database (Denmark)

Barsberg, Søren Talbro; Thygesen, Lisbeth Garbrecht; Sanadi, Anand Ramesh

2014-01-01

Lignin is an abundant plant polymer usually regarded as waste material. In the present work, antioxidant properties of lignin preparations with differing lipid solubility were studied using biodiesel as a convenient lipid test substrate. In place of formerly used assays, we used attenuated total...... reflectance (ATR) FT-IR spectroscopy to follow in situ biodiesel autoxidation on a heated ATR crystal as a function of time. The study demonstrates that a complex balance between intrinsic (chemical) efficiency, solubility, and particle formation controls the antioxidant efficiency of differently prepared...... lignin fractions. It was found that solubility and particle formation of lignin preparations strongly modulate its antioxidant efficiency and that these properties might depend on the presence of lipid components within the original lignin source....

The Paleozoic origin of enzymatic mechanisms for lignin degradation reconstructed using 31 fungal genomes

Energy Technology Data Exchange (ETDEWEB)

Floudas, Dimitrios; Binder, Manfred; Riley, Robert; Barry, Kerrie; Blanchette, Robert A; Henrissat, Bernard; Martinez, Angel T.; Otillar, Robert; Spatafora, Joseph W.; Yadav, Jagit S.; Aerts, Andrea; Benoit, Isabelle; Boyd, Alex; Carlson, Alexis; Copeland, Alex; Coutinho, Pedro M.; de Vries, Ronald P.; Ferreira, Patricia; Findley, Keisha; Foster, Brian; Gaskell, Jill; Glotzer, Dylan; Gorecki, Pawel; Heitman, Joseph; Hesse, Cedar; Hori, Chiaki; Igarashi, Kiyohiko; Jurgens, Joel A.; Kallen, Nathan; Kersten, Phil; Kohler, Annegret; Kues, Ursula; Kumar, T. K. Arun; Kuo, Alan; LaButti, Kurt; Larrondo, Luis F.; Lindquist, Erika; Ling, Albee; Lombard, Vincent; Lucas, Susan; Lundell, Taina; Martin, Rachael; McLaughlin, David J.; Morgenstern, Ingo; Morin, Emanuelle; Murat, Claude; Nagy, Laszlo G.; Nolan, Matt; Ohm, Robin A.; Patyshakuliyeva, Aleksandrina; Rokas, Antonis; Ruiz-Duenas, Francisco J.; Sabat, Grzegorz; Salamov, Asaf; Samejima, Masahiro; Schmutz, Jeremy; Slot, Jason C.; John, Franz; Stenlid, Jan; Sun, Hui; Sun, Sheng; Syed, Khajamohiddin; Tsang, Adrian; Wiebenga, Ad; Young, Darcy; Pisabarro, Antonio; Eastwood, Daniel C.; Martin, Francis; Cullen, Dan; Grigoriev, Igor V.; Hibbett, David S.

2012-03-12

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) suggest that lignin-degrading peroxidases expanded in the lineage leading to the ancestor of the Agaricomycetes, which is reconstructed as a white rot species, and then contracted in parallel lineages leading to brown rot and mycorrhizal species. Molecular clock analyses suggest that the origin of lignin degradation might have coincided with the sharp decrease in the rate of organic carbon burial around the end of the Carboniferous period.

Large-Scale Transcriptome Analysis of Two Sugarcane Genotypes Contrasting for Lignin Content.

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Renato Vicentini

Full Text Available Sugarcane is an important crop worldwide for sugar and first generation ethanol production. Recently, the residue of sugarcane mills, named bagasse, has been considered a promising lignocellulosic biomass to produce the second-generation ethanol. Lignin is a major factor limiting the use of bagasse and other plant lignocellulosic materials to produce second-generation ethanol. Lignin biosynthesis pathway is a complex network and changes in the expression of genes of this pathway have in general led to diverse and undesirable impacts on plant structure and physiology. Despite its economic importance, sugarcane genome was still not sequenced. In this study a high-throughput transcriptome evaluation of two sugarcane genotypes contrasting for lignin content was carried out. We generated a set of 85,151 transcripts of sugarcane using RNA-seq and de novo assembling. More than 2,000 transcripts showed differential expression between the genotypes, including several genes involved in the lignin biosynthetic pathway. This information can give valuable knowledge on the lignin biosynthesis and its interactions with other metabolic pathways in the complex sugarcane genome.

Catalytic biorefining of plant biomass to non-pyrolytic lignin bio-oil and carbohydrates through hydrogen transfer reactions.

Science.gov (United States)

Ferrini, Paola; Rinaldi, Roberto

2014-08-11

Through catalytic hydrogen transfer reactions, a new biorefining method results in the isolation of depolymerized lignin--a non-pyrolytic lignin bio-oil--in addition to pulps that are amenable to enzymatic hydrolysis. Compared with organosolv lignin, the lignin bio-oil is highly susceptible to further hydrodeoxygenation under low-severity conditions and therefore establishes a unique platform for lignin valorization by heterogeneous catalysis. Overall, the potential of a catalytic biorefining method designed from the perspective of lignin utilization is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of altered lignin composition on mechanical properties of CINNAMYL ALCOHOL DEHYDROGENASE (CAD) deficient poplars.

Science.gov (United States)

Özparpucu, Merve; Gierlinger, Notburga; Burgert, Ingo; Van Acker, Rebecca; Vanholme, Ruben; Boerjan, Wout; Pilate, Gilles; Déjardin, Annabelle; Rüggeberg, Markus

2018-04-01

CAD-deficient poplars enabled studying the influence of altered lignin composition on mechanical properties. Severe alterations in lignin composition did not influence the mechanical properties. Wood represents a hierarchical fiber-composite material with excellent mechanical properties. Despite its wide use and versatility, its mechanical behavior has not been entirely understood. It has especially been challenging to unravel the mechanical function of the cell wall matrix. Lignin engineering has been a useful tool to increase the knowledge on the mechanical function of lignin as it allows for modifications of lignin content and composition and the subsequent studying of the mechanical properties of these transgenics. Hereby, in most cases, both lignin composition and content are altered and the specific influence of lignin composition has hardly been revealed. Here, we have performed a comprehensive micromechanical, structural, and spectroscopic analysis on xylem strips of transgenic poplar plants, which are downregulated for cinnamyl alcohol dehydrogenase (CAD) by a hairpin-RNA-mediated silencing approach. All parameters were evaluated on the same samples. Raman microscopy revealed that the lignin of the hpCAD poplars was significantly enriched in aldehydes and reduced in the (relative) amount of G-units. FTIR spectra indicated pronounced changes in lignin composition, whereas lignin content was not significantly changed between WT and the hpCAD poplars. Microfibril angles were in the range of 18°-24° and were not significantly different between WT and transgenics. No significant changes were observed in mechanical properties, such as tensile stiffness, ultimate stress, and yield stress. The specific findings on hpCAD poplar allowed studying the specific influence of lignin composition on mechanics. It can be concluded that the changes in lignin composition in hpCAD poplars did not affect the micromechanical tensile properties.