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Sample records for acid-precipitable polymeric lignin

  1. Biologically produced acid precipitable polymeric lignin

    DOEpatents

    Crawford, Don L.; Pometto, III, Anthony L.

    1984-01-01

    A water soluble, acid precipitable polymeric degraded lignin (APPL), having a molecular weight of at least 12,000 daltons, and comprising, by percentage of total weight, at least three times the number of phenolic hydroxyl groups and carboxylic acid groups present in native lignin. The APPL may be modified by chemical oxidation and reduction to increase its phenolic hydroxyl content and reduce the number of its antioxidant inhibitory side chains, thereby improving antioxidant properties.

  2. Chemical factors that control lignin polymerization.

    PubMed

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

    2014-01-01

    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.

  3. Chemical factors that control lignin polymerization

    SciTech Connect

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

    2014-01-01

    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). 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 ( - or -5) react poorly and tend to cap the polymer. In general, -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.

  4. Acidic precipitation

    SciTech Connect

    Martin, H.C.

    1987-01-01

    At the International Symposium on Acidic Precipitation, over 400 papers were presented, and nearly 200 of them are included here. They provide an overview of the present state of the art of acid rain research. The Conference focused on atmospheric science (monitoring, source-receptor relationships), aquatic effects (marine eutrophication, lake acidification, impacts on plant and fish populations), and terrestrial effects (forest decline, soil acidification, etc.).

  5. Polymerization reactivity of sulfomethylated alkali lignin modified with horseradish peroxidase.

    PubMed

    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. PMID:24534439

  6. Polymerization reactivity of sulfomethylated alkali lignin modified with horseradish peroxidase.

    PubMed

    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.

  7. p-Hydroxyphenyl (H) Units Lower the Degree of Polymerization in Lignin: Chemical Control in Lignin Biosynthesis

    SciTech Connect

    Sangha, A. K.; Parks, J. M.; Davis, M. F.; Smith, J. C.

    2013-01-01

    Lignin, composed predominantly of p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) subunits, is a major component of plant cell walls that imparts resistance toward chemical and microbial deconstruction of plant biomass, rendering its conversion inefficient and costly. Previous studies have shown that alterating lignin composition, i.e., the relative abundance of H, G and S subunits, promises more efficient extraction of sugars from plant biomass. Smaller and less branched lignin chains are more easily extracted during pretreatment, making cellulose more readily degradable. Here, using density functional theory calculations, we show that the incorporation of H subunits into lignin via b-b and b-5 interunit linkages reduces the degree of polymerization in lignin. Frontier molecular orbital analyses of lignin dimers and trimers show that H as a terminal subunit on a growing lignin polymer linked via b-b and b-5 linkage cannot undergo radical formation, preventing further chain growth by endwise polymerization resulting in lignin polymers with lower degree of polymerization. These results indicate that, for endwise polymerization in lignin synthesis, there exists a chemical control that may lay a significant role in determining the structure of lignin.

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

    PubMed

    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 < 4000 g/mol) was carried out in the same solvent system. 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. PMID:24432339

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

    PubMed

    Gupta, Chetali; Washburn, Newell R

    2014-08-12

    Kraft lignin grafted with hydrophilic polymers has been prepared using reversible addition-fragmentation chain-transfer (RAFT) polymerization and investigated for use as a surfactant. In this preliminary study, polyacrylamide and poly(acrylic acid) were grafted from a lignin RAFT macroinitiator at average initiator site densities estimated to be 2 per particle and 17 per particle. The target degrees of polymerization were 50 and 100, but analysis of cleaved polyacrylamide was consistent with a higher average molecular weight, suggesting not all sites were able to participate in the polymerization. All materials were readily soluble in water, and dynamic light scattering data indicate polymer-grafted lignin coexisted in isolated and aggregated forms in aqueous media. The characteristic size was 15-20 nm at low concentrations, and aggregation appeared to be a stronger function of degree of polymerization than graft density. These species were surface active, reducing the surface tension to as low as 60 dyn/cm at 1 mg/mL, and a greater decrease was observed than for polymer-grafted silica nanoparticles, suggesting that the lignin core was also surface active. While these lignin surfactants were soluble in water, they were not soluble in hexanes. Thus, it was unexpected that water-in-oil emulsions formed in all surfactant compositions and solvent ratios tested, with average droplet sizes of 10-20 μm. However, although polymer-grafted lignin has structural features similar to nanoparticles used in Pickering emulsions, its interfacial behavior was qualitatively different. While at air-water interfaces, the hydrophilic grafts promote effective reductions in surface tension, we hypothesize that the low grafting density in these lignin surfactants favors partitioning into the hexanes side of the oil-water interface because collapsed conformations of the polymer grafts improve interfacial coverage and reduce water-hexanes interactions. We propose that polymer-grafted lignin

  10. Acid Precipitation; (USA)

    SciTech Connect

    Rushing, J.W.; Hicks, S.C.

    1991-01-01

    This publication, Acid Precipitation (APC) announces on a monthly basis the current worldwide information on acid precipitation and closely related subjects, including wet and dry deposition, long-range transport, environmental effects, modeling, and socioeconomic factors. Information on the following subjects is included within the scope of this publication, but all subjects may not appear in each issue: Pollution sources and pollution control technology; atmospheric transport and chemistry; terrestrial transport and chemistry; aquatic transport and chemistry; biological effects; corrosive effects; and socioeconomics, policy, and legislation.

  11. Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-Tg Polymeric Materials

    PubMed Central

    2016-01-01

    As viable precursors to a diverse array of macromolecules, biomass-derived compounds must impart wide-ranging and precisely controllable properties to polymers. Herein, we report the synthesis and subsequent reversible addition–fragmentation chain-transfer polymerization of a new monomer, syringyl methacrylate (SM, 2,6-dimethoxyphenyl methacrylate), that can facilitate widespread property manipulations in macromolecules. Homopolymers and heteropolymers synthesized from SM and related monomers have broadly tunable and highly controllable glass transition temperatures ranging from 114 to 205 °C and zero-shear viscosities ranging from ∼0.2 kPa·s to ∼17,000 kPa·s at 220 °C, with consistent thermal stabilities. The tailorability of these properties is facilitated by the controlled polymerization kinetics of SM and the fact that one vs two o-methoxy groups negligibly affect monomer reactivity. Moreover, syringol, the precursor to SM, is an abundant component of depolymerized hardwood (e.g., oak) and graminaceous (e.g., switchgrass) lignins, making SM a potentially sustainable and low-cost candidate for tailoring macromolecular properties. PMID:27213117

  12. Preparation of porous carbons from polymeric precursors modified with acrylated kraft lignin

    NASA Astrophysics Data System (ADS)

    Sobiesiak, M.

    2016-04-01

    The presented studies concern the preparation of porous carbons from a BPA.DA-St polymer containing acrylated kraft lignin as a monomer. The porous polymeric precursor in the form of microspheres was synthesized in suspension polymerization process. Next samples of the polymer were impregnated with acetic acid or aqueous solution of acetates (potassium or ammonia), dried and carbonised in nitrogen atmosphere at 450°C. After carbonization microspherical shape of the materials was remained, that is desired feature for potential application in chromatography or SPE technique. Chemical and textural properties of the porous carbon adsorbents were characterized using infrared spectroscopy (ATR-FTIR), thermogravimetry analyses with mass spectrometry of released gases (TG-MS) and nitrogen sorption experiments. The presented studies revealed the impregnation is useful method for development of porous structure of carbonaceous materials. The highest values of porous structure parameters were obtained when acetic acid and ammonium acetate were used as impregnating substances. On the surface of the materials oxygen functional groups are present that is important for specific interactions during sorption processes. The highest contents of functionalities were observed for carbon BPA.DA-St-LA-C-AcNH4.

  13. Acid Precipitation: Causes and Consequences.

    ERIC Educational Resources Information Center

    Babich, Harvey; And Others

    1980-01-01

    This article is the first of three articles in a series on the acid rain problem in recent years. Discussed are the causes of acid precipitation and its consequences for the abiotic and biotic components of the terrestrial and aquatic ecosystems, and for man-made materials. (Author/SA)

  14. Lignin nanoparticle synthesis

    DOEpatents

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

    2015-08-11

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

  15. Strategies for the Conversion of Lignin to High-Value Polymeric Materials: Review and Perspective.

    PubMed

    Upton, Brianna M; Kasko, Andrea M

    2016-02-24

    The majority of commodity plastics and materials are derived from petroleum-based chemicals, illustrating the strong dependence on products derived from non-renewable energy sources. As the most accessible, renewable form of carbon (in comparison to CO2), lignocellulosic biomass (defined as organic matter available on a renewable basis) has been acknowledged as the most logical carbon-based feedstock for a variety of materials such as biofuels and chemicals. This Review focuses on methods developed to synthesize polymers derived from lignin, monolignols, and lignin-derived chemicals. Major topics include the structure and processing of lignocellulosic biomass to lignin, polymers utilizing lignin as a macromonomer, synthesis of monomers and polymers from monolignols, and polymers from lignin-derived chemicals, such as vanillin. PMID:26654678

  16. Polymerization of pentachlorophenol and ferulic acid by fungal extracellular lignin-degrading enzymes.

    PubMed Central

    Rüttimann-Johnson, C; Lamar, R T

    1996-01-01

    High-molecular-weight polymers were produced by a crude concentrated supernatant from ligninolytic Phanerochaete chrysosporium cultures in a reaction mixture containing pentachlorophenol and a humic acid precursor (ferulic acid) in the presence of a detergent and H2O2. Pure manganese peroxidase, lignin peroxidase, and laccase were also shown to catalyze the reaction. PMID:8967777

  17. Acid Precipitation and the Forest Ecosystem

    ERIC Educational Resources Information Center

    Dochinger, Leon S.; Seliga, Thomas A.

    1975-01-01

    The First International Symposium on Acid Precipitation and the Forest Ecosystem dealt with the potential magnitude of the global effects of acid precipitation on aquatic ecosystems, forest soils, and forest vegetation. The problem is discussed in the light of atmospheric chemistry, transport, and precipitation. (Author/BT)

  18. Acid precipitation and human health: Final report

    SciTech Connect

    Hoffman, S.

    1989-08-01

    This report, written for environmental managers in electric utilities, reviews potential indirect human health effects of acid precipitation. Possible exposure routes and materials examined in this review include drinking water contamination (aluminum and mercury), corrosion of metals (lead, cadmium, arsenic, selenium, copper, and zinc) and asbestos from water piping, bioaccumulation of mercury and other metals in fish and game, and uptake of mobilized metals in crops. No direct effects (e.g., skin or eye irritation) of human exposure to acid precipitation have been identified, and air pollutant impacts on health are not included in this review, because these pollutants are acid precipitation precursors, not acid precipitation per se. The literature is summarized, presenting results from researchers' studies to support their conclusions. The review discusses potential acid precipitation impacts on metal levels in drinking water and food, summarizes the health effects of ingestion of these materials, and identifies areas of needed research. Metal-metal interactions in humans that may be related to acid precipitation are identified. Current research programs and planned assessments of the indirect human health effects of acid precipitation are summarized. 136 refs., 38 figs., 17 tabs

  19. Acid precipitation. (Latest citations from the Compendex database). Published Search

    SciTech Connect

    Not Available

    1993-06-01

    The bibliography contains citations concerning the causes, effects, sources, and controls of acid precipitation and acidification. Techniques and technology for measurement and analysis of acid precipitation are considered. (Contains 250 citations and includes a subject term index and title list.)

  20. Acid precipitation. (Latest citations from Pollution abstracts). Published Search

    SciTech Connect

    Not Available

    1994-03-01

    The bibliography contains citations concerning the research of acid precipitation, and the resultant acidification of land and water. Topics include composition, causes, effects, sources, measurements, and controls of acid precipitation. Worldwide geographical distribution of acid precipitation and acidification are covered. (Contains 250 citations and includes a subject term index and title list.)

  1. Acid precipitation. (Latest citations from Pollution Abstracts database). Published Search

    SciTech Connect

    Not Available

    1993-09-01

    The bibliography contains citations concerning the research of acid precipitation, and the resultant acidification of land and water. Topics include composition, causes, effects, sources, measurements, and controls of acid precipitation. Worldwide geographical distribution of acid precipitation and acidification are covered. (Contains 250 citations and includes a subject term index and title list.)

  2. Genetic manipulation of ligninolytic streptomyces and generation of improved lignin-to-chemical bioconversion strains

    SciTech Connect

    Crawford, D.L.; Pettey, T.M.; Thede, B.M.; Deobald, L.A.

    1984-01-01

    Streptomyces viridosporus T7A, when used in solid-state fermentation, degrades lignin at high yields to a water-soluble modified polymer, acid precipitable polymeric lignin (APPL) that is useful as an antioxidant, surfactant, and potentially as a component of adhesives and resins. Enhanced strains generated from ultraviolet irradiation mutagenesis and protoplast fusion produced up to 90% more APPL from corn stover lignocellulose than did the wildtype, and they were stable and produced APPL at a faster rate and to a higher final yield than did parental strain T7A. APPLs produced by the wildtype and selected mutants were chemicaly similar polyphenols, but some catabolic enzymes of the genetically manipulated strains were produced in greater amounts.

  3. Acid Precipitation: A current awareness bulletin

    SciTech Connect

    Blackburn, P.S.

    1988-01-01

    Acid Precipition (APC) announces on a monthly basis the current worldwide information on acid precipation and closely related subjects, including wet and dry deposition, long-range transport, environmental effects, modeling, and socioeconomic factors. This publication contains the abstracts of DOE reports, journal articles, conference papers, patents, theses, and monographs added to the Energy Data Base (EDB) during the past month. Also included are US information obtained through acquisition programs or interagency agreements and international agreements and international information obtained through the International Energy Agency's Energy Technology Data Exchange or goverment-to-government agreements.

  4. Primer on acid precipitation. A killing rain: the global threat of acid precipitation

    SciTech Connect

    Pawlick, T.

    1984-01-01

    This article reviews the book A Killing Rain: The Global Threat of Acid Precipitation by Thomas Pawlick which presents an overview of the problems associated with acid rain. The book covers the effects of acid rain on aquatic ecosystems, forests materials, and agriculture. It also deals with abatement technologies and sociopolitical topics associated with acid rain.

  5. Effects of acid precipitation on Daphnia magna

    SciTech Connect

    Parent, S.; Cheetham, R.D.

    1980-08-01

    Pollutants derived from fossil fuel combustion and precipitated from the atmosphere have substantially increased in the past decades. These materials, precipitated in such industrialized areas as southeastern Canada, have caused considerable alterations in aquatic ecosystems. Precipitation over most of the eastern United States is presently 10 to 500 times more acidic than is natural. Most affected aquatic ecosystems contain oligotrophic waters in regions of thin poorly buffered soils. Zooplankton are an important link in food chains of aquatic ecosystems and their disappearance or decline could drastically affect trophic relationships. Declines in zooplankton density in response to acid precipitation have been reported and short term survival of Daphnia pulex between pH 4.3 and 10.4; however, its potential for reproduction was limited to a fairly narrow range. Anderson (1944) noted the advantages of using daphnia as test organisms, and concluded that Daphnia magna was representative of other abundant zooplankton in sensitivity to toxic substances.

  6. Comment on acid precipitation in historical perspective and effects of acid precipitation

    SciTech Connect

    Richter, D.D.

    1983-01-01

    An overview is presented of the history of the problem of acid rain. Lake and stream water are classified as sensitive to acid rain largely on the basis of buffering capacity of soils and geological substrate. Evidence for acid precipitation causing the acidification of lakes and streams on a regional basis is not conclusive. However, soil genesis and forest development can be acidifying processes in humid climates. Acid rain is increasing soil aluminum solubility and leaching to surface water in concentrations toxic to fish. Under natural conditions of podzolization, aluminum is mobilized in surface soils and subsequently retained by spodic subsoils. Whether acid rain appreciably accelerates aluminum leaching from soils is hypothetical. It is concluded from one report that acid precipitation is related to increases in the accumulation and spatial variations of forest floors, soil acidification, exchangeable aluminum, aluminum released from clay, and internal ecosystem H/sup +/ ion production. But, these conclusions are based on limited sampling. 28 references.

  7. Through Lignin Biodegradation to Lignin-based Plastics

    NASA Astrophysics Data System (ADS)

    Wang, Yun-Yan

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

  8. Acid precipitation. (Latest citations from Pollution Abstracts). Published Search

    SciTech Connect

    Not Available

    1992-06-01

    The bibliography contains citations concerning the wet and dry precipitation of acid, and the resultant acidification of land and water. Topics include composition, causes, effects, sources, measurements, and controls of acid precipitation. Some attention is focused upon the worldwide geographical distribution of acid precipitation and acidification. (Contains 250 citations and includes a subject term index and title list.)

  9. Lignin-Based Thermoplastic Materials.

    PubMed

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

    2016-04-21

    Lignin-based thermoplastic materials have attracted increasing interest as sustainable, cost-effective, and biodegradable alternatives for petroleum-based thermoplastics. As an amorphous thermoplastic material, lignin has a relatively high glass-transition temperature and also undergoes radical-induced self-condensation at high temperatures, which limits its thermal processability. Additionally, lignin-based materials are usually brittle and exhibit poor mechanical properties. To improve the thermoplasticity and mechanical properties of technical lignin, polymers or plasticizers are usually integrated with lignin by blending or chemical modification. This Review attempts to cover the reported approaches towards the development of lignin-based thermoplastic materials on the basis of published information. Approaches reviewed include plasticization, blending with miscible polymers, and chemical modifications by esterification, etherification, polymer grafting, and copolymerization. Those lignin-based thermoplastic materials are expected to show applications as engineering plastics, polymeric foams, thermoplastic elastomers, and carbon-fiber precursors. PMID:27059111

  10. Lignin-Based Thermoplastic Materials.

    PubMed

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

    2016-04-21

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

  11. Comment on comment on ''acid precipitation in historical perspective and effects of acid precipitation''

    SciTech Connect

    Henriksen, A.; Richter, D.D.

    1984-01-01

    The author criticizes the fact that some soil scientists have difficulties in accepting that lakes and stream waters have become acid due to acid rain, because the natural production of acidity in ecosystems is large compared to the contribution from acid rain. He points out that Richter concludes that many of the reported changes, where real, may well result from natural processes with relatively minor contributions from acid precipitation. The author also disagrees with Krug and Frink who recently suggested that SO/sub 4/ from acid rain is exchanged with organic anions originally present in the water, leaving pH essentially unchanged. The author rebuts Henriksen who he says appears to have misunderstood the intent of the original correspondence, which was not to document evidence but rather to assert two generalities; (1) adverse effects of acid deposition on ecosystems are commonly overstated, and (2) the biogeochemistry of ecosystems is easily oversimplified, and natural sources of acidity are often ignored.

  12. Lignin valorization: improving lignin processing in the biorefinery.

    PubMed

    Ragauskas, Arthur J; Beckham, Gregg T; Biddy, Mary J; Chandra, Richard; Chen, Fang; Davis, Mark F; Davison, Brian H; Dixon, Richard A; Gilna, Paul; Keller, Martin; Langan, Paul; Naskar, Amit K; Saddler, Jack N; Tschaplinski, Timothy J; Tuskan, Gerald A; Wyman, Charles E

    2014-05-16

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

  13. Lignin Valorization: Improving Lignin Processing in the Biorefinery

    SciTech Connect

    Ragauskas, Arthur; Beckham, Gregg; Biddy, Mary J; Chandra, Richard; Chen, Fang; Davis, Dr. Mark F.; Davison, Brian H; Dixon, Richard; Gilna, Paul; Keller, Martin; Langan, Paul; Naskar, Amit K; Saddler, Jack N; Tschaplinski, Timothy J; Tuskan, Gerald A; Wyman, Charles E,; Harber, Karen S

    2014-01-01

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

  14. NAPAP (National Acid Precipitation Assessment Program) results on acid rain

    SciTech Connect

    Not Available

    1990-06-01

    The National Acid Precipitation Assessment Program (NAPAP) was mandated by Congress in 1980 to study the effects of acid rain. The results of 10 years of research on the effect of acid deposition and ozone on forests, particularly high elevation spruce and fir, southern pines, eastern hardwoods and western conifers, will be published this year.

  15. Acid Precipitation Awareness Curriculum Materials in the Life Sciences.

    ERIC Educational Resources Information Center

    Stubbs, Harriett S.

    1983-01-01

    Provides an outline of course content for acid precipitation and two acid rain activities (introduction to pH and effects of acid rain on an organism). Information for obtaining 20 additional activities as well as an information packet containing booklets, pamphlets, and articles are also provided. (JN)

  16. Teacher's Resource Guide on Acidic Precipitation with Laboratory Activities.

    ERIC Educational Resources Information Center

    Barrow, Lloyd H.

    The purpose of this teacher's resource guide is to help science teachers incorporate the topic of acidic precipitation into their curricula. A survey of recent junior high school science textbooks found a maximum of one paragraph devoted to the subject; in addition, none of these books had any related laboratory activities. It was on the basis of…

  17. Preparation and Analysis of Biomass Lignins

    SciTech Connect

    Compere, A L; Griffith, William {Bill} L

    2009-01-01

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

  18. Preparation and Analysis of Biomass Lignins

    NASA Astrophysics Data System (ADS)

    Compere, Alicia L.; Griffith, William L.

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

  19. Characterisation of Dyp-type peroxidases from Pseudomonas fluorescens Pf-5: Oxidation of Mn(II) and polymeric lignin by Dyp1B.

    PubMed

    Rahmanpour, Rahman; Bugg, Timothy D H

    2015-05-15

    Members of the DyP family of peroxidases in Gram-positive bacteria have recently been shown to oxidise Mn(II) and lignin model compounds. Gram-negative pseudomonads, which also show activity for lignin oxidation, also contain dyp-type peroxidase genes. Pseudomonas fluorescens Pf-5 contains three dyp-type peroxidases (35, 40 and 55kDa), each of which has been overexpressed in Escherichia coli, purified, and characterised. Each of the three enzymes shows activity for oxidation of phenol substrates, but the 35kDa Dyp1B enzyme also shows activity for oxidation of Mn(II) and Kraft lignin. Treatment of powdered lignocellulose with Dyp1B in the presence of Mn(II) and hydrogen peroxide leads to the release of a low molecular weight lignin fragment, which has been identified by mass spectrometry as a β-aryl ether lignin dimer containing one G unit and one H unit bearing a benzylic ketone. A mechanism for release of this fragment from lignin oxidation is proposed.

  20. Acidic precipitation: a technical amplification of NAPAP's findings

    SciTech Connect

    Lefohn, A.S.; Krupa, S.V.

    1988-06-01

    In September 1987, NAPAP released a 4-volume, 925 page interim report that summarized the effects of acidic precipitation on crops, forests, aquatic ecosystems, visibility, and human health. Following the release of the report, APCA coordinated an international conference to provide a forum for the technical amplification of the conclusions reached in NAPAP's report. Scientists from the United States and Canada were invited to participate in the conference. The focus of the meeting was concerned only with the technical aspects of the NAPAP report. At the conference, there were important research concepts presented that may require further attention before definitive, bottom line statements can be made concerning the effects of acid precipitation on the environment. The purpose of this paper is to summarize the key technical points made at the conference and provide NAPAP with additional scientific inputs as it begins to prepare for its 1990 Final Assessment Report.

  1. Acid precipitation--effects on trace elements and human health.

    PubMed

    Gerhardsson, L; Oskarsson, A; Skerfving, S

    1994-08-22

    Environmental pollution by acid precipitation increases the solubilization and mobilization of toxic metals. Through the food chain, this may alter the intake of toxic and essential elements in man. Potential adverse health effects could follow after increased human exposure. For the general population, the exposure pattern and health effects caused by aluminium, cadmium, lead and mercury are of particular concern. Although there are several indications that the exposure to toxic elements (e.g. aluminium, cadmium, lead and methylmercury), as well as the intake of essential elements (e.g. selenium), may be affected by acid precipitation, there is presently no firm evidence of adverse health effects in man. However, the present data clearly indicate that the safety margins are small. Thus, the ongoing acidification in many areas must be stopped before such effects become evident. The effects on trace element status and human health by acid precipitation were discussed at the ISTERH (International Society for Trace Element Research in Humans) Conference in Stockholm, May, 1992. The main findings are briefly summarized here.

  2. Acidic precipitation, Vol. 2: Biological and ecological effects

    SciTech Connect

    Adriano, D.C.; Johnson, A.H.

    1989-01-01

    Acidic precipitation has its origin in emissions to the atmosphere of numerous compounds from both natural and man-made sources. The chapters in this volume cover a wide array of topics on the biological and ecological effects of acidic precipitation. A chapter on soil productivity emphasizes changes in biological and chemical characters of forest soils impacted by acidic deposition. Additional chapters discuss specific effects on soil microorganisms, trees, and crops. The importance of aluminum in this environmental issue is highlighted by a discussion on the mobility and phytotoxicity of this element in acidic soils. This chapter puts into perspective the biology of Al stressed plants. Two major chapters discuss the effect of acidic precipitation on forest ecosystems; one emphasizing North America, and the other Europe. Effects of soil acidification on key soil processes, including litter decomposition and depletion of essential plant nutrients in the soil profile are emphasized. Finally, three major chapters comprehensively cover limnological ecosystems and their response to acidic perturbation. These chapters discuss the response of stream and lake communities, both floral and faunal, to water acidification, including reduced biodiversity in these systems. Ten chapters have been processed separately for inclusion in the appropriate data bases.

  3. Impact of effects of acid precipitation on toxicity of metals.

    PubMed

    Nordberg, G F; Goyer, R A; Clarkson, T W

    1985-11-01

    Acid precipitation may increase human exposure to several potentially toxic metals by increasing metal concentrations in major pathways to man, particularly food and water, and in some instances by enhancing the conversion of metal species to more toxic forms. Human exposures to methylmercury are almost entirely by way of consumption of fish and seafood. In some countries, intakes by this route may approach the levels that can give rise to adverse health effects for population groups with a high consumption of these food items. A possible increase in methylmercury concentrations in fish from lakes affected by acid precipitation may thus be of concern to selected population groups. Human exposures to lead reach levels that are near those associated with adverse health effects in certain sensitive segments of the general population in several countries. The possibility exists that increased exposures to lead may be caused by acid precipitation through a mobilization of lead from soils into crops. A route of exposure to lead that may possibly be influenced by acid precipitation is an increased deterioration of surface materials containing lead and a subsequent ingestion by small children. A similar situation with regard to uptake from food exists for cadmium (at least in some countries). Human metal exposures via drinking water may be increased by acid precipitation. Decreasing pH increases corrosiveness of water enhancing the mobilization of metal salts from soil; metallic compounds may be mobilized from minerals, which may eventually reach drinking water. Also, the dissolution of metals (Pb, Cd, Cu) from piping systems for drinking water by soft acidic waters of high corrosivity may increase metal concentrations in drinking water. Exposures have occasionally reached concentrations which are in the range where adverse health effects may be expected in otherwise healthy persons. Dissolution from piping systems can be prevented by neutralizing the water before

  4. Acidic precipitation: considerations for an air-quality standard

    SciTech Connect

    Evans, L.S.; Hendrey, G.R.; Stensland, G.J.; Johnson, D.W.; Francis, A.J.

    1980-01-01

    Acidic precipitation, wet or frozen deposition with a hydrogen ion concentration greatern than 2.5 ..mu..eq l/sup -1/ is a significant air pollution problem in the United States. The chief anions accounting for the hydrogen ions in rainfall are nitrate and sulfate. Agricultural systems are more likely to derive net nutritional benefits from increasing inputs of acidic rain than are forest systems when soils alone are considered. Agricultural soils may benefit because of the high N and S requirements of agricultural plants. Detrimental effects to forest soils may result if atmospheric H/sup +/ inputs significantly add to or exceed H/sup +/ production by soils. Acidification of fresh waters of southern Scandinavia, southwestern Scotland, southeastern Canada, and northeastern United States is caused by acid deposition. Areas of these regions in which this acidification occurs have in common, highly acidic precipitation with volume weighted mean annual H/sup +/ concentrations of 25 ..mu..eq l/sup -1/ or higher and slow weathering granitic or precambrian bedrock with thin soils deficient in minerals which would provide buffer capacity. Biological effects of acidification of fresh waters are detectable below pH 6.0. As lake and stream pH levels decrease below pH. 6.0, many species of plants, invertebrates, and vertebrates are progressively eliminated. Generally, fisheries are impacted below pH 5.0 and are completely destroyed below pH 4.8. There are few studies that document effects of acidic precipitation on terrestrial vegetation to establish an air quality standard. It must be demonstrated that current levels of precipitation acidity alone significantly injure terrestrial vegetation. In terms of documented damanges, current research indicates that establishing a standard for precipitation for the volume weighted annual H/sup +/ concentration at 25 ..mu..eq l/sup -1/ may protect the most sensitive areas from permanent lake acidification.

  5. Acid precipitation impacts on agricultural soil management practices

    SciTech Connect

    Moskowitz, P.D.; Medeiros, W.H.; Coveney, E.A.; Lewin, K.F.; Rosenthal, R.E.

    1986-02-01

    Acid precipitation can have positive (reduced nitrogen fertilizer requirements) and negative (increased need to neutralize soil acidity) impacts on agricultural soil management practices. This paper compares the total annual deposition of nitrogen in acid precipitation with farmer applied fertilizer use and with nitrogen uptake for major crops. It also estimates the amount of lime needed to neutralize soil acidity originating from wet H/sup +/ deposition. First-order estimates indicate that the quantity of nitrogen annually deposited in the eastern US by wet acid deposition on croplands is 6% of the amount applied as fertilizer. Nitrogen deposited as wet deposition may be relatively important to unmanaged nonleguminous crops (e.g., hay) which are grown over extensive land areas. Soil acidity, which can be increased by natural (e.g., nitrogen fixation) and anthropogenic mechanisms (e.g., fertilizer application, acidic deposition) is often neutralized by the application of lime. Estimates indicate that in the eastern US, approx.2% of applied lime is used to neutralize acidity caused by wet acid deposition.

  6. Ten-year study on acid precipitation nears conclusion

    SciTech Connect

    Olem, H. )

    1990-04-01

    Results from the National Acid Precipitation Assessment Program (NAPAP) are discussed. Final results are contained in 26 state of the science reports. Seven of the reports provide information on acid rain and aquatic ecosystems. They describe the current state of acidic surface waters, watershed processes affecting surface water chemistry, historical evidence for surface water acidification, methods for forecasting future changes, and the response of acidic surface water to liming. Six areas of the country were found to be of special interest: southwest Adirondacks, New England, forested areas of the mid-Atlantic highlands, the Atlantic coastal plain, the northern Florida highlands, parts of northeastern Wisconsin and the Upper Peninsula of Michigan. Environmental effects, mitigation efforts and possible legislation are briefly discussed.

  7. Potential impact of acid precipitation on arsenic and selenium.

    PubMed Central

    Mushak, P

    1985-01-01

    The potential impact of acidic precipitation on the environmental mobility of the metalloids arsenic (As) and selenium (Se) has not been given much attention and is poorly understood. As with other elements, the interest here is the potential effect of environmental acidification on environmental behavior in ways that are relevant to human exposure to these metalloids. Available information on acid precipitation and the environmental behavior of these metalloids do, however, permit some preliminary conclusions to be drawn. Both As and Se appear to be mobilized from household plumbing into tap water by the corrosive action of soft, mildly acidic water, while surface water catchment systems in areas impacted by acidic deposition may contain elevated soluble As levels. Acidification of aquatic ecosystems that are drinking water sources may pose the prospect of enhanced release of As from sediment to water as well as reduction in water levels of Se. Acidification of ground waters, where As appears to be especially mobile, is of particular concern in this regard. The potential impact of acidic deposition on As and Se in soils cannot readily be assessed with respect to human exposure, but it would appear that the behavior of these metalloids in poorly buffered, poorly immobilizing soils, e.g., sandy soils of low metal hydrous oxide content, would be most affected. The effect is opposite for the two elements; lowered pH would appear to enhance As mobility and to reduce Se availability. Altered acidity of both soil and aquatic systems poses a risk for altered biotransformation processes involving both As and Se, thereby affecting the relative amounts of different chemical forms varying in their toxicity to humans as well as influencing biogeochemical cycling. PMID:4076075

  8. Potential impact of acid precipitation on arsenic and selenium.

    PubMed

    Mushak, P

    1985-11-01

    The potential impact of acidic precipitation on the environmental mobility of the metalloids arsenic (As) and selenium (Se) has not been given much attention and is poorly understood. As with other elements, the interest here is the potential effect of environmental acidification on environmental behavior in ways that are relevant to human exposure to these metalloids. Available information on acid precipitation and the environmental behavior of these metalloids do, however, permit some preliminary conclusions to be drawn. Both As and Se appear to be mobilized from household plumbing into tap water by the corrosive action of soft, mildly acidic water, while surface water catchment systems in areas impacted by acidic deposition may contain elevated soluble As levels. Acidification of aquatic ecosystems that are drinking water sources may pose the prospect of enhanced release of As from sediment to water as well as reduction in water levels of Se. Acidification of ground waters, where As appears to be especially mobile, is of particular concern in this regard. The potential impact of acidic deposition on As and Se in soils cannot readily be assessed with respect to human exposure, but it would appear that the behavior of these metalloids in poorly buffered, poorly immobilizing soils, e.g., sandy soils of low metal hydrous oxide content, would be most affected. The effect is opposite for the two elements; lowered pH would appear to enhance As mobility and to reduce Se availability. Altered acidity of both soil and aquatic systems poses a risk for altered biotransformation processes involving both As and Se, thereby affecting the relative amounts of different chemical forms varying in their toxicity to humans as well as influencing biogeochemical cycling.

  9. Impact of acid precipitation on recreation and tourism in Ontario: an overview

    SciTech Connect

    Not Available

    1984-01-01

    The impacts of acid precipitation on fishing opportunities, waterfowl and moose hunting, water contact activities, and the perception of the environment in Ontario are analyzed. Economic effects and future research needs are also estimated and discussed. These questions have been examined by identifying the likely links between acidic precipitation and recreation and tourism, by developing estimates of the importance of aquatic-based recreation and tourism, by describing the current and estimated future effects of acid precipitation. 101 references, 9 figures, 19 tables.

  10. Bacterial extracellular lignin peroxidase

    DOEpatents

    Crawford, Donald L.; Ramachandra, Muralidhara

    1993-01-01

    A newly discovered lignin peroxidase enzyme is provided. The enzyme is obtained from a bacterial source and is capable of degrading the lignin portion of lignocellulose in the presence of hydrogen peroxide. The enzyme is extracellular, oxidative, inducible by lignin, larch wood xylan, or related substrates and capable of attacking certain lignin substructure chemical bonds that are not degradable by fungal lignin peroxidases.

  11. ''The control of lignin synthesis''

    SciTech Connect

    Carlson, John E.

    2005-04-07

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

  12. Unravelling lignin formation and structure

    SciTech Connect

    Lewis, N.G. . Inst. of Biological Chemistry)

    1991-01-01

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

  13. Creation of degenerative copolymers and plastics of lignin

    SciTech Connect

    Meister, J.J.; Chen, M.J.; McNichols, W.

    1995-12-01

    Polymers and plastics which degrade under environmental conditions can be made by graft copolymerization on lignin. The reaction can be run by solution, bulk, and precipitation polymerization. Poly(lignin-g-(1-phenylethylene)) and poly(lignin-g-(1-methyl-l-(1-oxo-2-oxypropyl)ethylene)) can be made by combining lignin, monomer, calcium chloride, and a hydroperoxide in such solvents as 1-methyl-2-pyrrolidinone, dimethylsulfoxide, dimethylacetamide, dimethylformamide, pyridine, or water-polar organic solvent mixtures. The products contain 4 to 50 wt. percent lignin with the rest of the material being polymeric sidechain if the copolymer is properly purified. Properties of the products depend on and are controlled by the sidechain attached to the lignin. Properties such as solubility, tensile strength, surface activity, glass transition temperature, and modulus can be altered by altering the sidechain structure and length.

  14. Specific lignin accumulation in granulated juice sacs of Citrus maxima.

    PubMed

    Wu, Jia-Ling; Pan, Teng-Fei; Guo, Zhi-Xiong; Pan, Dong-Ming

    2014-12-17

    Juice sac granulation occurring in pummelo fruits [Citrus maxima (Burm.) Merr.] is an undesirable trait, and the underlying mechanism remains unresolved. Previous studies have shown that lignin metabolism is closely associated with the process of juice sac granulation. Here, a method suitable for lignin isolation from pummelo tissues is established. Acetylated lignins from different pummelo tissues and cultivars were analyzed by HSQC NMR. The results showed that lignins in granulated juice sacs were characterized by an extremely high abundance of guaiacyl units (91.13-96.82%), in contrast to lignins from other tissues, including leaves, stems, and segment membranes. The abnormally accumulated lignins in granulated juice sacs were specific and mainly polymerized from coniferyl alcohol. No significant difference was found in lignin types among various cultivars. These findings indicated that the mechanism of juice sac granulation might be similar among various cultivars, although very different degrees of juice sac granulation can be observed.

  15. Sequestration and Transport of Lignin Monomeric Precursors

    SciTech Connect

    Liu, C.J.; Miao, Y.-C.; Zhang, K.-W.

    2011-01-18

    Lignin is the second most abundant terrestrial biopolymer after cellulose. It is essential for the viability of vascular plants. Lignin precursors, the monolignols, are synthesized within the cytosol of the cell. Thereafter, these monomeric precursors are exported into the cell wall, where they are polymerized and integrated into the wall matrix. Accordingly, transport of monolignols across cell membranes is a critical step affecting deposition of lignin in the secondarily thickened cell wall. While the biosynthesis of monolignols is relatively well understood, our knowledge of sequestration and transport of these monomers is sketchy. In this article, we review different hypotheses on monolignol transport and summarize the recent progresses toward the understanding of the molecular mechanisms underlying monolignol sequestration and transport across membranes. Deciphering molecular mechanisms for lignin precursor transport will support a better biotechnological solution to manipulate plant lignification for more efficient agricultural and industrial applications of cell wall biomass.

  16. Lignin profiling in extracted xylans by size-exclusion chromatography.

    PubMed

    Hutterer, Christian; Schild, Gabriele; Kliba, Gerhard; Potthast, Antje

    2016-10-20

    Utilization of the polymeric parts of lignocellulose is expected to gain increasing importance in future biorefinery scenarios. In that respect, a particular focus is placed on hemicelluloses from different wood species gained from an industrially feasible upgrading step in the production of dissolving pulps from paper pulps. During alkaline post-extractions for hemicellulose removal, residual lignins are extracted as well. They are either covalently linked to the extracted hardwood xylans or simply co-dissolved in the alkaline lye. In order to better describe the lignin in xylan containing lyes, a method for lignin profiling was set up by hyphenating size-exclusion chromatography of xylans with UV detection which facilitates visualization of the residual lignin distribution. Simultaneous lignin quantification was achieved with lignin standards prepared from Kraft cooking liquors. The setup presented may serve as advanced characterization for novel xylan products. PMID:27474629

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

    PubMed

    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.

  18. Chemical linkage of pine polysaccharides to lignin

    SciTech Connect

    Minor, J.L.

    1982-01-01

    Methylation analysis was used to investigate the bonds to lignin of the carbohydrates remaining after enzymatic hydrolysis and alkaline reduction of ball-milled loblolly pine wood and red pine compression wood. The carbohydrates exist as oligomeric chains with degrees of polymerization of 7-14. Approximately one sugar unit per oligomer chain is bonded to lignin. Bonding at C-6 of the hexose units if favored, and the arabinose is bonded exclusively at C-5. Galactan and arabinan are structurally of the so-called ''pectin group substances''. 16 references.

  19. Modulating lignin in plants

    SciTech Connect

    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.

  20. National Acid Precipitation Assessment Program annual report, 1988, to the President and Congress

    SciTech Connect

    Not Available

    1989-01-13

    The Acid Precipitation Act of 1980 (Title VII of the Energy Security Act of 1980, Public Law 96-294) established the Interagency Task Force on Acid Precipitation to develop and implement the National Acid Precipitation Assessment Program (NAPAP). The purpose of NAPAP is to increase the authors understanding of the causes and effects of acidic deposition, and to produce scientific information to support decisionmaking regarding acidic deposition control and abatement strategies. The Report, the Program's seventh, is divided into three major sections. The first section describes the Program's organizational structure, external coordination activities, peer reviews, and budgetary status. It also includes a discussion of the NAPAP assessment process, and provides a synopsis of NAPAP's plan and schedule for 1989 and 1990 assessment reports.

  1. Considerations of an air-quality standard to protect terrestrial vegetation from acidic precipitation

    SciTech Connect

    Evans, L.S.

    1981-01-01

    Studies on the effects of acidic precipitation which is here defined as wet or frozen deposition with a hydrogen ion concentration greater than 2.5 ..mu..eq 1/sup -1/, are reviewed. At the present time there is an inadequate amount of information that shows decreases in crop growth except for one field study. Most studies with plants (crops and forests) are inadequate for standard setting because they are not conducted in the field with adequate randomization of plots coupled with rigorous statistical analyses. Although visible injury to foliage has been documented in a variety of greenhouse studies, no experimental evidence demonstrates loss of field crop value or reduction in plant productivity due to visible foliar injury. Acidic precipitation can contribute nutrients to vegetation and could also influence leaching rates of nutrients from vegetation. Although these processes occur, there are no data that show changes in nutrient levels in foliage that relate to crop or natural ecosystem productivity. Experimental results show that fertilization of ferns is inhibited by current levels of acidic precipitation in the northeastern United States. However, the overall impacts of inhibited fertilization on perpetuation of the species or ecosystem productivity have not been evaluated. Simulated acidic precipitation has been shown to effect plant pathogens in greenhouse and field experiments. Simulated acidic precipitation inhibited pathogen activities under some circumstances and promoted pathogen activities under other circumstances. No conclusion can be drawn about the effects of current levels of precipitation acidity on plant pathogen-host interactions. From these data it must be concluded that research on the effects of acidic precipitation on terrestrial vegetation is too meager to draw any conclusions with regard to an air quality standard.

  2. Deciphering the Enigma of Lignification: Precursor Transport, Oxidation, and the Topochemistry of Lignin Assembly

    SciTech Connect

    Liu C. J.

    2012-03-01

    Plant lignification is a tightly regulated complex cellular process that occurs via three sequential steps: the synthesis of monolignols within the cytosol; the transport of monomeric precursors across plasma membrane; and the oxidative polymerization of monolignols to form lignin macromolecules within the cell wall. Although we have a reasonable understanding of monolignol biosynthesis, many aspects of lignin assembly remain elusive. These include the precursors transport and oxidation, and the initiation of lignin polymerization. This review describes our current knowledge of the molecular mechanisms underlying monolignol transport and oxidation, discusses the intriguing yet least-understood aspects of lignin assembly, and highlights the technologies potentially aiding in clarifying the enigma of plant lignification.

  3. Acid Precipitation Learning Materials: Science, Environmental and Social Studies, Grades 6-12.

    ERIC Educational Resources Information Center

    Hessler, Edward W.

    The major environmental problem of acid precipition is addressed through a series of activities contained in this guide for teachers of grades 6 through 12. Exercises are provided to help students learn science inquiry skills, facts, and concepts while focusing on the acid rain situation. Activities are organized by content areas. These include:…

  4. Lignin oxidation and pulp delignification by laccase and mediators

    SciTech Connect

    Bourbonnais, R.; Paice, M.G.; Reid, I.D.

    1996-10-01

    The phenol oxidizing enzyme laccase is produced abundantly by the lignin-degrading fungus Trametes versicolor. We found previously that laccase can oxidize veratryl alcohol and other non-phenolic lignin model compounds when a mediator such as 2,2{prime}-azinobis(3-ethylbenzthiazoline-5-sulphonate) (ABTS) was present. The laccase/mediator couple was also shown to be effective for delignification of kraft pulps. Two different isozymes of laccase produced by this fungus were purified and their reactivities towards lignins and kraft pulps were studied. The mediator ABTS was shown to be essential for pulp delignification and to reverse the polymerization of kraft lignin by either laccase. Pulp delignification with laccase and ABTS was also optimized. resulting in up to 55% lignin removal from kraft pulp following sequential enzyme treatments and alkaline extractions. Several variables were surveyed including enzyme and mediator dosage, oxygen pressure, temperature, reaction time, and pH.

  5. Conformations of Low-Molecular-Weight Lignin Polymers in Water.

    PubMed

    Petridis, Loukas; Smith, Jeremy C

    2016-02-01

    Low-molecular-weight lignin binds to cellulose during the thermochemical pretreatment of biomass for biofuel production, which prevents the efficient hydrolysis of the cellulose to sugars. The binding properties of lignin are influenced strongly by the conformations it adopts. Here, we use molecular dynamics simulations in aqueous solution to investigate the dependence of the shape of lignin polymers on chain length and temperature. Lignin is found to adopt collapsed conformations in water at 300 and 500 K. However, at 300 K, a discontinuous transition is found in the shape of the polymer as a function of the chain length. Below a critical degree of polymerization, Nc =15, the polymer adopts less spherical conformations than above Nc. The transition disappears at high temperatures (500 K) at which only spherical shapes are adopted. An implication relevant to cellulosic biofuel production is that lignin will self-aggregate even at high pretreatment temperatures.

  6. Conformations of low-molecular-weight lignin polymers in water

    DOE PAGES

    Petridis, Loukas; Smith, Jeremy C.

    2016-01-13

    Low-molecular-weight lignin binds to cellulose during the thermochemical pretreatment of biomass for biofuel production, which prevents the efficient hydrolysis of the cellulose to sugars. The binding properties of lignin are influenced strongly by the conformations it adopts. Here, we use molecular dynamics simulations in aqueous solution to investigate the dependence of the shape of lignin polymers on chain length and temperature. Lignin is found to adopt collapsed conformations in water at 300 and 500 K. However, at 300 K, a discontinuous transition is found in the shape of the polymer as a function of the chain length. Below a criticalmore » degree of polymerization, Nc=15, the polymer adopts less spherical conformations than above Nc. The transition disappears at high temperatures (500 K) at which only spherical shapes are adopted. As a result, an implication relevant to cellulosic biofuel production is that lignin will self-aggregate even at high pretreatment temperatures.« less

  7. Production of chelating agents through the enzymatic oxidation of acetosolv sugarcane bagasse lignin.

    PubMed

    Gonçalves, Adilson R; Soto-Oviedo, Mauro A

    2002-01-01

    Oxidation of lignin obtained from Acetosolv pulping of sugarcane bagasse was performed by polyphenoloxidase (PPO) using glycerol or polyethyleneglycol to increase the number of carbonyl and hydroxyl groups in lignin, and to improve its chelating capacity. Increase in the absorption in UV-spectrum related to alpha-carbonylphenolic and alpha,beta-unsaturated structures was observed in all the experiments. The chelating properties of the original and oxidized lignins were compared by monitoring the amount of Cu2+ bound to lignin by gel permeation chromatography. The chelating capacity of original Acetosolv lignin was 354 mg Cu2+/g lignin. On the other hand, lignin oxidized with PPO/O2 showed an increase of 73% in chelating capacity in relation to the original lignin. The chelating capacity of lignin oxidized with PPO/O2/glycerol was 110% higher than that of the original lignin. Glycerol stabilizes PPO, increasing its half-life. Average molecular weight (MW), measured by size-exclusion chromatography, was smaller for the oxidized lignins than for the original Acetosolv lignin. This result suggests that quinones can eventually be formed through the action of PPO, but are not polymerized. The chelating capacity of oxidized lignins increases with the incorporation of vicinal hydroxyl groups. PMID:12018263

  8. Coexistence but Independent Biosynthesis of Catechyl and Guaiacyl/Syringyl Lignin Polymers in Seed Coats[W][OPEN

    PubMed Central

    Tobimatsu, Yuki; Chen, Fang; Nakashima, Jin; Escamilla-Treviño, Luis L.; Jackson, Lisa; Dixon, Richard A.; Ralph, John

    2013-01-01

    Lignins are phenylpropanoid polymers, derived from monolignols, commonly found in terrestrial plant secondary cell walls. We recently reported evidence of an unanticipated catechyl lignin homopolymer (C lignin) derived solely from caffeyl alcohol in the seed coats of several monocot and dicot plants. We previously identified plant seeds that possessed either C lignin or traditional guaiacyl/syringyl (G/S) lignins, but not both. Here, we identified several dicot plants (Euphorbiaceae and Cleomaceae) that produce C lignin together with traditional G/S lignins in their seed coats. Solution-state NMR analyses, along with an in vitro lignin polymerization study, determined that there is, however, no copolymerization detectable (i.e., that the synthesis and polymerization of caffeyl alcohol and conventional monolignols in vivo is spatially and/or temporally separated). In particular, the deposition of G and C lignins in Cleome hassleriana seed coats is developmentally regulated during seed maturation; C lignin appears successively after G lignin within the same testa layers, concurrently with apparent loss of the functionality of O-methyltransferases, which are key enzymes for the conversion of C to G lignin precursors. This study exemplifies the flexible biosynthesis of different types of lignin polymers in plants dictated by substantial, but poorly understood, control of monomer supply by the cells. PMID:23903315

  9. Acid Precipitation

    ERIC Educational Resources Information Center

    Likens, Gene E.

    1976-01-01

    Discusses the fact that the acidity of rain and snow falling on parts of the U.S. and Europe has been rising. The reasons are still not entirely clear and the consequences have yet to be well evaluated. (MLH)

  10. Pathways for Biomass-Derived Lignin to Hydrocarbon Fuels

    SciTech Connect

    Laskar, Dhrubojyoti; Yang, Bin; Wang, Huamin; Lee, Guo-Shuh J.

    2013-09-01

    Production of hydrocarbon fuel from biomass-derived lignin sources with current version of biorefinery infrastructure would significantly improve the total carbon use in biomass and make biomass conversion more economically viable. Thus, developing specialty and commodity products from biomass derived-lignin has been an important industrial and scientific endeavor for several decades. However, deconstruction of lignin’s complex polymeric framework into low molecular weight reactive moieties amenable for deoxygenation and subsequent processing into hydrocarbons has been proven challenging. This review offers a comprehensive outlook on the existing body of work that has been devoted to catalytic processing of lignin derivatives into hydrocarbon fuels, focusing on: (1) The intrinsic complexity and characteristic structural features of biomass-derived lignin; (2) Existing processing technologies for the isolation and depolymerization of bulk lignin (including detailed mechanistic considerations); (3) Approaches aimed at significantly improving the yields of depolymerized lignin species amenable to catalytic upgrading, and; (4) Catalytic upgrading, using aqueous phase processes for transforming depolymerized lignin to hydrocarbon derivatives. Technical barriers and challenges to the valorization of lignin are highlighted throughout. The central goal of this review is to present an array of strategies that have been reported to obtain lignin, deconstruct it to reactive intermediates, and reduce its substantial oxygen content to yield hydrocarbon liquids. In this regard, reaction networks with reference to studies of lignin model compounds are exclusively surveyed. Special attention is paid to catalytic hydrodeoxygenation, hydrogenolyis and hydrogenation. Finally, this review addresses important features of lignin that are vital to economic success of hydrocarbon production.

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

    PubMed Central

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

    2015-01-01

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

  12. Effect of simulated acid precipitation on algal fixation of nitrogen and carbon dioxide in forest soils

    SciTech Connect

    Chang, F.H.; Alexander, M.

    1983-01-01

    Three forest soils from areas exposed to acid precipitation were incubated for 21 days in the light to enhance the development of indigenous algae. The rates of nitrogen fixation (acetylene reduction) in the light and dark were significantly less if the soils were treated with simulated rain at pH 3.5 than at pH 5.6. The inhibition increased with increasing amounts of simulated rain at pH 3.5. The fixation of CO/sub 2/ in the light was significantly less in the three soils following their exposure to simulated precipitation at pH 3.5 than to the same solutions at pH 5.6, and the extent of suppression rose with increasing amounts of synthetic rain. It is suggested that algae in terrestrial ecosystems may be especially susceptible to acid precipitation.

  13. Acid precipitation. (Latest citations from the Selected Water Resources Abstracts database). Published Search

    SciTech Connect

    Not Available

    1993-07-01

    The bibliography contains citations concerning the causes, and ecological and economic consequences of acid precipitation and deposition. Emissions of sulfur and nitrogen compounds, loading rates at specific study sites, the role of buffering materials on the acidification of lakes and streams, and the effects on aquatic life are considered. The effects on soil chemistry and vegetation are also discussed. (Contains 250 citations and includes a subject term index and title list.)

  14. Exploring bacterial lignin degradation.

    PubMed

    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. PMID:24780273

  15. Effects of acid precipitation on cation transport in New Hampshire forest soils. Technical completion report

    SciTech Connect

    Cronan, C.S.

    1981-07-01

    This report describes the results of our investigation of the effects of regional acid precipitation on forest soils and watershed biogeochemistry in New England. The report provides descriptions of the following research findings: (1) acid precipitation may cause increased aluminum mobilization and leaching from soils to sensitive aquatic systems; (2) acid deposition may shift the historic carbonic acid/organic acid leaching regime in forest soils to one dominated by atmospheric H/sub 2/SO/sub 4/; (3) acid precipitation may accelerate nutrient cation leaching from forest soils and may pose a particular threat to the potassium resources of northeastern forested ecosystems; (4) while acid rain may pass through some coniferous canopies without being neutralized, similar inputs of acid rainfall to hardwood canopies may be neutralized significantly by Bronsted base leaching and by leaf surface ion exchange mechanisms; and (5) progressive acid dissolution of soils in the laboratory may provide an important tool for predicting the patterns of aluminum leaching from soils exposed to acid deposition.

  16. Peroxidases Bound to the Growing Lignin Polymer Produce Natural Like Extracellular Lignin in a Cell Culture of Norway Spruce

    PubMed Central

    Warinowski, Tino; Koutaniemi, Sanna; Kärkönen, Anna; Sundberg, Ilari; Toikka, Merja; Simola, Liisa Kaarina; Kilpeläinen, Ilkka; Teeri, Teemu H.

    2016-01-01

    Lignin, an important component of plant cell walls, is a polymer of monolignols derived from the phenylpropanoid pathway. Monolignols are oxidized in the cell wall by oxidative enzymes (peroxidases and/or laccases) to radicals, which then couple with the growing lignin polymer. We have investigated the characteristics of the polymerization reaction by producing lignin polymers in vitro using different oxidative enzymes and analyzing the structures formed with NMR. The ability of the enzymes to oxidize high-molecular-weight compounds was tested using cytochrome c as a substrate. The results support an idea that lignin structure is largely determined by the concentration ratios of the monolignol (coniferyl alcohol) and polymer radicals involved in the coupling reaction. High rate of the lignin polymer oxidation compared to monolignol oxidation leads to a natural-like structure. The high relative rate can be achieved by an open active site of the oxidative enzyme, close proximity of the enzyme with the polymeric substrate or simply by high enzymatic activity that consumes monolignols rapidly. Monolignols, which are oxidized efficiently, can be seen as competitive inhibitors of polymer oxidation. Our results indicate that, at least in a Norway spruce (Picea abies L. Karst.) cell culture, a group of apoplastic, polymer-oxidizing peroxidases bind to the lignin polymer and are responsible for production of natural-like lignin in cell suspension cultures in vivo, and also in vitro. The peroxidases bound to the extracellular lignin had the highest ability to bind to various cell wall polymers in vitro. Extracellular lignin contains pectin-type sugars, making them possible attachment points for these cationic peroxidases. PMID:27803704

  17. National Acid Precipitation Assessment Program: Acidic deposition: An inventory of non-Federal research, monitoring, and assessment information

    SciTech Connect

    Herrick, C.N.

    1990-01-01

    The Acid Precipitation Act of 1990 (Title VII of the Energy Security Act of 1980, P.L. 96-294) established the Interagency Task Force on Acid Precipitation to develop and implement the National Acid Precipitation Assessment Program (NAPAP). The information included in the document was provided to NAPAP's Task Group Leaders and State-of-Science and State-of-Technology authors in July 1989. The early release was intended to assure that the authors would be aware of the information at an early phase in the assessment production process.

  18. Lignin isolated from steam-exploded eucalyptus wood chips by phase separation and its affinity to Trichoderma reesei cellulase.

    PubMed

    Nonaka, Hiroshi; Kobayashi, Ai; Funaoka, Masamitsu

    2013-07-01

    Steam-exploded eucalyptus wood chips were treated with p-cresol and 72% sulfuric acid at ambient temperature. Steam-exploded lignin was isolated as acetone-soluble and diethyl ether-insoluble compounds from the cresol layer. The lignin extraction yield was only 47%, and the amount of cresol grafted to lignin was much less than that in the case of eucalyptus lignin without steam explosion. Clearly, the steam explosion process depolymerized native lignin, and simultaneously, promoted polymerization via labile benzyl positions. The steam-exploded eucalyptus lignin adsorbed more Trichoderma reesei cellulase; however, its enzymatic activity was less than that of eucalyptus lignin that did not undergo steam explosion. It is evident that pretreatment potentially affects the affinity between lignin and cellulase and the resultant saccharification efficiency.

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

    SciTech Connect

    Henry, Nathan; Harper, David; Dadmun, Mark D

    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.

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

    SciTech Connect

    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.

  1. Occurrence of acid precipitation on the West Coast of the United States

    SciTech Connect

    Powers, C.F.; Rambo, D.L.

    1981-01-01

    Compilation of published and unpublished data shows acid precipitation to be more widespread in the Pacific coastal states than is generally recognized. Although information is scattered and discontinuous, precipitation is definitely acidic in the Los Angeles Basin and north-central California and in the Puget Sound region in Washington. Acid-rain occurrences were observed in western and eastern Oregon, but data are inadequate for regional generalization. New stations currently being established in Washington and Oregon, largely in response to the recently renewed activity of Mount St. Helens, will greatly facilitate assessment of precipitation acidity in the Northwest.

  2. The occurrence of acid precipitation on the west coast of the United States.

    PubMed

    Powers, C F; Rambo, D L

    1981-06-01

    Compilation of published and unpublished data shows acid precipitation to be more widespread in the Pacific coastal states than is generally recognized. Although information is scattered and discontinuous, precipitation is definitely acidic in the Los Angeles Basin and north-central california, and in the Puget Sound region in Washington. Acid rain occurrences have been observed in western and eastern Oregon, but data are inadequate for regional generalization. New stations currently being established in Washington and Oregon, largely in resposnse to the recently renewed activity of Mount St. Helens, will greatly facilitate assessment of precipitation acidity in the Northwest.

  3. National Acid Precipitation Assessment Program annual report 1987 to the President and Congress

    SciTech Connect

    Not Available

    1988-04-01

    The document reports on 1987 research activities of the National Acid Precipitation Assessment Program (NAPAP). It outlines 1987 research highlights, future research activities, major deliverables, and the program's 1990 research objectives. Its seven substantive chapters cover NAPAP research in the areas of: Emissions and controls; Atmospheric chemistry; Atmospheric modeling and transport; Atmospheric deposition and air-quality monitoring; Terrestrial effects (on forests and crops); Aquatic effects; and Effects on materials and cultural resources. The document includes introductory materials on the National Program's organizational structure, efforts at research coordination, peer and program review activities, and budget. A complete listing of the program's 1987 publications is also included.

  4. Tunable Pickering emulsions with polymer-grafted lignin nanoparticles (PGLNs).

    PubMed

    Silmore, Kevin S; Gupta, Chetali; Washburn, Newell R

    2016-03-15

    activities, and polymer-nanoparticle interactions are critical for optimizing interfacial activities. Controlled radical polymerization is a powerful tool for polymer grafting that can leverage the intrinsic interfacial functions of lignin for the formation of Pickering emulsions.

  5. Effectiveness of coagulation and acid precipitation processes for the pre-treatment of diluted black liquor.

    PubMed

    Garg, Anurag; Mishra, I M; Chand, S

    2010-08-15

    The effectiveness of coagulation (using aluminium-based chemicals and ferrous sulfate) and acid precipitation (using H(2)SO(4)) processes for the pre-treatment of diluted black liquor obtained from a pulp and paper mill is reported. Commercial alum was found to be the most economical among all the aluminium and ferrous salts used as a coagulant. A maximum removal of chemical oxygen demand (COD) (ca. 63%) and colour reduction (ca. 90%) from the wastewater (COD = 7000 mg l(-1)) at pH 5.0 was obtained with alum. During the acid precipitation process, at pH < 5.0, significant COD reductions (up to 64%) were observed. Solid residue obtained from the alum treatment at a temperature of 95 degrees C showed much better (3 times) settling rate than that for the residue obtained after treatment with the same coagulant at a temperature of 25 degrees C. The settling curves had three parts, namely, hindered, transition and compression zones. Tory plots were used to determine the critical height of suspension-supernatant interface that is used in the design of a clarifier-thickener unit. High heating values and large biomass fraction of the solid residues can encourage the fuel users to use this waste derived sludge as a potential renewable energy source.

  6. A numerical simulation of the distribution of acid precipitation in Chongqing area of China

    NASA Astrophysics Data System (ADS)

    Lei, Xiao'en; Jia, Xinyuan; Yuan, Suzhen; Luo, Qiren; Chen, Silong; Xu, Yu

    1987-09-01

    A numerical model for the study of the regional acid precipitation is developed. The model consists of five parts: the distribution patterns of SO2 concentration, the mesoscale flow fields, the parameterization of SO2 transformation into SO{4/-}, the parameterization of precipitation scavenging process, and the relationship between SO2 content in precipitation and ground level concentration of SO2 in the air. The distribution of SO2, SO{2/-} and pH for all precipitations in Chongqing area during the period of July to October 1982 are simulated with the model. A comparison of the simulated results with experimental data shows that high SO2 concentration centres correspond to low pH centres. The source of the acid rain in Chongqing area is local air pollution which is due to the lower effective stack height, low wind velocity in the area, basin topography, and the use of coal with high sulphur content. The mechanism for the formation of the acid precipitation here may be different from that in the United States of America and the Western Europe, where acid rain appears in the area far from pollution source.

  7. Natural acidity of waters in podzolized soils and potential impacts from acid precipitation

    SciTech Connect

    Stednick, J.D.; Johnson, D.W.

    1982-01-01

    Nutrient movements through sites in southeast Alaska and Washington were documented to determine net changes in chemical composition of precipitation water as it passed through a forest soil and became stream-flow. These sites were not subject to acid precipitation (rainfall pH 5.8 to 7.2), yet soil water was acidified to 4.2 by natural organic acid-forming processes in the podzol soils. Organic acids precipitated in the subsoils, allowing a pH increase. Streamwater pH ranged from 6.5 to 7.2 indicating a natural buffering capacity that may exceed any additional acid input from acid rain. Precipitation composition was dominated by calcium, magnesium, sodium, and chloride due to the proximity of the ocean at the southeast Alaska site. Anionic constituents of the precipitation were dominated by bicarbonate at the Washington site. Soil podzolization processes concurrently increased solution color and iron concentrations in the litter and surface horizons leachates. The anion flux through the soil profile was dominated by chloride and sulfate at the southeast Alaska site, whereas at the Washington site anion flux appeared to be dominated by organic acids. Electroneutrality calculations indicated a cation deficit for the southeast Alaska site.

  8. Natural acidity of waters in podzolized soils and potential impacts from acid precipitation

    SciTech Connect

    Stednick, J.D.; Johnson, D.W.

    1982-01-01

    Nutrient movements through sites in southeast Alaska and Washington were documented to determine net changes in chemical composition of precipitation water as it passed through a forest soil and became stream flow. These sites were not subject to acid precipitation (rainfall pH 5.8 to 7.2), yet soil water was acidified to 4.2 by natural organic acid forming processes in the podzol soils. Organic acids precipitated in the subsoils, allowing a pH increase. Stream water pH ranged from 6.5 to 7.2 indicating a natural buffering capacity that may exceed any additional acid input from acid rain. Precipitation composition was dominated by magnesium, sodium, and chloride due to the proximity of the ocean at the southeast Alaska site. Anionic constituents of the precipitation were dominated by bicarbonate at the Washington site. Soil podzolization processes concurrently increased solution color and iron concentrations in the litter and surface horizons leachates. The anion flux through the soil profile was dominated by chloride and sulfate at the southwast Alaska site, whereas at the Washington site anion flux appeared to be dominated by organic acids. Electroneutrality calculations indicated a cation deficit for the southeast Alaska site. 10 references, 2 tables.

  9. Effect of atmospheric sulfur pollutants derived from acid precipitation on the benthic dynamics of lakes

    SciTech Connect

    Mitchell, M.J.

    1982-11-01

    Sulfuric acid is a major contributor to acid precipitation in the United States. The relationship of acid precipitation to the sulfur dynamics of three lakes in New York was studied. For South Lake, which has probably been acidified, the sulfur profile in the sediment corresponded to historical changes in anthropogenic sulfur inputs. In all three study lakes, the organic sulfur constituents, which generally have been ignored in limnological investigations, played a major role in sulfur dynamics. The transformations and fluxes of inorganic and organic sulfur differed among the lakes and reflected characteristic abiotic and biotic properties, including productivity parameters. The community structure and secondary production of the invertebrate benthos were ascertained and, for South Lake, were similar to other acidified lakes. The importance of benthic insects on sulfur dynamics was demonstrated. Further studies on sulfur in lakes will enhance the understanding of the role of these anthropogenic inputs on lake systems and permit a more accurate appraisal of the present and future impacts of acidic deposition on water quality. 10 references.

  10. The acid precipitation provisions of the 1990 Clean Air Act Amendments and minorities' energy consumption

    SciTech Connect

    Nieves, L.A.; Wernette, D.

    1991-01-01

    In November 1990 Congress passed a comprehensive set of amendments to the Clean Air Act of 1977 with potentially very high compliance costs. The provisions pertaining to control of acid precipitation have been specified with sufficient detail to examine their cost impacts. These provisions will require investment in emissions control technology, mainly by electric utilities. Production costs will increase due to the required investment, resulting in higher electricity prices. This paper examines the possible magnitude of these effects and whether there might be differential impacts on racial/ethnic minority groups. Differential impacts were considered a possibility because of the differences in the percentage of total income spent on energy by various population subgroups. In 1989, the Majority group (defined as non-Black, non-Hispanic) spent about three percent of household income on energy, while Blacks spent double that, six percent, and Hispanics spent about four percent. (The differences in income underlying these figures are greater, however, than the differences in energy expenditures). To address these issues, we compare projected electricity consumption and expenditures and total energy expenditures for Black, Hispanic, and Majority households. The distribution of benefits from reducing acid precipitation is not addressed since the possible effects on ambient air quality in specific geographical areas that are directly attributable to reducing utilities' sulfur dioxide emissions are highly uncertain.

  11. The acid precipitation provisions of the 1990 Clean Air Act Amendments and minorities` energy consumption

    SciTech Connect

    Nieves, L.A.; Wernette, D.

    1991-12-31

    In November 1990 Congress passed a comprehensive set of amendments to the Clean Air Act of 1977 with potentially very high compliance costs. The provisions pertaining to control of acid precipitation have been specified with sufficient detail to examine their cost impacts. These provisions will require investment in emissions control technology, mainly by electric utilities. Production costs will increase due to the required investment, resulting in higher electricity prices. This paper examines the possible magnitude of these effects and whether there might be differential impacts on racial/ethnic minority groups. Differential impacts were considered a possibility because of the differences in the percentage of total income spent on energy by various population subgroups. In 1989, the Majority group (defined as non-Black, non-Hispanic) spent about three percent of household income on energy, while Blacks spent double that, six percent, and Hispanics spent about four percent. (The differences in income underlying these figures are greater, however, than the differences in energy expenditures). To address these issues, we compare projected electricity consumption and expenditures and total energy expenditures for Black, Hispanic, and Majority households. The distribution of benefits from reducing acid precipitation is not addressed since the possible effects on ambient air quality in specific geographical areas that are directly attributable to reducing utilities` sulfur dioxide emissions are highly uncertain.

  12. Fluorescence analyzer for lignin

    DOEpatents

    Berthold, John W.; Malito, Michael L.; Jeffers, Larry

    1993-01-01

    A method and apparatus for measuring lignin concentration in a sample of wood pulp or black liquor comprises a light emitting arrangement for emitting an excitation light through optical fiber bundles into a probe which has an undiluted sensing end facing the sample. The excitation light causes the lignin concentration to produce fluorescent emission light which is then conveyed through the probe to analyzing equipment which measures the intensity of the emission light. Measures a This invention was made with Government support under Contract Number DOE: DE-FC05-90CE40905 awarded by the Department of Energy (DOE). The Government has certain rights in this invention.

  13. Extracting lignins from mill wastes

    NASA Technical Reports Server (NTRS)

    Humphrey, M. F.

    1977-01-01

    Addition of quaternary ammonium compound and activated charcoal to pulp and mill wastes precipitates lignins in sludge mixture. Methanol dissolves lignins for separation from resulting slurry. Mineral acid reprecipitates lignins in filtered solution. Quaternary ammonium compound, activated charcoal, as well as water may be recovered and recycled from this process.

  14. Starch-Lignin Baked Foams

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Starch-kraft lignin foams were prepared by a baking process. Replacing up to 20% of the starch with lignin has no effect on foam density or overall morphology. At 10% replacement, lignin marginally increases water resistance and modulus of elasticity but decreases strain at maximum stress. At 20% re...

  15. Effects of acid precipitation on reproduction in alpine plant species. [Erythronium grandiflorum; Aquilegia caerulea

    SciTech Connect

    McKenna, M.A.; Hille-Salgueiro, M.; Musselman, R.C. Dept. of Agriculture, Fort Collins, CO )

    1990-01-01

    A series of experiments were designed to determine the impact of acid rain on plant reproductive processes, a critical component of a species life history. Research was carried out in herbaceous alpine communities at the USDA (United States Department of Agriculture) Forest Service Glacier Lakes Ecosystem Experiments Site in the Snowy Mts. of Wyoming. A range of species were surveyed to monitor the sensitivity of pollen to acidification during germination and growth, and all species demonstrated reduced in vitro pollen germination in acidified media. Field pollinations were carried out in Erythronium grandiflorum and Aquilegia caerulea to determine the reproductive success of plants exposed to simulated ambient precipitation (pH 5.6) or simulated acid precipitation (pH 3.6) prior to pollination. In Erythronium, no differences were observed in seed set and seed weight of fruits resulting from the two pollination treatments. In Aquilegia, fruits resulting from the acid spray treatment produced fewer seeds and lighter seeds.

  16. Evaluation of simulated acid precipitation effects on forest microcosms. Final report

    SciTech Connect

    Kelly, J.M.; Strickland, R.C.; Weatherford, F.P.; Noggle, J.C.

    1984-04-01

    Microcosms were treated for a 30-month period with simulated precipitation acidified to four pH levels (5.7, 4.5, 4.0, and 3.5) to evaluate the impact of acid precipitation on foliar leaching, plant nutrient content, soil leaching, soil nutrient content, and litter decomposition. Direct effects of acid precipitation on diameter growth, bud break, leaf senescence, chlorophyll content, stomatal size, stomatal density, photosynthesis, respiration, transpiration, and cuticle erosion were evaluated on tulip poplar, white oak, and Virginia pine seedlings growing as mixed stands in the microcosms. None of the plant physiological or morphological parameters evaluated responded in a statistically significant manner as a result of treatment. A significant treatment canopy interaction was observed in the form of a 60 percent increase in calcium input in throughfall in response to the pH 3.5 treatment. Foliar nutrient content did not change in response to treatment nor did field measurements of decomposer activity. Soil analysis indicated a significantly lower concentration of exchangeable calcium and magnesium in the top 3.5 cm of the mineral soil in association with the pH 3.5 treatment. Soil leachate concentrations exhibited significant increases at both the 25 and 50 cm depths. However, at the 100 cm depth no significant response in concentration or elemental loss from the system was observed. Laboratory respiration measurements indicated a small, but statistically significant reduction in decomposer activity in the lower litter (02) horizon. This reduction was masked in the field measurements of decomposer activity due to the relatively small contribution of the 02 to total soil respiration. 38 references, 12 figures, 18 tables.

  17. Microbial degradation of lignin-derived compounds under anaerobic conditions

    SciTech Connect

    Colberg, P.J.

    1983-01-01

    Lignin is the second most abundant form of organic carbon in the biosphere. Recent laboratory studies indicate that a large fraction of polymeric lignin is incompletely degraded by aerobic lignolytic microorganisms and is subsequently released as lignin fragments of reduced molecular size. If such lignin-derived compounds become available in the anaerobic environment, they may serve as potential sources of organic carbon for organisms which release methane precursors. The methanogenic bacteria, in turn, serve as terminal members of the anaerobic food chain, and thus, limit the accumulation of organic carbon in anaerobic sinks. This thesis presents evidence to suggest that lignin-derived compounds which have molecular sizes greater than those of single-ring aromatic compounds (MW > 200) are anaerobically biodegradable to methane. This research involved development of selective enrichment cultures capable of utilizing oligolignols as sole carbon sources. Radiolabeled water-soluble catabolites, released during aerobic lignin degradation by the white rot fungus Phanerochaete chrysosporium, were subjected to anaerobic degradation. The second phase of work involved capillary gas chromatographic analyses of enrichment cultures fed a /sup 14/C-labeled, lignin-derived substrate of average molecular weight 600. 2-Bromoethanesulfonic acid was used to inhibit methane formation and enhance buildup of metabolic intermediates, resulting in the accumulation of volatile fatty acids, phenylacetate, benzoate, catechol, 3-phenyl-propionate, vanillin, syringic acid, vanillic acid, ferulic acid, and caffeic acid. A conceptual model for the anaerobic degradation of two- and three-ring lignin fragments is proposed which overlaps both the ferulate and benzoate degradation pathways at the level of single-ring aromatic compounds.

  18. Lignin blockers and uses thereof

    SciTech Connect

    Yang, Bin; Wyman, Charles E.

    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.

  19. Fluorescence analyzer for lignin

    SciTech Connect

    Berthold, J.W.; Malito, M.L.; Jeffers, L.

    1993-06-01

    An apparatus for measuring lignin concentration with time resolved fluorescence in an undiluted wood pulp or black liquor sample, on a real-time, in situ basis is described, comprising: light source means for applying excitation light pulses at a selected wavelength and at known time intervals to the undiluted sample for causing the lignin concentration to produce fluorescent emission light with a fluorescence intensity that monotonically decreases in a quenched fluorescence regime; light detector means for measuring the emission light at the known time intervals and establishing signals indicative thereof; switching means for turning said light detector means on at precise specified time intervals after each excitation light pulse; and signal processing means connected to the light source means and the light detector means for comparing intensities of the emission light from the lignin in the quenched fluorescence regime to the intensities of the excitation light pulses on a time resolved basis for providing a measurement of the lignin concentration in the undiluted sample as a function of the time resolved emission light intensity.

  20. Biodegradation of lignin by fungi, bacteria and laccases.

    PubMed

    Asina, Fnu; Brzonova, Ivana; Voeller, Keith; Kozliak, Evguenii; Kubátová, Alena; Yao, Bin; Ji, Yun

    2016-11-01

    Indulin AT biodegradation by basidiomycetous fungi, actinobacteria and commercial laccases was evaluated using a suite of chemical analysis methods. The extent of microbial degradation was confirmed by novel thermal carbon analysis (TCA), as the treatments altered the carbon desorption and pyrolysis temperature profiles in supernatants. Laccase treatments caused only minor changes, though with increases occurring in the 850°C and char precursor fractions. After fungal treatments, lignin showed a similar change in the TCA profile, along with a gradual decrease of the total carbon, signifying lignin mineralization (combined with polymerization). By contrast, bacteria produced phenolic monomers without their further catabolism. After 54days of cultivation, a 20wt% weight loss was observed only for fungi, Coriolus versicolor, corroborating the near-80% carbon mass balance closure obtained by TCA. Compositional changes in lignin as a result of biodegradation were confirmed by thermal desorption (TD)-pyrolysis-GC-MS validating the carbon fractionation obtained by TCA.

  1. Biodegradation of lignin by fungi, bacteria and laccases.

    PubMed

    Asina, Fnu; Brzonova, Ivana; Voeller, Keith; Kozliak, Evguenii; Kubátová, Alena; Yao, Bin; Ji, Yun

    2016-11-01

    Indulin AT biodegradation by basidiomycetous fungi, actinobacteria and commercial laccases was evaluated using a suite of chemical analysis methods. The extent of microbial degradation was confirmed by novel thermal carbon analysis (TCA), as the treatments altered the carbon desorption and pyrolysis temperature profiles in supernatants. Laccase treatments caused only minor changes, though with increases occurring in the 850°C and char precursor fractions. After fungal treatments, lignin showed a similar change in the TCA profile, along with a gradual decrease of the total carbon, signifying lignin mineralization (combined with polymerization). By contrast, bacteria produced phenolic monomers without their further catabolism. After 54days of cultivation, a 20wt% weight loss was observed only for fungi, Coriolus versicolor, corroborating the near-80% carbon mass balance closure obtained by TCA. Compositional changes in lignin as a result of biodegradation were confirmed by thermal desorption (TD)-pyrolysis-GC-MS validating the carbon fractionation obtained by TCA. PMID:27598570

  2. Analysis of lignin-carbohydrate and lignin-lignin linkages after hydrolase treatment of xylan-lignin, glucomannan-lignin and glucan-lignin complexes from spruce wood.

    PubMed

    Du, Xueyu; Pérez-Boada, Marta; Fernández, Carmen; Rencoret, Jorge; del Río, José C; Jiménez-Barbero, Jesús; Li, Jiebing; Gutiérrez, Ana; Martínez, Angel T

    2014-05-01

    Xylan-lignin (XL), glucomannan-lignin (GML) and glucan-lignin (GL) complexes were isolated from spruce wood, hydrolyzed with xylanase or endoglucanase/β-glucosidase, and analyzed by analytical pyrolysis and 2D-NMR. The enzymatic hydrolysis removed most of the polysaccharide moieties in the complexes, and the lignin content and relative abundance of lignin-carbohydrate linkages increased. Analytical pyrolysis confirmed the action of the enzymatic hydrolysis, with strong decreases of levoglucosane and other carbohydrate-derived products. Unexpectedly it also revealed that the hydrolase treatment alters the pattern of lignin breakdown products, resulting in higher amounts of coniferyl alcohol. From the anomeric carbohydrate signals in the 2D-NMR spectra, phenyl glycoside linkages (undetectable in the original complexes) could be identified in the hydrolyzed GML complex. Lower amounts of glucuronosyl and benzyl ether linkages were also observed after the hydrolysis. From the 2D-NMR spectra of the hydrolyzed complexes, it was concluded that the lignin in GML is less condensed than in XL due to its higher content in β-O-4' ether substructures (62 % of side chains in GML vs 53 % in XL) accompanied by more coniferyl alcohol end units (16 vs 13 %). In contrast, the XL lignin has more pinoresinols (11 vs 6 %) and dibenzodioxocins (9 vs 2 %) than the GML (and both have ~13 % phenylcoumarans and 1 % spirodienones). Direct 2D-NMR analysis of the hydrolyzed GL complex was not possible due to its low solubility. However, after sample acetylation, an even less condensed lignin than in the GML complex was found (with up to 72 % β-O-4' substructures and only 1 % pinoresinols). The study provides evidence for the existence of structurally different lignins associated to hemicelluloses (xylan and glucomannan) and cellulose in spruce wood and, at the same time, offers information on some of the chemical linkages between the above polymers.

  3. Self-similar multiscale structure of lignin revealed by neutron scattering and molecular dynamics simulation

    SciTech Connect

    Petridis, Loukas; Pingali, Sai Venkatesh; Urban, Volker; Heller, William T; O'Neill, Hugh Michael; Foston, Marcus B; Ragauskas, Arthur J; Smith, Jeremy C

    2011-01-01

    Lignin, a major polymeric component of plant cell walls, forms aggregates in vivo and poses a barrier to cellulosic ethanol production. Here, neutron scattering experiments and molecular dynamics simulations reveal that lignin aggregates are characterized by a surface fractal dimension that is invariant under change of scale from 1 1000 A. The simulations also reveal extensive water penetration of the aggregates and heterogeneous chain dynamics corresponding to a rigid core with a fluid surface.

  4. A Versatile Click-Compatible Monolignol Probe to Study Lignin Deposition in Plant Cell Walls

    PubMed Central

    Pandey, Jyotsna L.; Wang, Bo; Diehl, Brett G.; Richard, Tom L.; Chen, Gong; Anderson, Charles T.

    2015-01-01

    Lignin plays important structural and functional roles in plants by forming a hydrophobic matrix in secondary cell walls that enhances mechanical strength and resists microbial decay. While the importance of the lignin matrix is well documented and the biosynthetic pathways for monolignols are known, the process by which lignin precursors or monolignols are transported and polymerized to form this matrix remains a subject of considerable debate. In this study, we have synthesized and tested an analog of coniferyl alcohol that has been modified to contain an ethynyl group at the C-3 position. This modification enables fluorescent tagging and imaging of this molecule after its incorporation into plant tissue by click chemistry-assisted covalent labeling with a fluorescent azide dye, and confers a distinct Raman signature that could be used for Raman imaging. We found that this monolignol analog is incorporated into in vitro-polymerized dehydrogenation polymer (DHP) lignin and into root epidermal cell walls of 4-day-old Arabidopsis seedlings. Incorporation of the analog in stem sections of 6-week-old Arabidopsis thaliana plants and labeling with an Alexa-594 azide dye revealed the precise locations of new lignin polymerization. Results from this study indicate that this molecule can provide high-resolution localization of lignification during plant cell wall maturation and lignin matrix assembly. PMID:25884205

  5. A versatile click-compatible monolignol probe to study lignin deposition in plant cell walls.

    PubMed

    Pandey, Jyotsna L; Wang, Bo; Diehl, Brett G; Richard, Tom L; Chen, Gong; Anderson, Charles T

    2015-01-01

    Lignin plays important structural and functional roles in plants by forming a hydrophobic matrix in secondary cell walls that enhances mechanical strength and resists microbial decay. While the importance of the lignin matrix is well documented and the biosynthetic pathways for monolignols are known, the process by which lignin precursors or monolignols are transported and polymerized to form this matrix remains a subject of considerable debate. In this study, we have synthesized and tested an analog of coniferyl alcohol that has been modified to contain an ethynyl group at the C-3 position. This modification enables fluorescent tagging and imaging of this molecule after its incorporation into plant tissue by click chemistry-assisted covalent labeling with a fluorescent azide dye, and confers a distinct Raman signature that could be used for Raman imaging. We found that this monolignol analog is incorporated into in vitro-polymerized dehydrogenation polymer (DHP) lignin and into root epidermal cell walls of 4-day-old Arabidopsis seedlings. Incorporation of the analog in stem sections of 6-week-old Arabidopsis thaliana plants and labeling with an Alexa-594 azide dye revealed the precise locations of new lignin polymerization. Results from this study indicate that this molecule can provide high-resolution localization of lignification during plant cell wall maturation and lignin matrix assembly.

  6. Geological and hydrochemical sensitivity of the eastern United States to acid precipitation

    SciTech Connect

    Hendrey, G.R.; Galloway, J.N.; Norton, S.A.; Schofield, C.L.; Shaffer, P.W.; Burns, D.A.

    1980-03-01

    A new analysis of bedrock geology maps of the eastern US constitutes a simple model for predicting areas which might be impacted by acid precipitation and it allows much greater resolution for detecting sensitivity than has previously been available for the region. Map accuracy has been verified by examining current alkalinities and pH's of waters in several test states, including Maine, New Hampshire, New York, Virginia and North Carolina. In regions predicted to be highly sensitive, alkalinities in upstream sites were generally low. Many areas of the eastern US are pinpointed in which some of the surface waters, especially upstream reaches, may be sensitive to acidification. Pre-1970 data were compared to post-1975 data, revealing marked declines in both alkalinity and pH of sensitive waters of two states tested, North Carolina, where pH and alkalinity have decreased in 80% of 38 streams and New Hampshire, where pH in 90% of 49 streams and lakes has decreased since 1949. These sites are predicted to be sensitive by the geological map on the basis of their earlier alkalinity values. The map is to be improved by the addition of a soils component.

  7. National Acid Precipitation Assessment Program Report to Congress: An Integrated Assessment

    SciTech Connect

    Uhart, M.; et al,

    2005-08-01

    Under Title IX of the 1990 Clean Air Act Amendments, Congress reauthorized the National Acid Precipitation Assessment Program (NAPAP) to continue coordinating acid rain research and monitoring, as it had done during the previous decade, and to provide Congress with periodic reports. In particular, Congress asked NAPAP to assess all available data and information to answer two questions: (1) What are the costs, benefits, and effectiveness of Title IV? This question addresses the costs and economic impacts of complying with the Acid Rain Program as well as benefit analyses associated with the various human health and welfare effects, including reduced visibility, damages to materials and cultural resources, and effects on ecosystems. (2) What reductions in deposition rates are needed to prevent adverse ecological effects? This complex questions addresses ecological systems and the deposition levels at which they experience harmful effects. The results of the assessment of the effects of Title IV and of the relationship between acid deposition rates and ecological effects were to be reported to Congress quadrennially, beginning with the 1996 report to Congress. The objective of this Report is to address the two main questions posed by Congress and fully communicate the results of the assessment to decision-makers. Given the primary audience, most of this report is not written as a technical document, although information supporting the conclusions is provided along with references.

  8. Design and performance of an acidic precipitation delivery system for field investigations with plants.

    PubMed

    Lauver, T L; Laurence, J A; Kohut, R J

    1990-01-01

    An acidic precipitation delivery system is described that was designed and constructed for use in a field investigation of the response of red spruce saplings (Picea rubens Sarg.) to the interactive stresses of ozone and acid rain. The system utilizes hydraulic, solid-cone spray nozzles to produce simulated rainfall with droplet size distributions approximating natural rain events, which are of low intensity, i.e., about 1-1.5 cm hr(-1), and are relatively uniform in distribution of volume over a 2.4 m diameter plot. Three different pH treatments (3.1, 4.1, 5.1) were dispensed randomly to each of three treatment subplots located in twelve open-top field chambers and three ambient control chambers. Storage capacity of the system permitted a 2.3 hr rain event. Construction materials used were chosen for resistance to the corrosive nature of the rain simulant, stability to ambient UV radiation, and resistance to penetration by sunlight. Simulated events were not synchronized to ambient events, but were scheduled to prevent moisture deficits.

  9. Interactions of 57Co, 85Sr and 137Cs with peat under acidic precipitation conditions.

    PubMed

    Sanchez, A L; Schell, W R; Thomas, E D

    1988-03-01

    Following the burial of low-level wastes in nuclear waste repositories, the interactions of radionuclides with surrounding soil infiltrated by acid precipitation could cause radionuclide migration and transport into nearby wells. To evaluate this migration through organically rich soil in the unsaturated zone, we measured sorption and desorption distribution ratios (Rd) of 57Co, 85Sr and 137Cs onto peat at pH 4. Peat samples rich in organic C showed relatively higher sorption Rd values for 57Co and 85Sr compared to soil samples with less organic C. The sorption and desorption Rd values for these radionuclides are similar, indicating the reversibility of the sorption process. The measurements suggest the importance of organic complexes for the retention of these radionuclides at the pH range (pH 4), where hydrolysis of the metals is not important and sorption is expected to be low. Cesium-137, on the other hand, appears to be associated more strongly with inorganic components of the soil samples, with its Rd value significantly higher in the peat material containing less organic C. The 137Cs desorption Rd on the same peat sample is also comparable to the sorption Rd indicating equilibrium. Both the organic and inorganic components of peat are thus able to retard the migration of radionuclides which may be found in nuclear waste repositories. The design of such a repository may be improved using a peat barrier to restrict radionuclide migration.

  10. Lignin blockers and uses thereof

    SciTech Connect

    Yang, Bin; Wyman, Charles E

    2013-11-12

    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.

  11. From gene towards selective biomass valorization: bacterial β-etherases with catalytic activity on lignin-like polymers.

    PubMed

    Picart, Pere; Müller, Christoph; Mottweiler, Jakob; Wiermans, Lotte; Bolm, Carsten; Domínguez de María, Pablo; Schallmey, Anett

    2014-11-01

    Microbial β-etherases, which selectively cleave the β-O-4 aryl ether linkage present in lignin, hold great promise for future applications in lignin valorization. However, very few members have been reported so far and little is known about these enzymes. By using a database mining approach, four novel bacterial β-etherases were identified, recombinantly produced in Escherichia coli, and investigated together with known β-etherases in the conversion of various lignin and non-lignin-type model compounds. The resulting activities revealed the significant influence of the substituents at the phenyl ring adjacent to the ether bond. Finally, β-etherase activity on polymeric substrates, measured by using a fluorescently labeled synthetic lignin, was also proven; this underlined the applicability of the enzymes for the conversion of lignin into renewable chemicals. PMID:25186983

  12. Identifying new lignin bioengineering targets: impact of epicatechin, quercetin glycoside, and gallate derivatives on the lignification and fermentation of maize cell walls

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Apoplastic targeting of secondary metabolites compatible with monolignol polymerization may provide new avenues for designing lignins that are less inhibitory toward fiber fermentation. To identify suitable monolignol substitutes, we artificially lignified maize cell walls with normal monolignols pl...

  13. Potential effects of clean coal technologies on acid precipitation, greenhouse gases, and solid waste disposal

    SciTech Connect

    Blasing, T.J.; Miller, R.L.; McCold, L.N.

    1993-11-01

    The US Department of Energy`s (DOE`s) Clean Coal Technology Demonstration Program (CCTDP) was initially funded by Congress to demonstrate more efficient, economically feasible, and environmentally acceptable coal technologies. Although the environmental focus at first was on sulfur dioxide (SO{sub 2}) and nitrogen oxides (NO{sub x}) because their relationship to acid precipitation, the CCTDP may also lead to reductions in carbon dioxide (CO{sub 2}) emissions and in the volume of solid waste produced, compared with conventional technologies. The environmental effects of clean coal technologies (CCTs) depend upon which (if any) specific technologies eventually achieve high acceptance in the marketplace. In general, the repowering technologies and a small group of retrofit technologies show the most promise for reducing C0{sub 2} emissions and solid waste. These technologies also compare favorably with other CCTs in terms of SO{sub 2} and NO{sub x} reductions. The upper bound for CO{sup 2} reductions in the year 2010 is only enough to reduce global ``greenhouse`` warming potential by about 1%. However, CO{sub 2} emissions come from such variety of sources around the globe that no single technological innovation or national policy change could realistically be expected to reduce these emissions by more than a few percent. Particular CCTs can lead to either increases or decreases in the amount of solid waste produced. However, even if decreases are not achieved, much of the solid waste from clean coal technologies would be dry and therefore easier to dispose of than scrubber sludge.

  14. Potential health implications for acid precipitation, corrosion, and metals contamination of drinking water.

    PubMed

    Sharpe, W E; DeWalle, D R

    1985-11-01

    Potential health effects of drinking water quality changes caused by acid precipitation are presented. Several different types of water supply are discussed and their roles in modifying acid rain impacts on drinking water are explained. Sources of metals contamination in surface water supplies are enumerated. The authors present some results from their research into acid rain impacts on roof-catchment cisterns, small surface water supplies, and lead mobilization in acid soils. A good correlation was obtained between cistern water corrosivity as measured by the Ryznar Index (RI) values and standing tapwater copper concentrations. However, lead concentrations in tapwater did not correlate well with cistern water RI. A modified linear regression model that accounted for Ryznar Index change during storage in vinyl-lined cisterns was used to predict the Ryznar Index value at a copper concentration of 1000 micrograms/L. The predicted RI was greater than the RI of precipitation with a pH of 5.3, indicating that anthropogenically acidified precipitation may result in cistern tapwater copper concentrations in excess of the 1000 micrograms/L suggested drinking water limit. Good correlations between tapwater Ryznar Index and tapwater copper and lead concentrations were not obtained for the small surface water supply. Aluminum concentrations in reservoir water were similar to those in stream source water. Limited data were also presented that indicated lead was present in acid forest soil leachate and streams draining such soils in relatively small concentrations. Where appropriate, recommendations for future research are included with the discussions of research results.

  15. Effect of acid precipitation on retention and excretion of elements in man.

    PubMed

    Bensryd, I; Rylander, L; Högstedt, B; Aprea, P; Bratt, I; Fåhraéus, C; Holmén, A; Karlsson, A; Nilsson, A; Svensson, B L

    1994-05-01

    From a population of 8918 farmers, 237 were selected whose consumption of locally produced foods was high. The subjects' water sources, private wells, were of different degrees of acidity. Significant associations between pH (median 6.7, range 4.7-8.6) of the drinking water and element concentrations were found. The correlation was negative for aluminium (Al; median 0.07 mumol/l), cadmium (Cd; 0.44 nmol/l), copper (Cu; 0.24 mumol/l) and lead (Pb; 1.9 nmol/l), and positive for calcium (Ca; 0.62 mmol/l) and magnesium (Mg; 0.21 mmol/l). Associations could not be found between the pH of, or element concentrations in, the water and concentrations of A1 (0.17 mumol/l), Mg (0.86 mmol/l) and selenium (Se; 1.0 mumol/l) in plasma, Cd (2.0 nmol/l), Pb (0.19 mumol/l) and mercury (Hg; 13 nmol/l) in blood, or A1 (12 mumol/mol creatinine) and Cu (11 mumol/mol creatinine) in urine. The concentrations of Hg in blood and Se in plasma were related to fish consumption, Cd and Pb in blood to smoking, A1 in urine to antacid intake, Pb in blood to rifle activities and hunting, and Hg in blood to hunting. Acid precipitation has an effect on element concentrations in drinking water, but not on the retention of those elements in the subjects investigated.

  16. Microscopic evaluation of trace metals in cloud droplets in an acid precipitation region.

    PubMed

    Li, Weijun; Wang, Yan; Collett, Jeffrey L; Chen, Jianmin; Zhang, Xiaoye; Wang, Zifa; Wang, Wenxing

    2013-05-01

    Mass concentrations of soluble trace metals and size, number, and mixing properties of nanometal particles in clouds determine their toxicity to ecosystems. Cloud water was found to be acidic, with a pH of 3.52, at Mt. Lu (elevation 1,165 m) in an acid precipitation region in South China. A combination of Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Transmission Electron Microscopy (TEM) for the first time demonstrates that the soluble metal concentrations and solid metal particle number are surprisingly high in acid clouds at Mt. Lu, where daily concentrations of SO2, NO2, and PM10 are 18 μg m(-3), 7 μg m(-3), and 22 μg m(-3). The soluble metals in cloudwater with the highest concentrations were zinc (Zn, 200 μg L(-1)), iron (Fe, 88 μg L(-1)), and lead (Pb, 77 μg L(-1)). TEM reveals that 76% of cloud residues include metal particles that range from 50 nm to 1 μm diameter with a median diameter of 250 nm. Four major metal-associated particle types are Pb-rich (35%), fly ash (27%), Fe-rich (23%), and Zn-rich (15%). Elemental mapping shows that minor soluble metals are distributed within sulfates of cloud residues. Emissions of fine metal particles from large, nonferrous industries and coal-fired power plants with tall stacks were transported upward to this high elevation. Our results suggest that the abundant trace metals in clouds aggravate the impacts of acid clouds or associated precipitation on the ecosystem and human health.

  17. Effect of acid precipitation on retention and excretion of elements in man.

    PubMed

    Bensryd, I; Rylander, L; Högstedt, B; Aprea, P; Bratt, I; Fåhraéus, C; Holmén, A; Karlsson, A; Nilsson, A; Svensson, B L

    1994-05-01

    From a population of 8918 farmers, 237 were selected whose consumption of locally produced foods was high. The subjects' water sources, private wells, were of different degrees of acidity. Significant associations between pH (median 6.7, range 4.7-8.6) of the drinking water and element concentrations were found. The correlation was negative for aluminium (Al; median 0.07 mumol/l), cadmium (Cd; 0.44 nmol/l), copper (Cu; 0.24 mumol/l) and lead (Pb; 1.9 nmol/l), and positive for calcium (Ca; 0.62 mmol/l) and magnesium (Mg; 0.21 mmol/l). Associations could not be found between the pH of, or element concentrations in, the water and concentrations of A1 (0.17 mumol/l), Mg (0.86 mmol/l) and selenium (Se; 1.0 mumol/l) in plasma, Cd (2.0 nmol/l), Pb (0.19 mumol/l) and mercury (Hg; 13 nmol/l) in blood, or A1 (12 mumol/mol creatinine) and Cu (11 mumol/mol creatinine) in urine. The concentrations of Hg in blood and Se in plasma were related to fish consumption, Cd and Pb in blood to smoking, A1 in urine to antacid intake, Pb in blood to rifle activities and hunting, and Hg in blood to hunting. Acid precipitation has an effect on element concentrations in drinking water, but not on the retention of those elements in the subjects investigated. PMID:8016632

  18. Potential health implications for acid precipitation, corrosion, and metals contamination of drinking water.

    PubMed

    Sharpe, W E; DeWalle, D R

    1985-11-01

    Potential health effects of drinking water quality changes caused by acid precipitation are presented. Several different types of water supply are discussed and their roles in modifying acid rain impacts on drinking water are explained. Sources of metals contamination in surface water supplies are enumerated. The authors present some results from their research into acid rain impacts on roof-catchment cisterns, small surface water supplies, and lead mobilization in acid soils. A good correlation was obtained between cistern water corrosivity as measured by the Ryznar Index (RI) values and standing tapwater copper concentrations. However, lead concentrations in tapwater did not correlate well with cistern water RI. A modified linear regression model that accounted for Ryznar Index change during storage in vinyl-lined cisterns was used to predict the Ryznar Index value at a copper concentration of 1000 micrograms/L. The predicted RI was greater than the RI of precipitation with a pH of 5.3, indicating that anthropogenically acidified precipitation may result in cistern tapwater copper concentrations in excess of the 1000 micrograms/L suggested drinking water limit. Good correlations between tapwater Ryznar Index and tapwater copper and lead concentrations were not obtained for the small surface water supply. Aluminum concentrations in reservoir water were similar to those in stream source water. Limited data were also presented that indicated lead was present in acid forest soil leachate and streams draining such soils in relatively small concentrations. Where appropriate, recommendations for future research are included with the discussions of research results. PMID:4076096

  19. A transport model of the dissolution of limestone and marble due to acid precipitation

    SciTech Connect

    Kishiyama, G.E.

    1991-01-01

    The dissolution rate of calcite is known to be a function of the hydrogen ion activity in a contacting solution. This is important in the case of accelerated weathering by acid precipitation, where the decrease in the natural pH of rainwater can cause significant damage. Experimental studies on inclined slabs of Salem Limestone and Shelburne Marble are being conducted both in the field and in the laboratory. This study is a theoretical model based on the laboratory experiments, and an attempt to relate the results to that obtained in the field studies. The laboratory experiments are modeled after failing film theory, where the flux of species into and out of the system at the solid-liquid interface are defined by the Plummer et al. reaction expressions. Electrochemical effects and chemical reactions in the bulk solution which contribute a buffering effect can alter the rate of mass transfer. A finite difference predictor-corrector method developed by Douglas was chosen to solve the coupled, non-linear equations describing this system. Hydrodynamics of rainfall onto a porous surface differ significantly from the well-known theory of laminar falling films. Hydrogen ion is quickly consumed after initial contact with the solid surface, resulting in large concentrations in the bulk fluid. The ensuing rate of mass transfer after consumption of acid closely resembles heat transfer into a semi-infinite slab with constant flux at the surface. Models for the distribution of raindrop sizes, descent velocity, and impact effect are developed based solely on rainfall intensity, which is provided from the field experiments. Addition of fresh fluid is quickly buffered by the flowing film, and dissolution due to acidity becomes less important for longer exposure lengths.

  20. Lignin Bioproducts to Enable Biofuels

    SciTech Connect

    Wyman, Charles E.; Ragauskas, Arthur J

    2015-09-15

    Here we report that today's and tomorrow's biofuels production facilities could benefit tremendously from increasing the value from the large amount of lignin that results from biofuels operations. Certainly, the scientific community, and biofuels industry has begun to recognize the challenges and opportunities associated with lignin.

  1. Polymeric microspheres

    DOEpatents

    Walt, David R.; Mandal, Tarun K.; Fleming, Michael S.

    2004-04-13

    The invention features core-shell microsphere compositions, hollow polymeric microspheres, and methods for making the microspheres. The microspheres are characterized as having a polymeric shell with consistent shell thickness.

  2. Acid deposition: State of science and technology. Summary report of the U. S. National Acid Precipitation Assessment Program

    SciTech Connect

    Irving, P.M.; Smith, E.

    1991-09-01

    The twenty-seven State-of-Science and State-of-Technology (SOS/T) Reports, published in 1990 as the definitive scientific and technical synthesis of information obtained during the first decade of the U.S. national Acid Precipitation Assessment Program (NAPAP), are summarized in the document. In most cases, these summaries were the final chapter of the complete SOS/T Report.

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

    PubMed

    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. PMID:26378240

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

    DOE PAGES

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

    2015-09-16

    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 anmore » 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. Lastly, the resulting enzyme variant represents an excellent candidate for modulating lignin composition and/or structure in planta.« less

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

    SciTech Connect

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

    2015-09-16

    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. Lastly, the resulting enzyme variant represents an excellent candidate for modulating lignin composition and/or structure in planta.

  6. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Lignin sulfonates. 573.600 Section 573.600 Food... Additive Listing § 573.600 Lignin sulfonates. Lignin sulfonates may be safely used in animal feeds in... feeds, as liquid lignin sulfonate, in an amount not to exceed 11 percent of the molasses. (4) As...

  7. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Lignin sulfonates. 573.600 Section 573.600 Food... Additive Listing § 573.600 Lignin sulfonates. Lignin sulfonates may be safely used in animal feeds in... feeds, as liquid lignin sulfonate, in an amount not to exceed 11 percent of the molasses. (4) As...

  8. Utilization of chemically modified lignin

    SciTech Connect

    Chem, M.J.

    1996-10-01

    A chemical modification method has been developed to convert lignin into lignin graft copolymers. The graft products are macromolecular surface active agents because, within each molecule, a hydrocarbon sidechain has been gown off of a natural oxyphenylpropyl backbone. Surface activity of the graft copolymers was indicated by their capacity to form stable emulsions between incompatible fluid phases and to adhesively bond to wood surfaces. Lignin has been grafted with ethenylbenzene (styrene), 4-methyl-2-oxy-3-oxopent-4-ene (methylmethacrylate), 2-propenamide(acrylamide), 2-propene nitrile (acrylonitrile), cationic monomers, and anionic monomers. Synthesis with anionic, cationic, or polar nonionic monomers produced water soluble, lignin copolymers that were effective dispersing, flocculating, and surface active agents. The nonionic polymers and their hydrolysis products are effective thinners and suspending agents for drilling mud formulations. In reactions with ethenylbenzene, lignin was used to make thermoplastic materials. These products have been shown to be poly(lignin-g-(1-phenylethylene))-containing materials by a series of solubility and extraction tests and are formed with 90% or more grafting efficiency for lignin. These materials have been shown to be thermoplastics, coupling agents for wood and plastic, and biodegradable plastics.

  9. The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

    PubMed

    Bährle, Christian; Custodis, Victoria; Jeschke, Gunnar; van Bokhoven, Jeroen A; Vogel, Frédéric

    2016-09-01

    Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene.

  10. The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

    PubMed

    Bährle, Christian; Custodis, Victoria; Jeschke, Gunnar; van Bokhoven, Jeroen A; Vogel, Frédéric

    2016-09-01

    Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene. PMID:27486717

  11. Towards the specification of consecutive steps in macromolecular lignin assembly

    NASA Technical Reports Server (NTRS)

    Nose, M.; Bernards, M. A.; Furlan, M.; Zajicek, J.; Eberhardt, T. L.; Lewis, N. G.

    1995-01-01

    When Pinus taeda cell suspension cultures are exposed to 8% sucrose solution, the cells undergo significant intracellular disruption, irregular wall thickening/lignification with concomitant formation of an 'extracellular lignin precipitate. However, addition of potassium iodide (KI), an H202 scavenger, inhibits this lignification response, while the ability to synthesize the monolignols, p-coumaryl and coniferyl alcohols, is retained. Lignin synthesis (i.e. polymerization) is thus temporarily correlated with H202 generation, strongly implying a regulatory role for the latter. Time course analyses of extracellular metabolites leading up to polymer formation reveal that coniferyl alcohol, but not p-coumaryl alcohol, undergoes substantial coupling reactions to give various lignans. Of these, the metabolites, dihydrodehydrodiconiferyl alcohol, shonanin (divanillyl tetrahydrofuran) and its apparent aryl tetralin derivative, cannot be explained simply on the basis of phenolic coupling. It is proposed that these moieties are the precursors of so-called reduced substructures in the lignin macromolecule. This adds a new perspective to the lignin assembly mechanism.

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

    PubMed

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

    2016-02-14

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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Epigallocatechin gallate (EGCG) was evaluated as a potential lignin bioengineering target for rendering biomass more amenable to processing for biofuel production. In vitro peroxidase-catalyzed polymerization experiments revealed that both gallate and pyrogalloyl (B-ring) moieties in EGCG underwent ...

  14. Synthesis and characterization of lignin-based carbon materials with tunable microstructure

    SciTech Connect

    Chatterjee, Sabornie; Clingenpeel, Amy; McKenna, Amy; Rios, Orlando; Johs, Alexander

    2013-01-01

    Lignin-based carbons can be used as a low-cost alternative to graphite and petroleum-based carbons enabling the production of sustainable, functional carbon materials for various applications. The microstructure development of these carbons can be controlled through chemical modification of the lignin precursor and choice of carbonization parameters. In this work, microstructured carbon materials are synthesized from lignin using a combination of chemical modification and carbon fiber processing techniques. Lignin is modified by incorporating different ester groups which results in a precursor highly compatible with melt processing using the fiber extrusion technique and conversion into microstructured carbons by oxidative stabilization and subsequent carbonization. Furthermore, the impact of esterifications on precursor chemistry and carbonizations is investigated. A nuclear magnetic resonance study of modified lignins shows characteristic spectral changes as a result of esterifications. Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry shows the modification process does not affect the polymeric character of the lignin backbone. Esterifications result in moderate shifts in O:C and H:C ratios. Thermogravimetric analysis of lignins reveals distinct differences in mass loss trends during oxidations and carbonizations.

  15. Modification of the activity of cell wall-bound peroxidase by hypergravity in relation to the stimulation of lignin formation in azuki bean epicotyls

    NASA Astrophysics Data System (ADS)

    Wakabayashi, Kazuyuki; Nakano, Saho; Soga, Kouichi; Hoson, Takayuki

    Lignin is a component of cell walls of terrestrial plants, which provides cell walls with the mechanical rigidity. Lignin is a phenolic polymer with high molecular mass and formed by the polymerization of phenolic substances on a cellulosic matrix. The polymerization is catalyzed by cell wall-bound peroxidase, and thus the activity of this enzyme regulates the rate of formation of lignin. In the present study, the changes in the lignin content and the activity of cell wall peroxidase were investigated along epicotyls of azuki bean seedlings grown under hypergravity conditions. The endogenous growth occurred primarily in the upper regions of the epicotyl and no growth was detected in the middle or basal regions. The amounts of acetyl bromide-soluble lignin increased from the upper to the basal regions of epicotyls. The lignin content per unit length in the basal region was three times higher than that in the upper region. Hypergravity treatment at 300 g for 6 h stimulated the increase in the lignin content in all regions of epicotyls, particularly in the basal regions. The peroxidase activity in the protein fraction extracted from the cell wall preparation with a high ionic strength buffer also increased gradually toward the basal region, and hypergravity treatment clearly increased the activity in all regions. There was a close correlation between the lignin content and the enzyme activity. These results suggest that gravity stimuli modulate the activity of cell wall-bound peroxidase, which, in turn, causes the stimulation of the lignin formation in stem organs.

  16. Engineering Monolignol 4-O-Methyltransferases to Modulate Lignin Biosynthesis

    SciTech Connect

    Bhuiya, M.W.; Liu, C.

    2010-01-01

    Lignin is a complex polymer derived from the oxidative coupling of three classical monolignols. Lignin precursors are methylated exclusively at the meta-positions (i.e. 3/5-OH) of their phenyl rings by native O-methyltransferases, and are precluded from substitution of the para-hydroxyl (4-OH) position. Ostensibly, the para-hydroxyls of phenolics are critically important for oxidative coupling of phenoxy radicals to form polymers. Therefore, creating a 4-O-methyltransferase to substitute the para-hydroxyl of monolignols might well interfere with the synthesis of lignin. The phylogeny of plant phenolic O-methyltransferases points to the existence of a batch of evolutionarily 'plastic' amino acid residues. Following one amino acid at a time path of directed evolution, and using the strategy of structure-based iterative site-saturation mutagenesis, we created a novel monolignol 4-O-methyltransferase from the enzyme responsible for methylating phenylpropenes. We show that two plastic residues in the active site of the parental enzyme are vital in dominating substrate discrimination. Mutations at either one of these separate the evolutionarily tightly linked properties of substrate specificity and regioselective methylation of native O-methyltransferase, thereby conferring the ability for para-methylation of the lignin monomeric precursors, primarily monolignols. Beneficial mutations at both sites have an additive effect. By further optimizing enzyme activity, we generated a triple mutant variant that may structurally constitute a novel phenolic substrate binding pocket, leading to its high binding affinity and catalytic efficiency on monolignols. The 4-O-methoxylation of monolignol efficiently impairs oxidative radical coupling in vitro, highlighting the potential for applying this novel enzyme in managing lignin polymerization in planta.

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

    NASA Astrophysics Data System (ADS)

    Guo, Xiaojie; Zhang, Jinwen; Xin, Junna

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

  18. From lignin association to nano-/micro-particle preparation: Extracting higher value of lignin

    DOE PAGES

    Zhao, Wenwen; Simmons, Blake; Singh, Seema; Ragauskas, Arthur J.; Cheng, Gang

    2016-09-26

    As the most abundant source of renewable aromatic compounds on the planet, lignin is gaining growing interest in replacing petroleum-based chemicals and products. Value-added applications of lignin are also essential for economic viability for future bio-refineries. It is however an under-utilized natural resource due to its structural heterogeneities. Lignin nanoparticles offer many opportunities for value-added applications of lignin. The solution structures of lignin were proposed as one of the key elements in controlling lignin nano-/micro-particle preparation. Fundamental understanding of solutionstructures of lignin aid in designing better fabrication of lignin nanoparticles. A deeper understanding of the observed experimental results also pointsmore » to the need for detailed studies of lignin in solution. Lastly, this review consists of two major topics, the solution structures of lignin and lignin nano-/micro-particle preparation. Suggestions for future studies regarding these two topics were also put forward.« less

  19. Lignin-Derived Advanced Carbon Materials.

    PubMed

    Chatterjee, Sabornie; Saito, Tomonori

    2015-12-01

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

  20. Lignin-Derived Advanced Carbon Materials

    SciTech Connect

    Chatterjee, Sabornie; Saito, Tomonori

    2015-11-16

    Lignin is a highly abundant source of renewable carbon that can be considered as a valuable sustainable source of biobased materials. By applying specific pretreatments and manufacturing methods, it has been found that lignin can be converted into a variety of value-added carbon materials. However, the physical and chemical heterogeneities of lignin complicate its use as a feedstock. Herein, we discuss the lignin manufacturing process, the effects of pretreatments and manufacturing methods on the properties of product lignin, and structure–property relationships in various applications of lignin-derived carbon materials, such as carbon fibers, carbon mats, activated carbons, carbon films, and templated carbon.

  1. The fate of lignin during hydrothermal pretreatment

    PubMed Central

    2013-01-01

    Background Effective enzymatic hydrolysis of lignocellulosic biomass benefits from lignin removal, relocation, and/or modification during hydrothermal pretreatment. Phase transition, depolymerization/repolymerization, and solubility effects may all influence these lignin changes. To better understand how lignin is altered, Populus trichocarpa x P. deltoides wood samples and cellulolytic enzyme lignin (CEL) isolated from P. trichocarpa x P. deltoides were subjected to batch and flowthrough pretreatments. The residual solids and liquid hydrolysate were characterized by gel permeation chromatography, heteronuclear single quantum coherence NMR, compositional analysis, and gas chromatography–mass spectrometry. Results Changes in the structure of the solids recovered after the pretreatment of CEL and the production of aromatic monomers point strongly to depolymerization and condensation being primary mechanisms for lignin extraction and redeposition. The differences in lignin removal and phenolic compound production from native P. trichocarpa x P. deltoides and CEL suggested that lignin-carbohydrate interactions increased lignin extraction and the extractability of syringyl groups relative to guaiacyl groups. Conclusions These insights into delignification during hydrothermal pretreatment point to desirable pretreatment strategies and plant modifications. Because depolymerization followed by repolymerization appears to be the dominant mode of lignin modification, limiting the residence time of depolymerized lignin moieties in the bulk liquid phase should reduce lignin content in pretreated biomass. In addition, the increase in lignin removal in the presence of polysaccharides suggests that increasing lignin-carbohydrate cross-links in biomass would increase delignification during pretreatment. PMID:23902789

  2. Does elevated N make lignin more recalcitrant?

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  3. Lignin-assisted coal depolymerization

    SciTech Connect

    Lalvani, S.B.

    1991-01-01

    Previous research has shown that addition of lignin-derived liquids to coal stirred in tetralin under mild reaction conditions (375{degree}C and 300--500 psig) results in a marked enhancement in the rate of coal depolymerization. A mathematical model was developed to study the kinetics of coal depolymerization in the presence of liquid-derived liquids. In the present study, a reaction pathway was formulated to explain the enhancement in coal depolymerization due to lignin (solid) addition. The model postulated assumes that the products of lignin obtained during thermolysis interact with the reactive moieties present in coal while simultaneous depolymerization of coal occurs. A good fit between the experimental data and the kinetic model was found. The results show that in addition to the enhancement in the rate of coal depolymerization, lignin also reacts (and enhances the extent of depolymerization of coal) with those reaction sites in coal that are not susceptible to depolymerization when coal alone is reacted in tetralin under identical reaction conditions. Additional work is being carried out to determine a thorough materials balance on the lignin-assisted coal depolymerization process. A number of liquid samples have been obtained which are being studied for their stability in various environments. 5 refs., 4 figs., 1 tab.

  4. Lignin analysis by FT-Raman spectroscopy

    SciTech Connect

    Agarwal, U.P.; Obst, J.R.; Cannon, A.B.

    1996-10-01

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

  5. ISSUES IN LIGNIN CHEMISTRY. "THE HELSINKI CONNECTION"

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This presentation covers advances in lignin chemistry (and our Helsinki connection) on dibenzodioxocins, spirodienones, and reduced structures in lignins. It also explores the various roles in defending lignification theory (based on Freudenberg's original hypothesis) against a supposed new contende...

  6. Fate of Residual Lignin during Delignification of Kraft Pulp by Trametes versicolor

    PubMed Central

    Reid, Ian D.

    1998-01-01

    The fungus Trametes versicolor can delignify and brighten kraft pulps. To better understand the mechanism of this biological bleaching and the by-products formed, I traced the transformation of pulp lignin during treatment with the fungus. Hardwood and softwood kraft pulps containing 14C-labelled residual lignin were prepared by laboratory pulping of lignin-labelled aspen and spruce wood and then incubated with T. versicolor. After initially polymerizing the lignin, the fungus depolymerized it to alkali-extractable forms and then to soluble forms. Most of the labelled carbon accumulated in the water-soluble pool. The extractable and soluble products were oligomeric; single-ring aromatic products were not detected. The mineralization of the lignin carbon to CO2 varied between experiments, up to 22% in the most vigorous cultures. The activities of the known enzymes laccase and manganese peroxidase did not account for all of the lignin degradation that took place in the T. versicolor cultures. This fungus may produce additional enzymes that could be useful in enzyme bleaching systems. PMID:9603823

  7. Lignin degradation during plant litter photodegradation

    NASA Astrophysics Data System (ADS)

    Lin, Y.; King, J. Y.

    2014-12-01

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

  8. Development of novel assays for lignin degradation: comparative analysis of bacterial and fungal lignin degraders.

    PubMed

    Ahmad, Mark; Taylor, Charles R; Pink, David; Burton, Kerry; Eastwood, Daniel; Bending, Gary D; Bugg, Timothy D H

    2010-05-01

    Two spectrophotometric assays have been developed to monitor breakdown of the lignin component of plant lignocellulose: a continuous fluorescent assay involving fluorescently modified lignin, and a UV-vis assay involving chemically nitrated lignin. These assays have been used to analyse lignin degradation activity in bacterial and fungal lignin degraders, and to identify additional soil bacteria that show activity for lignin degradation. Two soil bacteria known to act as aromatic degraders, Pseudomonas putida and Rhodococcus sp. RHA1, consistently showed activity in these assays, and these strains were shown in a small scale experiment to breakdown lignocellulose, producing a number of monocyclic phenolic products. Using milled wood lignin prepared from wheat straw, pine, and miscanthus, some bacterial lignin degraders were found to show specificity for lignin type. These assays could be used to identify novel lignin degraders for breakdown of plant lignocellulose. PMID:20567767

  9. Cationic electrodepositable coating composition comprising lignin

    DOEpatents

    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.

  10. Disinfection byproduct formation from lignin precursors.

    PubMed

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

    2014-10-15

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

  11. Liquid Fuels from Lignins: Annual Report

    SciTech Connect

    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.

  12. 40 CFR 721.5460 - Organosolv lignin.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Organosolv lignin. 721.5460 Section... Substances § 721.5460 Organosolv lignin. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an organosolv lignin (PMN P-95-1584; CAS No. 8068-03-9)...

  13. Enzymatic monitoring of lignin and lignin derivatives biooxidation.

    PubMed

    Ibrahim, Victor; Mamo, Gashaw

    2016-01-01

    Lignin oxidation was enzymatically monitored by measuring methanol released during the reaction. The methanol was oxidized to formaldehyde and hydrogen peroxide, and the latter used to oxidize ABTS to a product measured spectrophotometrically. The efficiency was comparable to the commonly used gas chromatography method. The assay was fast and inexpensive. PMID:26632344

  14. Integrated Lake-Watershed Acidification Study (ILWAS): contributions to the international conference on the ecological impact of acid precipitation

    SciTech Connect

    Not Available

    1981-05-01

    The Integrated Lake-Watershed Acidification Study (ILWAS) was initiated to study and detail lake acidification processes for three lake watershed basins in the Adirondack Park region of New York. The three basins (Woods, Sagamore, and Panther), receive similar amounts of acid deposition yet observable pH values for the lakes are very dissimilar indicating unequal acid neutralizing capacities among the watersheds. This volume contains a compilation of seven papers. Relevant topics include: a characterization of the geology, hydrology, limnology and vegetation of the three study sites, an analysis of acid precipitation quality and quantity, the effects of vegetative canopy, the effects of snowmelt, the effects of winter lake stratification, comparison of heavy metal transport, examination of acidic sources other than direct precipitation, assessment of lake acidification during spring thaw and integration of all acidification components with a mathematical model.

  15. Ammonia emission factors for the NAPAP (National Acid Precipitation Assessment Program) emission inventory. Final report, January 1985-December 1986

    SciTech Connect

    Misenheimer, D.C.; Warn, T.E.; Zelmanowitz, S.

    1987-01-01

    The report provides information on certain sources of ammonia emissions to the atmosphere for use in the National Acid Precipitation Assessment Program (NAPAP) emission inventories. Major anthropogenic sources of ammonia emissions to the atmosphere are identified, and emission factors for these sources are presented based on a review of the most recent data available. The emission factors developed are used to estimate nationwide emissions for base year 1980 and are compared to ammonia emission factors used in other emission inventories. Major anthropogenic source categories covered are cropland spreading of livestock wastes, beef cattle feedlots, fertilizer manufacture and use, fuel combustion, ammonia synthesis, petroleum refineries, and coke manufacture. Approximately 840,000 tons of ammonia is estimated to have been emitted in the U.S. in 1980; over 64% of which is estimated to have been from livestock wastes.

  16. Biogeochemical effects of forest vegetation on acid precipitation-related water chemistry: a case study in southwest China.

    PubMed

    Chen, Jing; Li, Wei; Gao, Fang

    2010-10-01

    The elemental composition of rainwater, throughfall, and soil solutions of a forest ecosystem in the acid rain control region of southwest China was investigated during 2007-2008 to assess the acid buffering capacity of different forest covers. A possible seasonal distribution of wet deposition was identified. Sulfur was determined as the dominant acidification precursor in this region. The chemical composition of rainfall intercepted by the forest canopy was modified substantially; generally the ion concentrations were increased by dry deposition and foliar leaching. As an exception, the concentration of NH(4)(+) and NO(3)(-) decreased in throughfall, which was probably due to the absorption of nitrogen by the leaves. Elemental concentrations in soil solutions decreased with depth. The water conservation capacity of different forests was also evaluated. The most appropriate forest vegetation for water conservation and remediation of acid precipitation in this region was explored for the sake of ecosystem management, ecological restoration and economic development.

  17. Biogeochemical effects of forest vegetation on acid precipitation-related water chemistry: a case study in southwest China.

    PubMed

    Chen, Jing; Li, Wei; Gao, Fang

    2010-10-01

    The elemental composition of rainwater, throughfall, and soil solutions of a forest ecosystem in the acid rain control region of southwest China was investigated during 2007-2008 to assess the acid buffering capacity of different forest covers. A possible seasonal distribution of wet deposition was identified. Sulfur was determined as the dominant acidification precursor in this region. The chemical composition of rainfall intercepted by the forest canopy was modified substantially; generally the ion concentrations were increased by dry deposition and foliar leaching. As an exception, the concentration of NH(4)(+) and NO(3)(-) decreased in throughfall, which was probably due to the absorption of nitrogen by the leaves. Elemental concentrations in soil solutions decreased with depth. The water conservation capacity of different forests was also evaluated. The most appropriate forest vegetation for water conservation and remediation of acid precipitation in this region was explored for the sake of ecosystem management, ecological restoration and economic development. PMID:20859590

  18. The effects of a simulated acid precipitation on leaf litter quality and the growth of a detritivore in a buffered lotic system.

    PubMed

    Garden, A; Davies, R W

    1988-01-01

    The effects of a simulated acid rain on leaf litter quality and the growth of a detritivore in a buffered lotic system were investigated. Exposure of Populus balsamifera L. saplings to a simulated acid precipitation prior to leaf abscission resulted in significant decreases in foliar nitrogen content and increases in carbon: nitrogen ratios. During decomposition of the leaf litter in a buffered lotic system, microbial activity was significantly reduced. Growth of Tipula commiscibilis Diane (Diptera: Tipulidae) larvae decreased significantly when fed conditioned leaves exposed to a simulated acid precipitation prior to abscission. Reductions in detritivore growth were correlated with lower potential quality of the leaf litter resulting from increased carbon: nitrogen ratios and reduced levels of microbial activity. Thus, even in well buffered freshwater ecosystems, acid precipitation can have significant indirect effects on microbial activity and macroinvertebrate growth.

  19. The effects of a simulated acid precipitation on leaf litter quality and the growth of a detritivore in a buffered lotic system.

    PubMed

    Garden, A; Davies, R W

    1988-01-01

    The effects of a simulated acid rain on leaf litter quality and the growth of a detritivore in a buffered lotic system were investigated. Exposure of Populus balsamifera L. saplings to a simulated acid precipitation prior to leaf abscission resulted in significant decreases in foliar nitrogen content and increases in carbon: nitrogen ratios. During decomposition of the leaf litter in a buffered lotic system, microbial activity was significantly reduced. Growth of Tipula commiscibilis Diane (Diptera: Tipulidae) larvae decreased significantly when fed conditioned leaves exposed to a simulated acid precipitation prior to abscission. Reductions in detritivore growth were correlated with lower potential quality of the leaf litter resulting from increased carbon: nitrogen ratios and reduced levels of microbial activity. Thus, even in well buffered freshwater ecosystems, acid precipitation can have significant indirect effects on microbial activity and macroinvertebrate growth. PMID:15092603

  20. Towards development of lignin reinforced elastomeric compounds with reduced energy dissipation

    NASA Astrophysics Data System (ADS)

    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

  1. Isolation and structural characterization of the milled wood lignin, dioxane lignin, and cellulolytic lignin preparations from brewer's spent grain.

    PubMed

    Rencoret, Jorge; Prinsen, Pepijn; Gutiérrez, Ana; Martínez, Ángel T; Del Río, José C

    2015-01-21

    The structure of the lignin from brewer's spent grain (BSG) has been studied in detail. Three different lignin preparations, the so-called "milled-wood" lignin (MWL), dioxane lignin (DL), and cellulolytic lignin (CEL), were isolated from BSG and then thoroughly characterized by pyrolysis GC/MS, 2D-NMR, and derivatization followed by reductive cleavage (DFRC). The data indicated that BSG lignin presents a predominance of guaiacyl units (syringyl/guaiacyl ratio of 0.4-0.5) with significant amounts of associated p-coumarates and ferulates. The flavone tricin was also present in the lignin from BSG, as also occurred in other grasses. 2D-NMR (HSQC) revealed that the main substructures present are β-O-4' alkyl-aryl ethers (77-79%) followed by β-5' phenylcoumarans (11-13%) and lower amounts of β-β' resinols (5-6%) and 5-5' dibenzodioxocins (3-5%). The results from 2D-NMR (HMBC) and DFRC indicated that p-coumarates are acylating the γ-carbon of lignin side chains and are mostly involved in condensed structures. DFRC analyses also indicated a minor degree of γ-acylation with acetate groups, which takes place preferentially on S lignin (6% of S units are acetylated) over G lignin (only 1% of G units are acetylated).

  2. Bacterial enzymes involved in lignin degradation.

    PubMed

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

    2016-10-20

    Lignin forms a large part of plant biomass. It is a highly heterogeneous polymer of 4-hydroxyphenylpropanoid units and is embedded within polysaccharide polymers forming lignocellulose. Lignin provides strength and rigidity to plants and is rather resilient towards degradation. To improve the (bio)processing of lignocellulosic feedstocks, more effective degradation methods of lignin are in demand. Nature has found ways to fully degrade lignin through the production of dedicated ligninolytic enzyme systems. While such enzymes have been well thoroughly studied for ligninolytic fungi, only in recent years biochemical studies on bacterial enzymes capable of lignin modification have intensified. This has revealed several types of enzymes available to bacteria that enable them to act on lignin. Two major classes of bacterial lignin-modifying enzymes are DyP-type peroxidases and laccases. Yet, recently also several other bacterial enzymes have been discovered that seem to play a role in lignin modifications. In the present review, we provide an overview of recent advances in the identification and use of bacterial enzymes acting on lignin or lignin-derived products. PMID:27544286

  3. Bacterial enzymes involved in lignin degradation.

    PubMed

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

    2016-10-20

    Lignin forms a large part of plant biomass. It is a highly heterogeneous polymer of 4-hydroxyphenylpropanoid units and is embedded within polysaccharide polymers forming lignocellulose. Lignin provides strength and rigidity to plants and is rather resilient towards degradation. To improve the (bio)processing of lignocellulosic feedstocks, more effective degradation methods of lignin are in demand. Nature has found ways to fully degrade lignin through the production of dedicated ligninolytic enzyme systems. While such enzymes have been well thoroughly studied for ligninolytic fungi, only in recent years biochemical studies on bacterial enzymes capable of lignin modification have intensified. This has revealed several types of enzymes available to bacteria that enable them to act on lignin. Two major classes of bacterial lignin-modifying enzymes are DyP-type peroxidases and laccases. Yet, recently also several other bacterial enzymes have been discovered that seem to play a role in lignin modifications. In the present review, we provide an overview of recent advances in the identification and use of bacterial enzymes acting on lignin or lignin-derived products.

  4. Biodegradable lignin/polyolefin composite films

    SciTech Connect

    Kosikova, B.; Demjanova, V.; Mikulasova, M.; Lora, J.H.

    1993-12-31

    From the view point of environmental protection, the plastic wastes, especially from packing materials, represent a potential waste problem. Various approaches were examined to develop partially or completely biodegradable plastics. New type of partially biodegradable polyolefins was prepared by blending of polypropylene with lignin, which was recovered in the ALCELL process, an organosolv pulping process that uses ethanol-water as the delignifying agent. Films of blends with up to 10% wt ALCELL lignin, prepared in absence of commercial stabilizers, had acceptable mechanical strengths. The effect of lignin on biodegradability of the composite films was examined by comparison of behaviour of both pure and lignin containing films during treatment with fungus Phanerochaete chrysosporium. It was found that this fungus is able to grow and to produce lignolytic enzymes in the presence of the films containing lignin. Biodegradation of lignin in the composite film was confirmed by the releasing of lignin fragments into the extracellular fluid. Because of measurement of mechanical properties offers a mean of direct estimation of polymer degradation, the degree of biodegradation of the films tested was followed by monitoring of elongation at break. The changes of break at elongation in the course of enzymatic treatment revealed that the lignin/PP composite films are potentially environmentally nonpersisting. The micrographs of the lignin containing films obtained by scanning electron microscopy show the significant changes of the film surface upon degradation with Phanerochaete chrysosporium in contrast to unchanged lignin free film.

  5. Looking for Arabidopsis thaliana peroxidases involved in lignin biosynthesis.

    PubMed

    Herrero, Joaquín; Esteban-Carrasco, Alberto; Zapata, José Miguel

    2013-06-01

    Monolignol polymerization into lignin is catalyzed by peroxidases or laccases. Recently, a Zinnia elegans peroxidase (ZePrx) that is considered responsible for monolignol polymerization in this plant has been molecularly and functionally characterized. Nevertheless, Arabidopsis thaliana has become an alternative model plant for studies of lignification, filling the gaps that may occur with Z. elegans. The arabidopsis genome offers the possibility of performing bioinformatic analyses and data mining that are not yet feasible with other plant species, in order to obtain preliminary evidence on the role of genes and proteins. In our search for arabidopsis homologs to the ZePrx, we performed an exhaustive in silico characterization of everything from the protein to the transcript of Arabidopsis thaliana peroxidases (AtPrxs) homologous to ZePrx, with the aim of identifying one or more peroxidases that may be involved in monolignol polymerization. Nine peroxidases (AtPrx 4, 5, 52, 68, 67, 36, 14, 49 and 72) with an E-value greater than 1e-80 with ZePrx were selected for this study. The results demonstrate that a high level of 1D, 2D and 3D homology between these AtPrxs and ZePrx are not always accompanied by the presence of the same electrostatic and mRNA properties that indicate a peroxidase is involved in lignin biosynthesis. In summary, we can confirm that the peroxidases involved in lignification are among AtPrx 4, 52, 49 and 72. Their structural and mRNA features indicate that exert their action in the cell wall similar to ZePrx.

  6. Simultaneously disrupting AtPrx2, AtPrx25 and AtPrx71 alters lignin content and structure in Arabidopsis stem.

    PubMed

    Shigeto, Jun; Itoh, Yoshitaka; Hirao, Sakie; Ohira, Kaori; Fujita, Koki; Tsutsumi, Yuji

    2015-04-01

    Plant class III heme peroxidases catalyze lignin polymerization. Previous reports have shown that at least three Arabidopsis thaliana peroxidases, AtPrx2, AtPrx25 and AtPrx71, are involved in stem lignification using T-DNA insertion mutants, atprx2, atprx25, and atprx71. Here, we generated three double mutants, atprx2/atprx25, atprx2/atprx71, and atprx25/atprx71, and investigated the impact of the simultaneous deficiency of these peroxidases on lignins and plant growth. Stem tissue analysis using the acetyl bromide method and derivatization followed by reductive cleavage revealed improved lignin characteristics, such as lowered lignin content and increased arylglycerol-β-aryl (β-O-4) linkage type, especially β-O-4 linked syringyl units, in lignin, supporting the roles of these genes in lignin polymerization. In addition, none of the double mutants exhibited severe growth defects, such as shorter plant stature, dwarfing, or sterility, and their stems had improved cell wall degradability. This study will contribute to progress in lignin bioengineering to improve lignocellulosic biomass.

  7. An Engineered Monolignol 4-O-Methyltransferase Depresses Lignin Biosynthesis and Confers Novel Metabolic Capability in Arabidopsis[C][W][OA

    PubMed Central

    Zhang, Kewei; Bhuiya, Mohammad-Wadud; Pazo, Jorge Rencoret; Miao, Yuchen; Kim, Hoon; Ralph, John; Liu, Chang-Jun

    2012-01-01

    Although the practice of protein engineering is industrially fruitful in creating biocatalysts and therapeutic proteins, applications of analogous techniques in the field of plant metabolic engineering are still in their infancy. Lignins are aromatic natural polymers derived from the oxidative polymerization of primarily three different hydroxycinnamyl alcohols, the monolignols. Polymerization of lignin starts with the oxidation of monolignols, followed by endwise cross-coupling of (radicals of) a monolignol and the growing oligomer/polymer. The para-hydroxyl of each monolignol is crucial for radical generation and subsequent coupling. Here, we describe the structure-function analysis and catalytic improvement of an artificial monolignol 4-O-methyltransferase created by iterative saturation mutagenesis and its use in modulating lignin and phenylpropanoid biosynthesis. We show that expressing the created enzyme in planta, thus etherifying the para-hydroxyls of lignin monomeric precursors, denies the derived monolignols any participation in the subsequent coupling process, substantially reducing lignification and, ultimately, lignin content. Concomitantly, the transgenic plants accumulated de novo synthesized 4-O-methylated soluble phenolics and wall-bound esters. The lower lignin levels of transgenic plants resulted in higher saccharification yields. Our study, through a structure-based protein engineering approach, offers a novel strategy for modulating phenylpropanoid/lignin biosynthesis to improve cell wall digestibility and diversify the repertories of biologically active compounds. PMID:22851762

  8. Lignin phenols derivatives in lichens.

    PubMed

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

    2015-01-01

    Lignin monophenols have been measured in the cupric oxide oxidation products from lichens of different systematic groups. It is shown for the first time that syringyl structures in most lichens strongly dominate over vanillyl and p-hydroxyl ones (S/V 7-583, S/P 3-30). This distinguishes lichens from algae and mosses (p-hydroxyl phenols are dominant) and from higher plants (S/V ratios are from 0 in gymnosperms to 1.1-5.2 in angiosperms). Molecular ratios of phenols as well as the ratios of acids to aldehydes in lichens were different from lignin of higher plants, suggesting contribution of non-lignin phenols in CuO oxidation products. The contents of syringyl and vanillyl phenols in some lichen species were comparable to non-woody tissues of higher plants. Results of the study suggest that lichens can be important source of aromatic structures in soils and hydrosphere, particularly in the regions were lichens are abundant. PMID:26728733

  9. Lignin phenols derivatives in lichens.

    PubMed

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

    2015-01-01

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

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

    SciTech Connect

    Lewis, N.G.

    1991-12-31

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

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

    PubMed Central

    2012-01-01

    Background Lignin is an integral component of the plant cell wall matrix but impedes the conversion of biomass into biofuels. The plasticity of lignin biosynthesis should permit the inclusion of new compatible phenolic monomers such as flavonoids into cell wall lignins that are consequently less recalcitrant to biomass processing. In the present study, epigallocatechin gallate (EGCG) was evaluated as a potential lignin bioengineering target for rendering biomass more amenable to processing for biofuel production. Results In vitro peroxidase-catalyzed polymerization experiments revealed that both gallate and pyrogallyl (B-ring) moieties in EGCG underwent radical cross-coupling with monolignols mainly by β–O–4-type cross-coupling, producing benzodioxane units following rearomatization reactions. Biomimetic lignification of maize cell walls with a 3:1 molar ratio of monolignols and EGCG permitted extensive alkaline delignification of cell walls (72 to 92%) that far exceeded that for lignified controls (44 to 62%). Alkali-insoluble residues from EGCG-lignified walls yielded up to 34% more glucose and total sugars following enzymatic saccharification than lignified controls. Conclusions It was found that EGCG readily copolymerized with monolignols to become integrally cross-coupled into cell wall lignins, where it greatly enhanced alkaline delignification and subsequent enzymatic saccharification. Improved delignification may be attributed to internal trapping of quinone-methide intermediates to prevent benzyl ether cross-linking of lignin to structural polysaccharides during lignification, and to the cleavage of ester intra-unit linkages within EGCG during pretreatment. Overall, our results suggest that apoplastic deposition of EGCG for incorporation into lignin would be a promising plant genetic engineering target for improving the delignification and saccharification of biomass crops. PMID:22889353

  12. cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization

    SciTech Connect

    Vardon, Derek R.; Rorrer, Nicholas A.; Salvachúa, Davinia; Settle, Amy E.; Johnson, Christopher W.; Menart, Martin J.; Cleveland, Nicholas S.; Ciesielski, Peter N.; Steirer, K. Xerxes; Dorgan, John R.; Beckham, Gregg T.

    2016-01-01

    cis,cis-Muconic acid is a polyunsaturated dicarboxylic acid that can be produced renewably via the biological conversion of sugars and lignin-derived aromatic compounds. Subsequently, muconic acid can be catalytically converted to adipic acid -- the most commercially significant dicarboxylic acid manufactured from petroleum. Nylon-6,6 is the major industrial application for adipic acid, consuming 85% of market demand; however, high purity adipic acid (99.8%) is required for polymer synthesis. As such, process technologies are needed to effectively separate and catalytically transform biologically derived muconic acid to adipic acid in high purity over stable catalytic materials. To that end, this study: (1) demonstrates bioreactor production of muconate at 34.5 g L-1 in an engineered strain of Pseudomonas putida KT2440, (2) examines the staged recovery of muconic acid from culture media, (3) screens platinum group metals (e.g., Pd, Pt, Rh, Ru) for activity and leaching stability on activated carbon (AC) and silica supports, (4) evaluates the time-on-stream performance of Rh/AC in a trickle bed reactor, and (5) demonstrates the polymerization of bio-adipic acid to nylon-6,6. Separation experiments confirmed AC effectively removed broth color compounds, but subsequent pH/temperature shift crystallization resulted in significant levels of Na, P, K, S and N in the crystallized product. Ethanol dissolution of muconic acid precipitated bulk salts, achieving a purity of 99.8%. Batch catalysis screening reactions determined that Rh and Pd were both highly active compared to Pt and Ru, but Pd leached significantly (1-9%) from both AC and silica supports. Testing of Rh/AC in a continuous trickle bed reactor for 100 h confirmed stable performance after 24 h, although organic adsorption resulted in reduced steady-state activity. Lastly, polymerization of bio-adipic acid with hexamethyldiamine produced nylon-6,6 with comparable properties to its petrochemical counterpart

  13. Preparing spherical lignin from rice husk.

    PubMed

    Zhang, Hongxi; Zhao, Xu; Ding, Xuefeng; Lei, Hong; Wang, Zichen

    2013-08-01

    Lignin is one of the important branched amorphous polymers, which generally has the irregular and fractal morphology. The preparation of regular sphere of lignin needs long steps and special conditions. In this study, the regular sphere of lignin can be simply prepared from rice husk (RH) under certain conditions. Namely, RH is mixed with 35% ethanol aqueous solution in the proportion of 1:10 (g:mL), non-isothermally heated to 493 K and kept for 5 h. After filtration and air-drying at room temperature, the regular lignin sphere with the diameter of 100-400 nm is obtained. The regular sphere of lignin has the potential utilization in fields such as reactive functional materials, photo sensing materials and surface active materials in cosmetics. The mechanism of formation of the regular spherical lignin is proposed and discussed in this paper.

  14. Lignin-Derived Advanced Carbon Materials

    DOE PAGES

    Chatterjee, Sabornie; Saito, Tomonori

    2015-11-16

    Lignin is a highly abundant source of renewable carbon that can be considered as a valuable sustainable source of biobased materials. By applying specific pretreatments and manufacturing methods, it has been found that lignin can be converted into a variety of value-added carbon materials. However, the physical and chemical heterogeneities of lignin complicate its use as a feedstock. Herein, we discuss the lignin manufacturing process, the effects of pretreatments and manufacturing methods on the properties of product lignin, and structure–property relationships in various applications of lignin-derived carbon materials, such as carbon fibers, carbon mats, activated carbons, carbon films, and templatedmore » carbon.« less

  15. Lignin-Based Triple Shape Memory Polymers.

    PubMed

    Sivasankarapillai, Gopakumar; Li, Hui; McDonald, Armando G

    2015-09-14

    Lignin-based triple shape memory polymers comprised of both permanent covalent cross-links and physical cross-links have been synthesized. A mixing phase with poly(ester-amine) and poly(ester-amide) network having two distinct glass transitions was hot mixed with more structurally homogenized methanol soluble lignin fraction by one-pot, two-step method. Triple shape properties arise from the combined effect of the glass transition of polyester copolymers and lignin and the dissociation of self-complementary hydrogen bonding and cross-link density. The percentage of recovery in each stage was investigated and it was proved that the first recovery is related with lignin-poly(ester-amine) rich network and the second recovery stage is related with lignin-poly(ester-amide) rich network. The thermal and mechanical properties of the lignin-copolymer networks were also investigated using differential scanning calorimetry and dynamic mechanical analysis.

  16. Use of a non-linear model in examining growth responses of loblolly pine to ozone and acid precipitation

    NASA Astrophysics Data System (ADS)

    Somerville, Matthew C.; Shadwick, Douglas S.; Meldahl, Ralph S.; Chappelka, Arthur H.; Lockaby, B. Graeme

    Monthly diameter 2 × height ( d 2h ) data were measured over two years in open-top chambers at Auburn University, Alabama. This study exposed seedlings from two half-sibling loblolly pine ( Pinus taeda L.) families to ozone and acid precipitation treatments. For these data, the accumulation of d 2h ) by individual trees over two years was efficiently represented by a six-parameter non-linear model of ln ( d 2h ) as a function of time. Multivariate analysis of variance using these six estimated parameters for each seedling resulted in greater sensitivity to treatment differences as measured by tests of hypotheses than did analysis of covariance on ln (final d 2h ). This result illustrates the importance of utilizing appropriate analyses that can bring as much of the data as is possible to bear on the question at hand. A test for additional information indicated that five of the six parameters contributed important information concerning treatment differences for at least one of the two families tested. It may be inferred that the treatments have an important effect on the nature of d 2h accumulation within a growing season as well as on the d 2h at the end of the growing season.

  17. The effects of acid precipitation runoff episodes on reservoir and tapwater quality in an Appalachian Mountain water supply.

    PubMed Central

    Sharpe, W E; DeWalle, D R

    1990-01-01

    The aluminum concentration and Ryznar Index increased and the pH decreased in a small Appalachian water supply reservoir following acid precipitation runoff episodes. Concomitant increases in tapwater aluminum and decreases in tapwater pH were also observed at two homes in the water distribution system. Lead concentrations in the tapwater of one home frequently exceeded recommended levels, although spatial and temporal variation in tapwater copper and lead concentrations was considerable. Since source water and reservoir water copper and lead concentrations were much lower, the increased copper and lead concentrations in tapwater were attributed to corrosion of household plumbing. Tapwater copper concentration correlated well with tapwater pH and tapwater temperature. Asbestos fibers were not detected in tapwater. The asbestos-cement pipe in the water distribution system was protected by a spontaneous metallic coating that inhibited fiber release from the pipe. Several simultaneous reactions were hypothesized to be taking place in the distribution system that involved corrosion of metallic components and coating of asbestos-cement pipe components in part with corrosion products and in part by cations of watershed origin. Greater water quality changes might be expected in areas of higher atmospheric deposition. Images FIGURE 5. FIGURE 6. PMID:2088742

  18. The effects of acid precipitation runoff episodes on reservoir and tapwater quality in an Appalachian Mountain water supply

    SciTech Connect

    Sharpe, W.E.; DeWalle, D.R. )

    1990-11-01

    The aluminum concentration and Ryznar Index increased and the pH decreased in a small Appalachian water supply reservoir following acid precipitation runoff episodes. Concomitant increases in tapwater aluminum and decreases in tapwater pH were also observed at two homes in the water distribution system. Lead concentrations in the tapwater of one home frequently exceeded recommended levels, although spatial and temporal variation in tapwater copper and lead concentrations was considerable. Since source water and reservoir water copper and lead concentrations were much lower, the increased copper and lead concentrations in tapwater were attributed to corrosion of household plumbing. Tapwater copper concentration correlated well with tapwater pH and tapwater temperature. Asbestos fibers were not detected in tapwater. The asbestos-cement pipe in the water distribution system was protected by a spontaneous metallic coating that inhibited fiber release from the pipe. Several simultaneous reactions were hypothesized to be taking place in the distribution system that involved corrosion of metallic components and coating of asbestos-cement pipe components in part with corrosion products and in part by cations of watershed origin. Greater water quality changes might be expected in areas of higher atmospheric deposition.

  19. The effects of acid precipitation runoff episodes on reservoir and tapwater quality in an Appalachian Mountain water supply.

    PubMed

    Sharpe, W E; DeWalle, D R

    1990-11-01

    The aluminum concentration and Ryznar Index increased and the pH decreased in a small Appalachian water supply reservoir following acid precipitation runoff episodes. Concomitant increases in tapwater aluminum and decreases in tapwater pH were also observed at two homes in the water distribution system. Lead concentrations in the tapwater of one home frequently exceeded recommended levels, although spatial and temporal variation in tapwater copper and lead concentrations was considerable. Since source water and reservoir water copper and lead concentrations were much lower, the increased copper and lead concentrations in tapwater were attributed to corrosion of household plumbing. Tapwater copper concentration correlated well with tapwater pH and tapwater temperature. Asbestos fibers were not detected in tapwater. The asbestos-cement pipe in the water distribution system was protected by a spontaneous metallic coating that inhibited fiber release from the pipe. Several simultaneous reactions were hypothesized to be taking place in the distribution system that involved corrosion of metallic components and coating of asbestos-cement pipe components in part with corrosion products and in part by cations of watershed origin. Greater water quality changes might be expected in areas of higher atmospheric deposition.

  20. Editorial: Acid precipitation

    SciTech Connect

    1995-09-01

    This editorial focuses on acid rain and the history of public and governmental response to acid rain. Comments on a book by Gwineth Howell `Acid Rain and Acid Waters` are included. The editor feels that Howells has provide a service to the environmental scientific community, with a textbook useful to a range of people, as well as a call for decision makers to learn from the acid rain issue and use it as a model for more sweeping global environmental issues. A balance is needed among several parameters such as level of evidence, probability that the evidence will lead to a specific direction and the cost to the global community. 1 tab.

  1. Method for recovering and using lignin in adhesive resins by extracting demethylated lignin

    DOEpatents

    Schroeder, Herbert A.

    1991-01-01

    Lignin, or a lignin derived material, which has been significantly demethylated (e.g., the demethylated lignin found in the raffinate produced as a by-product of dimethyl sulfide production which can be carried out using the spent liquor from wood pulping operations) can be isolated by a process wherein an organic solvent is added to a lignin-containing aqueous solution. The organic solvent is typically a polar, and at least a partially water-immiscible substance such as, for example, ethyl acetate. The resulting lignin-containing aqueous solution/organic solvent mixture is acidified to produce a water layer which is discarded and an organic solvent layer which contains the demethylated lignin. Upon its recovery, the demethylated lignin is preferably dried and stored until it is used (along with an alkali, an aldehyde and an adhesive filler) in compounding an adhesive of the type generally used in the manufacture of plywood.

  2. Method for recovering and using lignin in adhesive resins by extracting demethylated lignin

    DOEpatents

    Schroeder, Herbert A.

    1991-01-01

    Lignin, or a lignin derived material, which has been significantly demethylated (e.g., the demethylated lignin found in the raffinate produced as a by-product of dimethyl sulfide production which can be carried out using the spent liquor from wood pulping operations) can be isolated by a process wherein an organic solvent is added to a lignin-containing aqueous solution. The organic solvent is typically a polar, and at least a partially water-immiscible substance such as, for example, ethyl acetate. The resulting lignin-containing aqueous solution/organic solvent mixture is acidified to produce a water layer which is discarded and an organic solvent layer which contains the demethylated lignin. Upon its recovery, the demethylated lignin is dissolved in an alkaline solution to which an aldehyde source is added to produce a resol-type resin. The aldehyde source may be formaldehyde in solution, paraformaldehyde, hexamethylenetetramine, or other aldehydes including acetaldehyde, furfural, and their derivatives.

  3. (Characterization of lignin peroxidases from Phanerochaete)

    SciTech Connect

    Not Available

    1990-11-14

    Work has continued on characterizing the kinetics of lignin peroxidases and has now expanded to include the chemistry of Mn peroxidases. Progress in these two area in addition to the authors work on the molecular biology of lignin biodegradation is briefly described below. Copies of two reprints and one preprint which have resulted from the work are attached.

  4. Lignin: Characterization of a Multifaceted Crop Component

    PubMed Central

    2013-01-01

    Lignin is a plant component with important implications for various agricultural disciplines. It confers rigidity to cell walls, and is therefore associated with tolerance to abiotic and biotic stresses and the mechanical stability of plants. In animal nutrition, lignin is considered an antinutritive component of forages as it cannot be readily fermented by rumen microbes. In terms of energy yield from biomass, the role of lignin depends on the conversion process. It contains more gross energy than other cell wall components and therefore confers enhanced heat value in thermochemical processes such as direct combustion. Conversely, it negatively affects biological energy conversion processes such as bioethanol or biogas production, as it inhibits microbial fermentation of the cell wall. Lignin from crop residues plays an important role in the soil organic carbon cycling, as it constitutes a recalcitrant carbon pool affecting nutrient mineralization and carbon sequestration. Due to the significance of lignin in several agricultural disciplines, the modification of lignin content and composition by breeding is becoming increasingly important. Both mapping of quantitative trait loci and transgenic approaches have been adopted to modify lignin in crops. However, breeding goals must be defined considering the conflicting role of lignin in different agricultural disciplines. PMID:24348159

  5. Method for regulation of plant lignin composition

    DOEpatents

    Chapple, Clint

    1999-01-01

    A method is disclosed for the regulation of lignin composition in plant tissue. Plants are transformed with a gene encoding an active F5H gene. The expression of the F5H gene results in increased levels of syringyl monomer providing a lignin composition more easily degraded with chemicals and enzymes.

  6. Development of Lignin-Based Polyurethane Thermoplastics

    SciTech Connect

    Saito, Tomonori; Perkins, Joshua H; Jackson, Daniel C; Trammell, Neil E; Hunt, Marcus A; Naskar, Amit K

    2013-01-01

    In our continued effort to develop value-added thermoplastics from lignin, here we report utilizing a tailored feedstock to synthesize mechanically robust thermoplastic polyurethanes at very high lignin contents (75 65 wt %). The molecular weight and glass transition temperature (Tg) of lignin were altered through cross-linking with formaldehyde. The cross-linked lignin was coupled with diisocyanate-based telechelic polybutadiene as a network-forming soft segment. The appearance of two Tg s, around 35 and 154 C, for the polyurethanes indicates the existence of two-phase morphology, a characteristic of thermoplastic copolymers. A calculated Flory-Huggins interaction parameter of 7.71 also suggests phase immiscibility in the synthesized lignin polyurethanes. An increase in lignin loading increased the modulus, and an increase in crosslink-density increased the modulus in the rubbery plateau region of the thermoplastic. This path for synthesis of novel lignin-based polyurethane thermoplastics provides a design tool for high performance lignin-based biopolymers.

  7. Changes in acid precipitation-related water chemistry of lakes from southwestern New Brunswick, Canada, 1986-2001.

    PubMed

    Pilgrim, W; Clair, T A; Choate, J; Hughes, R

    2003-01-01

    Between 1986 and 2001, thirty-nine lakes in southwestern New Brunswick in Atlantic Canada were surveyed for acid precipitation-related water quality changes. Most of the study lakes are located on granite bedrock and represent the most acid sensitive lakes in the province. Between 1987 and 1992, hydrogen ion deposition to the lake study area averaged 452 eq ha(-1) yr(-1), compared to 338 eq ha(-1) yr(-1) between 1993 and 2000, a 25% reduction. The lake chemistry data were evaluated by dividing the lakes into four clusters for each survey year based on their acid neutralizing capacity. Twenty percent of the lakes (cluster IV) had an average ANC of 40 microeq L(-1) or greater and maintained an average pH of greater than 6 over the duration of the study period. A pH of 6 or greater is considered a healthy benchmark for maintaining biodiversity. The remaining 31 lakes (clusters I to III) had an average ANC of less than 40 microeq L(-1) and maintained an average pH of less than 6. Other lake chemistry changes included a general decline in lake sulphate and colour over the duration of the survey period, followed by more recent improvements in calcium ion, pH and ANC, and notably higher but declining aluminum levels in lower ANC and pH lakes. Nitrate accounted for 37% of the acid deposition to the study area, however it was not detectable in the lakes. Although acid deposition has declined and these lakes are beginning to show signs of acid recovery, 80% of the study lakes remain acid sensitive having little buffering capacity with low calcium, pH and ANC.

  8. Biodegradation of lignin by Agaricus Bisporus

    SciTech Connect

    Vane, C.H.; Abbott, G.D.; Head, I.M.

    1996-12-31

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

  9. Rocks, soils, and water quality. Relationships and implications for effects of acid precipitation on surface water in the northeastern United States

    SciTech Connect

    Kaplan, E.; Thode, H.C. Jr.; Protas, A.

    1981-05-01

    Distribution of rocks and soils in Northeast counties were investigated for the degree to which they influence pH and alkalinity in surface waters. Using 283 counties, path analysis resulted in two models of equivalent explanatory power. Each model indicated the importance of both rocks and soils as determinants of pH and alkalinity in surface waters, and as important factors in the sensitivity of natural waters to acidification from acid precipitation. Previous studies have emphasized the importance of bedrock geology, at the expense of knowledge about soils, in an understanding of waters sensitive to the effects of acid precipitation. Our regional analysis found that rocks were contributors to the buffering capacity of surface water; however, the presence of a large percentage of alfisol soils better indicates locations of waters with higher levels of alkalinity, and thus of greater resistance to effects of acid rain.

  10. Chain Reaction Polymerization.

    ERIC Educational Resources Information Center

    McGrath, James E.

    1981-01-01

    The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

  11. Methanol fractionation of softwood Kraft lignin: impact on the lignin properties.

    PubMed

    Saito, Tomonori; Perkins, Joshua H; Vautard, Frederic; Meyer, Harry M; Messman, Jamie M; Tolnai, Balazs; Naskar, Amit K

    2014-01-01

    The development of technologies to tune lignin properties for high-performance lignin-based materials is crucial for the utilization of lignin in various applications. Here, the effect of methanol (MeOH) fractionation on the molecular weight, molecular weight distribution, glass transition temperature (Tg ), thermal decomposition, and chemical structure of lignin were investigated. Repeated MeOH fractionation of softwood Kraft lignin successfully removed the low-molecular-weight fraction. The separated high-molecular-weight lignin showed a Tg of 211 °C and a char yield of 47 %, much higher than those of as-received lignin (Tg 153 °C, char yield 41 %). The MeOH-soluble fraction of lignin showed an increased low-molecular-weight fraction and a lower Tg (117 °C) and char yield (32%). The amount of low-molecular-weight fraction showed a quantitative correlation with both 1/Tg and char yield in a linear regression. This study demonstrated the efficient purification or fractionation technology for lignin; it also established a theoretical and empirical correlation between the physical characteristics of fractionated lignins. PMID:24458739

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

    SciTech Connect

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

    2004-11-10

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

  13. Gene silencing of BnTT10 family genes causes retarded pigmentation and lignin reduction in the seed coat of Brassica napus.

    PubMed

    Zhang, Kai; Lu, Kun; Qu, Cunmin; Liang, Ying; Wang, Rui; Chai, Yourong; Li, Jiana

    2013-01-01

    Yellow-seed (i.e., yellow seed coat) is one of the most important agronomic traits of Brassica plants, which is correlated with seed oil and meal qualities. Previous studies on the Brassicaceae, including Arabidopsis and Brassica species, proposed that the seed-color trait is correlative to flavonoid and lignin biosynthesis, at the molecular level. In Arabidopsis thaliana, the oxidative polymerization of flavonoid and biosynthesis of lignin has been demonstrated to be catalyzed by laccase 15, a functional enzyme encoded by the AtTT10 gene. In this study, eight Brassica TT10 genes (three from B. napus, three from B. rapa and two from B. oleracea) were isolated and their roles in flavonoid oxidation/polymerization and lignin biosynthesis were investigated. Based on our phylogenetic analysis, these genes could be divided into two groups with obvious structural and functional differentiation. Expression studies showed that Brassica TT10 genes are active in developing seeds, but with differential expression patterns in yellow- and black-seeded near-isogenic lines. For functional analyses, three black-seeded B. napus cultivars were chosen for transgenic studies. Transgenic B. napus plants expressing antisense TT10 constructs exhibited retarded pigmentation in the seed coat. Chemical composition analysis revealed increased levels of soluble proanthocyanidins, and decreased extractable lignin in the seed coats of these transgenic plants compared with that of the controls. These findings indicate a role for the Brassica TT10 genes in proanthocyanidin polymerization and lignin biosynthesis, as well as seed coat pigmentation in B. napus.

  14. Characterization of electrospun lignin based carbon fibers

    NASA Astrophysics Data System (ADS)

    Poursorkhabi, Vida; Mohanty, Amar; Misra, Manjusri

    2015-05-01

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

  15. Characterization of asparagus lignin by HPLC.

    PubMed

    Jaramillo-Carmona, S; Fuentes-Alventosa, J M; Rodríguez-Gutiérrez, G; Waldron, K W; Smith, A C; Guillén-Bejarano, R; Fernández-Bolaños, J; Jiménez-Araujo, A; Rodríguez-Arcos, R

    2008-09-01

    Lignin is the cell wall component most frequently associated with hardening. Its characterization and quantification are very important to understand the biochemical modifications related to the changes in texture of vegetables such as asparagus (Asparagus officinalis), in which this organoleptic attribute is a very important quality factor. In this study, asparagus lignin from the basal sections of fresh and stored spears was analyzed using 2 methods, the traditional (Klason lignin) and the recently developed derivatization, followed by reductive cleavage (DFRC) method. The latter is a simple and reproducible technique for lignin characterization based on a degradation procedure that produces analyzable monomers and dimers by cleaving alpha- and beta-aryl ethers in lignins. The primary monomers derived from DFRC degradation of lignins are essentially p-coumaryl peracetate, coniferyl peracetate, and sinapyl peracetate. To evaluate the efficiency of the DFRC method, our investigations have been carried on distinct sample types, including wood (data not shown), straw, and asparagus samples. The results have confirmed that lignin composition is affected by plant nature. It has been found that whereas wood samples mostly contain coniferyl units, plant foods, such as straw and asparagus, contain both coniferyl and guaiacyl units. PMID:18803697

  16. Lignin-derived phenols in Houston aerosols: implications for natural background sources.

    PubMed

    Shakya, Kabindra M; Louchouarn, Patrick; Griffin, Robert J

    2011-10-01

    Solvent-extractable monomeric methoxyphenols in aerosol samples conventionally have been used to indicate the influence of biomass combustion. In addition, the presence of lignin oxidation products (LOP), derived from the CuO oxidation of vascular plant organic matter, can help trace the source and inputs of primary biological particles in aerosols. Ambient aerosols (coarse and fine) collected in Houston during summer 2010 were analyzed by gas chromatography-mass spectrometry to characterize monomeric and polymeric sources of LOPs. This is the first time polymeric forms of the LOPs have been characterized in ambient aerosols. The absence or small concentrations of solvent-extractable monomeric LOPs and levoglucosan isomers point to the limited influence of biomass burning during the sampling period. The trace levels of anhydrosugar concentrations most likely result from long-range transport. This observation is supported by the absence of co-occurring lignin monomers that undergo photochemical degradation during transport. The larger concentration (142 ng m(-3)) of lignin polymers in coarse aerosols shows the relative importance of primary biological aerosol particles, even in the urban atmosphere. The LOP parameters suggest a predominant influence from woody tissue of angiosperms, with minor influence from soft tissues, gymnosperms, and soil organic matter.

  17. Regiochemical control of monolignol radical coupling: a new paradigm for lignin and lignan biosynthesis

    NASA Technical Reports Server (NTRS)

    Gang, D. R.; Costa, M. A.; Fujita, M.; Dinkova-Kostova, A. T.; Wang, H. B.; Burlat, V.; Martin, W.; Sarkanen, S.; Davin, L. B.; Lewis, N. G.

    1999-01-01

    BACKGROUND: Although the lignins and lignans, both monolignol-derived coupling products, account for nearly 30% of the organic carbon circulating in the biosphere, the biosynthetic mechanism of their formation has been poorly understood. The prevailing view has been that lignins and lignans are produced by random free-radical polymerization and coupling, respectively. This view is challenged, mechanistically, by the recent discovery of dirigent proteins that precisely determine both the regiochemical and stereoselective outcome of monolignol radical coupling. RESULTS: To understand further the regulation and control of monolignol coupling, leading to both lignan and lignin formation, we sought to clone the first genes encoding dirigent proteins from several species. The encoding genes, described here, have no sequence homology with any other protein of known function. When expressed in a heterologous system, the recombinant protein was able to confer strict regiochemical and stereochemical control on monolignol free-radical coupling. The expression in plants of dirigent proteins and proposed dirigent protein arrays in developing xylem and in other lignified tissues indicates roles for these proteins in both lignan formation and lignification. CONCLUSIONS: The first understanding of regiochemical and stereochemical control of monolignol coupling in lignan biosynthesis has been established via the participation of a new class of dirigent proteins. Immunological studies have also implicated the involvement of potential corresponding arrays of dirigent protein sites in controlling lignin biopolymer assembly.

  18. Challenging/interesting lignin times

    DOE PAGES

    Ragauskas, Arthur J.

    2016-08-31

    Anyone who is working in the fuels industry knows that we are living in challenging times. On a personal note, I recall that ~5 years ago, some of my children's friends headed out into the petroleum industry to start their careers and several have now returned because of the retrenching work force. Despite these challenging times, the cellulosic ethanol industry continues to develop commercial operations, but with today's cost structure, biofuels production facilities have certainly slowed their pace of development and roll-out. Furthermore, the biological technology platform for biorefining plant polysaccharides to biofuels has been reported to have an intrinsicmore » advantage, if it can convert its waste lignin stream to value-added components.[1]« less

  19. Pseudo-lignin formation and its impact on enzymatic hydrolysis.

    PubMed

    Hu, Fan; Jung, Seokwon; Ragauskas, Arthur

    2012-08-01

    Pseudo-lignin, which can be broadly defined as aromatic material that yields a positive Klason lignin value and is not derived from native lignin, has been recently reported to form during the dilute acid pretreatment of poplar holocellulose. To investigate the chemistry of pseudo-lignin formation, GPC, FT-IR and 13C NMR were utilized to characterize pseudo-lignin extracted from dilute-acid pretreated α-cellulose and holocellulose. The results showed that pseudo-lignin consisting of carbonyl, carboxylic, aromatic and aliphatic structures was produced from dilute acid pretreated cellulose and hemicellulose. Pseudo-lignin extracted from holocellulose pretreated at different conditions had similar molecular weights (Mn∼1000 g/mol; Mw∼5000 g/mol) and structural features (carbonyl, carboxylic, aromatic and methoxy structures). These characterizations have provided the pseudo-lignin formation mechanisms during pretreatment. The presence and structure of pseudo-lignin is important since pseudo-lignin decreases the enzymatic conversion. PMID:22609707

  20. Microbial conversions of lignin to useful chemicals using a lignin-degrading Streptomyces

    SciTech Connect

    Crawford, D.L.

    1981-01-01

    The lignocellulose-decomposing abilities of an actinomycete, Streptomyces viridosporus T7A, were studied in relation to the potential utilization of this strain for the bioconversion of lignin to useful chemicals. Both carbohydrate and lignin components were degraded. The grass and corn lignocelluloses were degraded much more extensively than the spruce and maple lignocelluloses; therefore the former were considered preferable as substrates for bioconversion. Both inoculated and control culture supernatants contained solvent extractible, phenolic, lignin-derived compounds with recoveries ranging between 3.1 and 12.2% of the initial lignin substrate. Lignin fragments that were identified included p-hydroxybenzoic acid, vanillic acid, protocatechuic acid, p-coumaric acid, syringic acid, ferulic acid, and the ketol (1-hydroxy-3-(4-hydroxy-3-methoxyphenyl)-2-propanone). The potential for using S. viridosporus in lignin to chemical bioconversions was discussed.

  1. Effects of Soluble Lignin on the Formic Acid-Catalyzed Formation of Furfural: A Case Study for the Upgrading of Hemicellulose.

    PubMed

    Dussan, Karla; Girisuta, Buana; Lopes, Marystela; Leahy, James J; Hayes, Michael H B

    2016-03-01

    A comprehensive study is presented on the conversion of hemicellulose sugars in liquors obtained from the fractionation of Miscanthus, spruce bark, sawdust, and hemp by using formic acid. Experimental tests with varying temperature (130-170 °C), formic acid concentration (10-80 wt%), carbohydrate concentrations, and lignin separation were carried out, and experimental data were compared with predictions obtained by reaction kinetics developed in a previous study. The conversions of xylose and arabinose into furfural were inherently affected by the presence of polymeric soluble lignin, decreasing the maximum furfural yields observed experimentally by up to 24%. These results were also confirmed in synthetic mixtures of pentoses with Miscanthus and commercial alkali lignin. This observation was attributed to side reactions involving intermediate stable sugar species reacting with solubilized lignin during the conversion of xylose into furfural.

  2. Lignin Sensor Based On Flash-Pyrolysis Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Kwack, Eug Y.; Lawson, Daniel D.; Shakkottai, Parthasarathy

    1990-01-01

    New lignin sensor takes only few minutes to measure lignin content of specimen of wood, pulp, paper, or similar material. Includes flash pyrolizer and ion-trap detector that acts as mass spectrometer. Apparatus measures amount of molecular fragments of lignin in pyrolysis products of samples. Helpful in controlling digestors in paper mills to maintain required lignin content, and also in bleaching plants, where good control of bleaching becomes possible if quick determination of lignin content made.

  3. Computational Design of Lignin Depolymerization Catalysts

    SciTech Connect

    Kim, S.; Chmely, S. C.; Sturgeon, M.; Katahira, R.; Paton, R. S.; Beckham, G. T.

    2012-01-01

    Lignin is a major component of plant cell walls that is typically underutilized in selective conversion strategies for renewable fuels and chemicals. The mechanisms by which thermal and catalytic treatments deconstruct lignin remain elusive, for which quantum mechanical calculations can offer fundamental insights. In this work, a computational approach has been used to elucidate the reductive deconstruction pathway of a ruthenium-catalyzed system. Transition states have been computed to determine the rate-limiting steps for a catalyst that cleaves arylether linkages. Our calculations are supported by experimental synthesis and kinetic and thermodynamic measurements of the deconstruction of model lignin dimers by a ruthenium catalyst with the ultimate objective of designing new catalysts to eventually utilize lignin in biorefineries.

  4. In vitro evaluation of the mixed xanthan/lignin hydrogels as vanillin carriers

    NASA Astrophysics Data System (ADS)

    Raschip, Irina Elena; Hitruc, Elena Gabriela; Oprea, Ana Maria; Popescu, Maria-Cristina; Vasile, Cornelia

    2011-09-01

    Various amounts of lignin from annual fiber crops (GL) exhibiting antioxidant properties were incorporated in xanthan to obtain hydrogel films. These mixed xanthan/lignin hydrogels were evaluated as matrices for vanillin release as active aroma ingredient. The new obtained biodegradable polymeric matrices, containing vanillin, have been characterized by the swelling/release experiments, FT-IR and AFM analysis. As a novelty, AFM microscopy was done on powder form. In FT-IR spectra after incorporation of the aroma, the shifting of the bands at 1618 and 1510 cm -1 (assigned to C dbnd C stretching vibration) to higher wavenumbers was observed, indicating interactions between components. The comparison of all the results afforded by the various characterization methods leads to the conclusion that the 70X/30GL hydrogel (15% within 100 min) slower releases the vanillin aroma more than 90X/10GL (18% within 100 min) one because of stronger inter- and intramolecular interactions between matrix and active substance.

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

    PubMed

    Fukushima, Romualdo S; Kerley, Monty S

    2011-04-27

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

  6. Metagenomic scaffolds enable combinatorial lignin transformation

    PubMed Central

    Strachan, Cameron R.; Singh, Rahul; VanInsberghe, David; Ievdokymenko, Kateryna; Budwill, Karen; Mohn, William W.; Eltis, Lindsay D.; Hallam, Steven J.

    2014-01-01

    Engineering the microbial transformation of lignocellulosic biomass is essential to developing modern biorefining processes that alleviate reliance on petroleum-derived energy and chemicals. Many current bioprocess streams depend on the genetic tractability of Escherichia coli with a primary emphasis on engineering cellulose/hemicellulose catabolism, small molecule production, and resistance to product inhibition. Conversely, bioprocess streams for lignin transformation remain embryonic, with relatively few environmental strains or enzymes implicated. Here we develop a biosensor responsive to monoaromatic lignin transformation products compatible with functional screening in E. coli. We use this biosensor to retrieve metagenomic scaffolds sourced from coal bed bacterial communities conferring an array of lignin transformation phenotypes that synergize in combination. Transposon mutagenesis and comparative sequence analysis of active clones identified genes encoding six functional classes mediating lignin transformation phenotypes that appear to be rearrayed in nature via horizontal gene transfer. Lignin transformation activity was then demonstrated for one of the predicted gene products encoding a multicopper oxidase to validate the screen. These results illuminate cellular and community-wide networks acting on aromatic polymers and expand the toolkit for engineering recombinant lignin transformation based on ecological design principles. PMID:24982175

  7. Partitioning and inactivation of viruses by the caprylic acid precipitation followed by a terminal pasteurization in the manufacturing process of horse immunoglobulins.

    PubMed

    Mpandi, M; Schmutz, P; Legrand, E; Duc, R; Geinoz, J; Henzelin-Nkubana, C; Giorgia, S; Clerc, O; Genoud, D; Weber, T

    2007-10-01

    Caprylic acid (octanoic acid), has been used for over 50 years as a stabilizer of human albumin during pasteurization. In addition caprylic acid is of great interest, by providing the advantage of purifying mammalian immunoglobulins and clearing viruses infectivity in a single step. Exploiting these two properties, we sequentially used the caprylic acid precipitation and the pasteurization to purify horse hyperimmune globulins used in the manufacturing of Sérocytol. To evaluate the effectiveness of the process for the removal/inactivation of viruses, spiking studies were carried out for each dedicated step. Bovine viral diarrhoea virus (BVDV), pseudorabies virus (PRV), encephalomyocarditis virus (EMCV) and minute virus of mice (MVM) were used for the virological validation. Our data show that the treatment with caprylic acid 5% (v/v) can effectively be used as well to purify or to ensure viral safety of immunoglobulins. Caprylic acid precipitation was very efficient in removing and/or inactivating enveloped viruses (PRV, BVDV) and moderately efficient against non-enveloped viruses (MVM, ECMV). However the combination with the pasteurization ensured an efficient protection against both enveloped and non-enveloped viruses. So that viruses surviving to the caprylic acid precipitation will be neutralized by pasteurization. Significant log reduction were achieved > or =9 log(10) for enveloped viruses and 4 log(10) for non-enveloped viruses, providing the evidence of a margin of viral safety achieved by our manufacturing process. Its a simple and non-expensive manufacturing process of immunoglobulins easily validated that we have adapted to a large production scale with a programmable operating system.

  8. Lignin conversion: Opportunities and challenges for the integrated biorefinery

    DOE PAGES

    Xie, Shangxian; Ragauskas, Arthur J.; Yuan, Joshua S.

    2016-06-21

    The utilization of lignin for fungible fuels and products represents one of the most imminent challenges in the modern biorefinery because most of the bioprocesses for lignocellulosic biofuels results in a lignin-containing waste stream. Considering lignin's abundance and relatively high energy content, this waste stream can be used as a feedstock for value-added products to improve the sustainability and economic feasibility of the biorefinery. Bioconversion of lignin with microbes recently emerged as an alternative lignin-valorization approach with significant potential. Typically, the microbial bioconversion of lignin requires three major steps: lignin depolymerization, aromatic compounds catabolism, and target product biosynthesis. In thismore » review, we summarize the most recent advances in lignin bioconversion to address the challenges in each of the three steps. In conclusion, we further discuss strategies and perspectives for future research to address the challenges in bioconversion of lignin.« less

  9. Accurate and reproducible determination of lignin molar mass by acetobromination.

    PubMed

    Asikkala, Janne; Tamminen, Tarja; Argyropoulos, Dimitris S

    2012-09-12

    The accurate and reproducible determination of lignin molar mass by using size exclusion chromatography (SEC) is challenging. The lignin association effects, known to dominate underivatized lignins, have been thoroughly addressed by reaction with acetyl bromide in an excess of glacial acetic acid. The combination of a concerted acetylation with the introduction of bromine within the lignin alkyl side chains is thought to be responsible for the observed excellent solubilization characteristics acetobromination imparts to a variety of lignin samples. The proposed methodology was compared and contrasted to traditional lignin derivatization methods. In addition, side reactions that could possibly be induced under the acetobromination conditions were explored with native softwood (milled wood lignin, MWL) and technical (kraft) lignin. These efforts lend support toward the use of room temperature acetobromination being a facile, effective, and universal lignin derivatization medium proposed to be employed prior to SEC measurements. PMID:22870925

  10. Top Value-Added Chemicals from Biomass - Volume II—Results of Screening for Potential Candidates from Biorefinery Lignin

    SciTech Connect

    Holladay, John E.; White, James F.; Bozell, Joseph J.; Johnson, David

    2007-10-01

    This report evaluates lignin’s role as a renewable raw material resource. Opportunities that arise from utilizing lignin fit into one of three categories: 1)power, fuel and syngas (generally near-term opportunities) 2) macromolecules (generally medium-term opportunities) 3) aromatics and miscellaneous monomers (long-term opportunities). Biorefineries will receive and process massive amounts of lignin. For this reason, how lignin can be best used to support the economic health of the biorefinery must be defined. An approach that only considers process heat would be shortsighted. Higher value products present economic opportunities and the potential to significantly increase the amount of liquid transportation fuel available from biomass. In this analysis a list of potential uses of lignin was compiled and sorted into “product types” which are broad classifications (listed above as power—fuel—syngas; macromolecules; and aromatics). In the first “product type” (power—fuel—gasification) lignin is used purely as a carbon source and aggressive means are employed to break down its polymeric structure. In the second “product type” (macromolecules) the opposite extreme is considered and advantage of the macromolecular structure imparted by nature is retained in high-molecular weight applications. The third “product type” (aromatics) lies somewhere between the two extremes and employs technologies that would break up lignin’s macromolecular structure but maintain the aromatic nature of the building block molecules. The individual opportunities were evaluated based on their technical difficulty, market, market risk, building block utility, and whether a pure material or a mixture would be produced. Unlike the “Sugars Top 10” report it was difficult to identify the ten best opportunities, however, the potential opportunities fell nicely into near-, medium- and long-term opportunities. Furthermore, the near-, medium- and long-term opportunities

  11. Characterization of electrospun lignin based carbon fibers

    SciTech Connect

    Poursorkhabi, Vida; Mohanty, Amar; Misra, Manjusri

    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.

  12. Lignin composition in cambial tissues of poplar.

    PubMed

    Christiernin, M

    2006-01-01

    The cambial tissues of a Populus balsamifera, Balsam poplar clone were studied during a growth season. The Klason and acid-soluble lignin contents were determined as well as the carbohydrate monomer distribution and the protein content. Both the phloem and the xylem sides of the cambial region were examined. The samples were analyzed by thioacidolysis and structures of dimeric products were determined by mass spectrometry after desulphuration. Chemical analysis of samples during the growth season was combined with microscopy of embedded specimens that showed the state of cell differentiation at the time of sampling. In spring and early summer, growth is very rapid and the intention was to collect tissue in which exclusively the middle lamella/primary cell wall had begun to lignify. The Klason lignin, protein content and carbohydrate monomer distribution showed that all the specimens from the cambial tissues sampled during a growth season contained predominantly middle lamella and primary walls; except for the developing xylem sampled in August where the carbohydrate composition showed that secondary walls were present. Thioacidolysis showed that the lignin from the cambial tissues had more condensed structures than the lignin from the reference balsam poplar clone wood. More guaiacyl than syringyl units were detected and mass spectrometry showed that the cambial tissues contained more lignin structures with end-groups than the reference sample. These results suggest that lignification in the cambial layer and early developing xylem may take place predominantly in a bulk fashion during the summer.

  13. Polymeric materials from renewable resources

    NASA Astrophysics Data System (ADS)

    Frollini, Elisabete; Rodrigues, Bruno V. M.; da Silva, Cristina G.; Castro, Daniele O.; Ramires, Elaine C.; de Oliveira, Fernando; Santos, Rachel P. O.

    2016-05-01

    The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called "biopolyethylene" (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.

  14. Incorporation of Epicatechin Esters into Lignin Enhances Cell Wall Fermentability

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Polyphenolic catechin esters are potentially attractive targets for lignin bioengineering because their copolymerization with monolignols could reduce lignin hydrophobicity and cross-linking to polysaccharides, or facilitate delignification by biomass pretreatments. To test this hypothesis, we biomi...

  15. Deconstruction of Lignin Model Compounds and Biomass-Derived Lignin using Layered Double Hydroxide Catalysts

    SciTech Connect

    Chmely, S. C.; McKinney, K. A.; Lawrence, K. R.; Sturgeon, M.; Katahira, R.; Beckham, G. T.

    2013-01-01

    Lignin is an underutilized value stream in current biomass conversion technologies because there exist no economic and technically feasible routes for lignin depolymerization and upgrading. Base-catalyzed deconstruction (BCD) has been applied for lignin depolymerization (e.g., the Kraft process) in the pulp and paper industry for more than a century using aqueous-phase media. However, these efforts require treatment to neutralize the resulting streams, which adds significantly to the cost of lignin deconstruction. To circumvent the need for downstream treatment, here we report recent advances in the synthesis of layered double hydroxide and metal oxide catalysts to be applied to the BCD of lignin. These catalysts may prove more cost-effective than liquid-phase, non-recyclable base, and their use obviates downstream processing steps such as neutralization. Synthetic procedures for various transition-metal containing catalysts, detailed kinetics measurements using lignin model compounds, and results of the application of these catalysts to biomass-derived lignin will be presented.

  16. Fungal biodegradation and enzymatic modification of lignin

    PubMed Central

    Dashtban, Mehdi; Schraft, Heidi; Syed, Tarannum A.; Qin, Wensheng

    2010-01-01

    Lignin, the most abundant aromatic biopolymer on Earth, is extremely recalcitrant to degradation. By linking to both hemicellulose and cellulose, it creates a barrier to any solutions or enzymes and prevents the penetration of lignocellulolytic enzymes into the interior lignocellulosic structure. Some basidiomycetes white-rot fungi are able to degrade lignin efficiently using a combination of extracellular ligninolytic enzymes, organic acids, mediators and accessory enzymes. This review describes ligninolytic enzyme families produced by these fungi that are involved in wood decay processes, their molecular structures, biochemical properties and the mechanisms of action which render them attractive candidates in biotechnological applications. These enzymes include phenol oxidase (laccase) and heme peroxidases [lignin peroxidase (LiP), manganese peroxidase (MnP) and versatile peroxidase (VP)]. Accessory enzymes such as H2O2-generating oxidases and degradation mechanisms of plant cell-wall components in a non-enzymatic manner by production of free hydroxyl radicals (·OH) are also discussed. PMID:21968746

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

    SciTech Connect

    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.

  18. Influence of Lignin modification on PAN-Lignin copolymers as potential carbon fiber precursors

    NASA Astrophysics Data System (ADS)

    Ramasubramanian, Gauri

    Carbon fiber based polymer composites have been recognized as advanced materials for structural applications. The unique reinforcing abilities of carbon fibers with their combination of high strength-to-weight ratio and excellent fatigue resistance have made carbon fiber based composites exceptional compared to other fiber reinforced composites. However, the high cost involved in current precursor materials for carbon fibers has limited the widespread applicability of carbon fibers. Hence, intensification of research efforts towards cheaper and easily available raw material for fabrication of carbon fibers is justified. The growing demand for low cost carbon fibers for mainstream composite applications has driven recent interests in using lignin as alternative choice of material for carbon fiber precursor. Lignin is a highly aromatic, plant-derived amorphous polymer and has been considered as potential low-cost, bio-based carbon fiber precursor. Copolymers of polyacrylonitrile/lignin were developed as alternative precursors for fabrication of raw fibers using conventional solution spinning techniques. Lignin/polyacrylonitrile copolymers were successfully synthesized and characterized using FT-IR and NMR techniques. The thermal properties of the copolymers were studied by DSC and TGA analysis. The effect of chemical modification on the morphology and stability of the carbon fibers from PAN-Lignin copolymers has been studied using Raman Spectroscopy, X-ray Diffraction and Scanning Electron Microscopy. Modification of lignin prior to copolymerization provided a significant advantage in the improvement of precursor processability using solution spinning. Additionally, carbon fibers obtained from copolymers containing different varieties of lignins were examined. Carbon fibers produced from organosolv lignin/polyacrylonitrile copolymers exhibit promising carbon fiber structure when compared to softwood/lignin polyacrylonitrile copolymers.

  19. Polymerization of perfluorobutadiene

    NASA Technical Reports Server (NTRS)

    Newman, J.; Toy, M. S.

    1970-01-01

    Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield.

  20. Selective conversion of biorefinery lignin into dicarboxylic acids.

    PubMed

    Ma, Ruoshui; Guo, Mond; Zhang, Xiao

    2014-02-01

    The emerging biomass-to-biofuel conversion industry has created an urgent need for identifying new applications for biorefinery lignin. This paper demonstrates a new route to producing dicarboxylic acids from biorefinery lignin through chalcopyrite-catalyzed oxidation in a highly selective process. Up to 95 % selectivity towards stable dicarboxylic acids was obtained for several types of biorefinery lignin and model compounds under mild, environmentally friendly reaction conditions. The findings from this study paved a new avenue to biorefinery lignin conversions and applications.

  1. Selective Conversion of Biorefinery Lignin into Dicarboxylic Acids

    SciTech Connect

    Ma, Ruoshui; Guo, Mond; Zhang, Xiao

    2014-02-01

    The emerging biomass-to-biofuel conversion industry has created an urgent need for identifying new applications for biorefinery lignin. This paper demonstrates a new route to producing dicarboxylic acids from biorefinery lignin through chalcopyrite-catalyzed oxidation in a highly selective process. Up to 95 % selectivity towards stable dicarboxylic acids was obtained for several types of biorefinery lignin and model compounds under mild, environmentally friendly reaction conditions. The findings from this study paved a new avenue to biorefinery lignin conversions and applications.

  2. Process for producing phenolic compounds from lignins

    DOEpatents

    Agblevor, Foster A.

    1998-01-01

    A process for the production of low molecular weight phenolic compounds from lignins through the pyrolysis of the lignins in the presence of a strong base. In a preferred embodiment, potassium hydroxide is present in an amount of from about 0.1% to about 5% by weight, the pyrolysis temperature is from about 400.degree. C. to about 600.degree. C. at atmospheric pressure, and the time period for substantial completion of the reaction is from about 1-3 minutes. Examples of low molecular weight phenolic compounds produced include methoxyphenols, non-methoxylated phenols, and mixtures thereof.

  3. Process for producing phenolic compounds from lignins

    DOEpatents

    Agblevor, F.A.

    1998-09-15

    A process is described for the production of low molecular weight phenolic compounds from lignins through the pyrolysis of the lignins in the presence of a strong base. In a preferred embodiment, potassium hydroxide is present in an amount of from about 0.1% to about 5% by weight, the pyrolysis temperature is from about 400 C to about 600 C at atmospheric pressure, and the time period for substantial completion of the reaction is from about 1--3 minutes. Examples of low molecular weight phenolic compounds produced include methoxyphenols, non-methoxylated phenols, and mixtures thereof. 16 figs.

  4. Structure and radical scavenging activity relationships of pyrolytic lignins

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This work deals with antioxidant properties of pyrolytic lignins against two free radicals, the 1,1-diphenyl-2-picrylhydrazyl and the 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid). Pyrolytic lignins produced by the thermal pyrolysis of the Etek lignin were extracted from the liquid pyrolysi...

  5. Caterpillar feeding responses to sorghum leaves with altered lignin levels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Production of liquid fuels from biomass is impeded by the presence of lignin. Plants with lower or altered lignin are more amenable to lignocellulosic conversion to ethanol and other biofuels, but may be more susceptible to insect damage where lignin is an important resistance factor. Sorghum, Sorg...

  6. Genetics and chemistry of lignin degradation by Streptomyces

    SciTech Connect

    Crawford, D.L.

    1992-01-01

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

  7. Genetic engineering of syringyl-enriched lignin in plants

    DOEpatents

    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.

  8. Solubilization of lignin by the ruminal anaerobic fungus Neocallimastix patriciarum.

    PubMed Central

    McSweeney, C S; Dulieu, A; Katayama, Y; Lowry, J B

    1994-01-01

    The ability of the ruminal anaerobic phycomycete Neocallimastix patriciarum to digest model lignin compounds and lignified structures in plant material was studied in batch culture. The fungus did not degrade or transform model lignin compounds that were representative of the predominant intermonomer linkages in lignin, nor did it solubilize acid detergent lignin that had been isolated from spear grass. In a stem fraction of sorghum, 33.6% of lignin was apparently solubilized by the fungus. Solubilization of ester- and either-linked phenolics accounted for 9.2% of the lignin released. The amounts of free phenolic acids detected in culture fluid were equivalent to the apparent loss of ester-linked phenolics from the sorghum substrate. However, the fungus was unable to cleave the ether bond in hydroxycinnamic acid bridges that cross-link lignin and polysaccharide. It is suggested that the majority of the solubilized lignin fraction was a lignin carbohydrate complex containing ether-linked hydroxycinnamic acids. The lignin carbohydrate complex was probably solubilized through dissolution of xylan in the lignin-xylan matrix rather than by lignin depolymerization. PMID:8085834

  9. Flocculation of high purity wheat straw soda lignin

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  10. Polymerization Reactor Engineering.

    ERIC Educational Resources Information Center

    Skaates, J. Michael

    1987-01-01

    Describes a polymerization reactor engineering course offered at Michigan Technological University which focuses on the design and operation of industrial polymerization reactors to achieve a desired degree of polymerization and molecular weight distribution. Provides a list of the course topics and assigned readings. (TW)

  11. 14C-[lignin]-lignocellulose biodegradation by bacteria isolated from polluted soil.

    PubMed

    Kumar, L; Rathore, V; Srivastava, H

    2001-06-01

    Four bacterial species [Branhamella catarrhalis (gram -ve), Brochothrix species (gram -ve), Micrococcus luteus (gram +ve) and Bacillus firmus (gram +ve)], isolated from the soil polluted with cane sugar factory effluents, were found capable of growing on solid media supplemented with indulin AT (a polymeric industrial lignin) as sole C source. All the four species could metabolize cinnamic acid (a non-hydroxylated phenylpropanoid) as sole carbon source with significant suppression on addition of readily metabolizable carbon source (glucose). However, Br. catarrhalis and Brochothrix sp. were capable of metabolizing ferulic acid, but could not do so on addition of glucose. Of the four species, Br. catarrhalis could evolve significant amount of 14CO2 from U-14C (lignin)-lignocellulose prepared from rice stalks (ca. 10% of the added radioactivity in 3 weeks), in addition to solubilization of another 11.7% radioactivity in culture filtrate. The other three species could not significantly evolve 14CO2, though a significant fraction of added 14C-lignin (6.1 to 11.2%) could be solubilized into culture filtrate, suggesting lack of ring-cleavage or other CO2 evolving mechanisms in these species.

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

    PubMed

    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.

  13. Propensity of lignin to associate: light scattering photometry study with native lignins.

    PubMed

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

    2008-12-01

    Many studies of lignins in solution invoke association and aggregation phenomena to explain their solution behavior (e.g., reprecipitation onto pulp fibers, condensation, etc.). Following their colloidal (apparent) molecular weights in solution as a function of time allows us to explore observable dissociation phenomena. These measurements were carried out using multiple angle laser light scattering (MALLS) photometry in the static mode. The challenges and opportunities of measuring the specific refractive index increment (dn/dC) of lignin solutions and determining the kinetics of the dissociation process were thus investigated. Hardwood and softwood representative lignins were isolated, and method for their full dissolution in THF was further developed, which then lead to accurate dn/dC values being obtained as a function of time. When coupled to additional work using light scattering static measurements and Zimm plots for the same solutions, this effort offers insight into the aggregation and ensuing dissociative events that operate within the lignin macromolecules.

  14. Identifying New Lignin Bioengineering Targets: 1. Monolignol Substitute Impacts on Lignin Formation and Cell Wall Fermentability

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 engineering efforts are primarily aimed at manipulating the biosynthesis of normal monolignols but,...

  15. Identifying New Lignin Bioengineering Targets: Monolignol Substitute Impacts on Lignin Formation and Cell Wall Utilization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recent discoveries highlighting the metabolic malleability of plant lignification indicate that lignin can be engineered to dramatically alter its composition and properties. Current plant engineering efforts are primarily aimed at manipulating the biosynthesis of normal monolignols, but in the futu...

  16. Lignin-blocking treatment of biomass and uses thereof

    DOEpatents

    Yang, Bin; Wyman, Charles E.

    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.

  17. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food... accordance with the following prescribed conditions: (a) For the purpose of this section, the food additive... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Lignin sulfonates. 573.600 Section 573.600...

  18. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food... accordance with the following prescribed conditions: (a) For the purpose of this section, the food additive... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Lignin sulfonates. 573.600 Section 573.600...

  19. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food... accordance with the following prescribed conditions: (a) For the purpose of this section, the food additive... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Lignin sulfonates. 573.600 Section 573.600...

  20. Kinetic Model Development for Lignin Pyrolysis

    SciTech Connect

    Clark, J.; Robichaud, D.; Nimlos, M.

    2012-01-01

    Lignin pyrolysis poses a significant barrier to the formation of liquid fuel products from biomass. Lignin pyrolyzes at higher temperatures than other biomass components (e.g. cellulose and hemi-cellulose) and tends to form radicals species that lead to cross-linking and ultimately char formation. A first step in the advancement of biomass-to-fuel technology is to discover the underlying mechanisms that lead to the breakdown of lignin at lower temperatures into more stable and usable products. We have investigated the thermochemistry of the various inter-linkage units found in lignin (B-O4, a-O4, B-B, B-O5, etc) using electronic structure calculations at the M06-2x/6-311++G(d,p) on a series of dimer model compounds. In addition to bond homolysis reactions, a variety of concerted elimination pathways are under investigation that tend to produce closed-shell stable products. Such a bottom-up approach could aid in the targeted development of catalysts that produce more desirable products under less severe reactor conditions.

  1. Flash vacuum pyrolysis of lignin model compounds

    SciTech Connect

    Cooney, M.J.; Britt, P.F.; Buchanan, A.C. III

    1997-03-01

    Despite the extensive research into the pyrolysis of lignin, the underlying chemical reactions that lead to product formation are poorly understood. Detailed mechanistic studies on the pyrolysis of biomass and lignin under conditions relevant to current process conditions could provide insight into utilizing this renewable resource for the production of chemicals and fuel. Currently, flash or fast pyrolysis is the most promising process to maximize the yields of liquid products (up to 80 wt %) from biomass by rapidly heating the substrate to moderate temperatures, typically 500{degrees}C, for short residence times, typically less than two seconds. To provide mechanistic insight into the primary reaction pathways under process relevant conditions, we are investigating the flash vacuum pyrolysis (FVP) of lignin model compounds that contain a {beta}-ether. linkage and {alpha}- or {gamma}-alcohol, which are key structural elements in lignin. The dominant products from the FVP of PhCH{sub 2}CH{sub 2}OPh (PPE), PhC(OH)HCH{sub 2}OPh, and PhCH{sub 2}CH(CH{sub 2}OH)OPh at 500{degrees}C can be attributed to homolysis of the weakest bond in the molecule (C-O bond) or 1,2-elimination. Surprisingly, the hydroxy-substituent dramatically increases the decomposition of PPE. It is proposed that internal hydrogen bonding is accelerating the reaction.

  2. Three-dimensional model of lignin structure

    SciTech Connect

    Jurasek, L.

    1995-12-01

    An attempt to build a three-dimensional model of lignin structure using a computer program is described. The program simulates the biosynthesis of spruce lignin by allowing coniferyl alcohol subunits to be added randomly by six different types of linkages, assumed to be most common. The simulated biosynthesis starts from a number of seed points within restricted space, corresponding to 50 mM initial concentration of coniferyl alcohol. Rules of three-dimensional packing of the subunits within the lignin macro-molecule are observed during the simulated biosynthetic process. Branched oligomeric structures thus generated form crosslinks at those positions where the chains grow close enough to form a link. Inter-chain crosslinking usually joins the oligomers into one macromolecule. Intra-chain crosslinks are also formed and result in closed loops. Typically, a macromolecule with molecular weight of approx. 2 x 105 is formed, with internal density of 1.35g/cm3. Various characteristics of the internal structure, such as branching, crosslinking, bond frequencies, and chain length distribution are described. Breakdown of the polymer was also simulated and the effect of closed loops on the weight average molecular weight is shown. The effect of the shape of the biosynthetic space on the degree of crosslinking is discussed and predictions of the overall molecular shape of lignin particles are made.

  3. Computational Mechanistic Studies of Acid-Catalyzed Lignin Model Dimers for Lignin Depolymerization

    SciTech Connect

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

    2013-01-01

    Lignin is a heterogeneous alkyl-aromatic polymer that constitutes up to 30% of plant cell walls, and is used for water transport, structure, and defense. The highly irregular and heterogeneous structure of lignin presents a major obstacle in the development of strategies for its deconstruction and upgrading. Here we present mechanistic studies of the acid-catalyzed cleavage of lignin aryl-ether linkages, combining both experimental studies and quantum chemical calculations. Quantum mechanical calculations provide a detailed interpretation of reaction mechanisms including possible intermediates and transition states. Solvent effects on the hydrolysis reactions were incorporated through the use of a conductor-like polarizable continuum model (CPCM) and with cluster models including explicit water molecules in the first solvation shell. Reaction pathways were computed for four lignin model dimers including 2-phenoxy-phenylethanol (PPE), 1-(para-hydroxyphenyl)-2-phenoxy-ethanol (HPPE), 2-phenoxy-phenyl-1,3-propanediol (PPPD), and 1-(para-hydroxyphenyl)-2-phenoxy-1,3-propanediol (HPPPD). Lignin model dimers with a para-hydroxyphenyl ether (HPPE and HPPPD) show substantial differences in reactivity relative to the phenyl ether compound (PPE and PPPD) which have been clarified theoretically and experimentally. The significance of these results for acid deconstruction of lignin in plant cell walls will be discussed.

  4. Phoma herbarum, a soil fungus able to grow on natural lignin and synthetic lignin (DHP) as sole carbon source and cause lignin degradation.

    PubMed

    Bi, Ran; Lawoko, Martin; Henriksson, Gunnar

    2016-08-01

    The fungus Phoma herbarum isolated from soil showed growth on highly pure lignin extracted from spruce wood and on synthetic lignin (DHP). The lignin remaining after cultivation was shown to have a lower molecular weight. The reduction in the numbers of ether linkages of the extracted lignins was also observed by derivatization followed by reductive cleavage (DFRC) in combination with (31)P NMR studies. The fungal strain showed an ability to degrade synthetic lignin by extracellular catalysts. GC-MS was applied to study the evolution of low molar mass adducts, e.g., monolignols and it was shown that a reduced coniferyl alcohol product was produced from DHP in a cell-free environment. The work has demonstrated the ability of soil microbes to grow on lignin as sole carbon source. The potential impact is in the production of low molar mass renewable phenols for material application. PMID:27260523

  5. Discovery of 12-mer peptides that bind to wood lignin.

    PubMed

    Yamaguchi, Asako; Isozaki, Katsuhiro; Nakamura, Masaharu; Takaya, Hikaru; Watanabe, Takashi

    2016-01-01

    Lignin, an abundant terrestrial polymer, is the only large-volume renewable feedstock composed of an aromatic skeleton. Lignin has been used mostly as an energy source during paper production; however, recent interest in replacing fossil fuels with renewable resources has highlighted its potential value in providing aromatic chemicals. Highly selective degradation of lignin is pivotal for industrial production of paper, biofuels, chemicals, and materials. However, few studies have examined natural and synthetic molecular components recognizing the heterogeneous aromatic polymer. Here, we report the first identification of lignin-binding peptides possessing characteristic sequences using a phage display technique. The consensus sequence HFPSP was found in several lignin-binding peptides, and the outer amino acid sequence affected the binding affinity of the peptides. Substitution of phenylalanine7 with Ile in the lignin-binding peptide C416 (HFPSPIFQRHSH) decreased the affinity of the peptide for softwood lignin without changing its affinity for hardwood lignin, indicating that C416 recognised structural differences between the lignins. Circular dichroism spectroscopy demonstrated that this peptide adopted a highly flexible random coil structure, allowing key residues to be appropriately arranged in relation to the binding site in lignin. These results provide a useful platform for designing synthetic and biological catalysts selectively bind to lignin. PMID:26903196

  6. Discovery of 12-mer peptides that bind to wood lignin

    PubMed Central

    Yamaguchi, Asako; Isozaki, Katsuhiro; Nakamura, Masaharu; Takaya, Hikaru; Watanabe, Takashi

    2016-01-01

    Lignin, an abundant terrestrial polymer, is the only large-volume renewable feedstock composed of an aromatic skeleton. Lignin has been used mostly as an energy source during paper production; however, recent interest in replacing fossil fuels with renewable resources has highlighted its potential value in providing aromatic chemicals. Highly selective degradation of lignin is pivotal for industrial production of paper, biofuels, chemicals, and materials. However, few studies have examined natural and synthetic molecular components recognizing the heterogeneous aromatic polymer. Here, we report the first identification of lignin-binding peptides possessing characteristic sequences using a phage display technique. The consensus sequence HFPSP was found in several lignin-binding peptides, and the outer amino acid sequence affected the binding affinity of the peptides. Substitution of phenylalanine7 with Ile in the lignin-binding peptide C416 (HFPSPIFQRHSH) decreased the affinity of the peptide for softwood lignin without changing its affinity for hardwood lignin, indicating that C416 recognised structural differences between the lignins. Circular dichroism spectroscopy demonstrated that this peptide adopted a highly flexible random coil structure, allowing key residues to be appropriately arranged in relation to the binding site in lignin. These results provide a useful platform for designing synthetic and biological catalysts selectively bind to lignin. PMID:26903196

  7. Method for recovering and using lignin in adhesive resins

    DOEpatents

    Schroeder, Herbert A.

    1993-01-01

    Lignin, or a lignin derived material, which has been significantly demethylated (e.g., the demethylated lignin found in the raffinate produced as a by-product of dimethyl sulfide production which can be carried out using the spent liquor from wood pulping operations) can be isolated by a process wherein an organic solvent is added to a lignin-containing aqueous solution. The organic solvent is typically a polar, and at least a partially water-immiscible substance such as, for example, ethyl acetate. The resulting lignin-containing aqueous solution/organic solvent mixture is acidified to produce a water layer which is discarded and an organic solvent layer which contains the demethylated lignin. Upon its recovery, the demethylated lignin is dissolved in an alkaline solution to which an aldehyde source is added to produce a resol-type resin. The aldehyde source may be formaldehyde in solution, paraformaldehyde, hexamethylenetetramine, or other aldehydes including acetaldehyde, furfural, and their derivatives.

  8. Isolation of a Bacterium Capable of Degrading Peanut Hull Lignin

    PubMed Central

    Kerr, Thomas J.; Kerr, Robert D.; Benner, Ronald

    1983-01-01

    Thirty-seven bacterial strains capable of degrading peanut hull lignin were isolated by using four types of lignin preparations and hot-water-extracted peanut hulls. One of the isolates, tentatively identified as Arthrobacter sp., was capable of utilizing all four lignin preparations as well as extracted peanut hulls as a sole source of carbon. The bacterium was also capable of degrading specifically labeled [14C]lignin-labeled lignocellulose and [14C]cellulose-labeled lignocellulose from the cordgrass Spartina alterniflora and could also degrade [14C]Kraft lignin from slash pine. After 10 days of incubation with [14C]cellulose-labeled lignocellulose or [14C]lignin-labeled lignocellulose from S. alterniflora, the bacterium mineralized 6.5% of the polysaccharide component and 2.9% of the lignin component. Images PMID:16346424

  9. Isolation of a bacterium capable of degrading peanut hull lignin

    SciTech Connect

    Kerr, T.A.; Kerr, R.D.; Benner, R.

    1983-11-01

    Thirty-seven bacterial strains capable of degrading peanut hull lignin were isolated by using four types of lignin preparations and hot-water-extracted peanut hulls. One of the isolates, tentatively identified as Arthrobacter species, was capable of utilizing all four lignin preparations as well as extracted peanut hulls as a sole source of carbon. The bacterium was also capable of degrading specifically labeled (/sup 14/C) lignin-labeled lignocellulose and (/sup 14/C)cellulose-labeled lignocellulose from the cordgrass Spartina alterniflora and could also degrade (/sup 14/C) Kraft lignin from slash pine. After 10 days of incubation with (/sup 14/C) cellulose-labeled lignocellulose or (/sup 14/C) lignin-labeled lignocellulose from S. alterniflora, the bacterium mineralized 6.5% of the polysaccharide component and 2.9% of the lignin component. (Refs. 24).

  10. Reactions of Lignin Model Compounds in Ionic Liquids

    SciTech Connect

    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.

  11. Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment

    DOE PAGES

    Sun, Qining; Foston, Marcus; Meng, Xianzhi; Sawada, Daisuke; Pingali, Sai Venkatesh; O’Neill, Hugh M.; Li, Hongjia; Wyman, Charles E.; Langan, Paul; Ragauskas, Art J.; et al

    2014-10-14

    Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultrastructural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultrastructure, which might ultimately have largemore » implications with respect to enzymatic deconstruction efforts. Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultrastructure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons’ stain (orange dye) adsorption from 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DPw) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%. We conclude that, overall, the results indicate a strong influence of lignin content on cellulose ultrastructural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of

  12. Computational inference of the structure and regulation of the lignin pathway in Panicum virgatum

    DOE PAGES

    Faraji, Mojdeh; Fonseca, Luis L.; Escamilla-Treviño, Luis; Dixon, Richard A.; Voit, Eberhard O.

    2015-09-17

    Switchgrass is a prime target for biofuel production from inedible plant parts and has been the subject of numerous investigations in recent years. Yet, one of the main obstacles to effective biofuel production remains to be the major problem of recalcitrance. Recalcitrance emerges in part from the 3-D structure of lignin as a polymer in the secondary cell wall. Lignin limits accessibility of the sugars in the cellulose and hemicellulose polymers to enzymes and ultimately decreases ethanol yield. Monolignols, the building blocks of lignin polymers, are synthesized in the cytosol and translocated to the plant cell wall, where they undergomore » polymerization. The biosynthetic pathway leading to monolignols in switchgrass is not completely known, and difficulties associated with in vivo measurements of these intermediates pose a challenge for a true understanding of the functioning of the pathway. In this study, a systems biological modeling approach is used to address this challenge and to elucidate the structure and regulation of the lignin pathway through a computational characterization of alternate candidate topologies. The analysis is based on experimental data characterizing stem and tiller tissue of four transgenic lines (knock-downs of genes coding for key enzymes in the pathway) as well as wild-type switchgrass plants. These data consist of the observed content and composition of monolignols. The possibility of a G-lignin specific metabolic channel associated with the production and degradation of coniferaldehyde is examined, and the results support previous findings from another plant species. The computational analysis suggests regulatory mechanisms of product inhibition and enzyme competition, which are well known in biochemistry, but so far had not been reported in switchgrass. By including these mechanisms, the pathway model is able to represent all observations. In conclusion, the results show that the presence of the coniferaldehyde channel is

  13. Computational inference of the structure and regulation of the lignin pathway in Panicum virgatum

    SciTech Connect

    Faraji, Mojdeh; Fonseca, Luis L.; Escamilla-Treviño, Luis; Dixon, Richard A.; Voit, Eberhard O.

    2015-09-17

    Switchgrass is a prime target for biofuel production from inedible plant parts and has been the subject of numerous investigations in recent years. Yet, one of the main obstacles to effective biofuel production remains to be the major problem of recalcitrance. Recalcitrance emerges in part from the 3-D structure of lignin as a polymer in the secondary cell wall. Lignin limits accessibility of the sugars in the cellulose and hemicellulose polymers to enzymes and ultimately decreases ethanol yield. Monolignols, the building blocks of lignin polymers, are synthesized in the cytosol and translocated to the plant cell wall, where they undergo polymerization. The biosynthetic pathway leading to monolignols in switchgrass is not completely known, and difficulties associated with in vivo measurements of these intermediates pose a challenge for a true understanding of the functioning of the pathway. In this study, a systems biological modeling approach is used to address this challenge and to elucidate the structure and regulation of the lignin pathway through a computational characterization of alternate candidate topologies. The analysis is based on experimental data characterizing stem and tiller tissue of four transgenic lines (knock-downs of genes coding for key enzymes in the pathway) as well as wild-type switchgrass plants. These data consist of the observed content and composition of monolignols. The possibility of a G-lignin specific metabolic channel associated with the production and degradation of coniferaldehyde is examined, and the results support previous findings from another plant species. The computational analysis suggests regulatory mechanisms of product inhibition and enzyme competition, which are well known in biochemistry, but so far had not been reported in switchgrass. By including these mechanisms, the pathway model is able to represent all observations. In conclusion, the results show that the presence of the coniferaldehyde channel is necessary

  14. Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment

    SciTech Connect

    Sun, Qining; Foston, Marcus; Meng, Xianzhi; Sawada, Daisuke; Pingali, Sai Venkatesh; O’Neill, Hugh M.; Li, Hongjia; Wyman, Charles E.; Langan, Paul; Ragauskas, Art J.; Kumar, Rajeev

    2014-10-14

    Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultrastructural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultrastructure, which might ultimately have large implications with respect to enzymatic deconstruction efforts. Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultrastructure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons’ stain (orange dye) adsorption from 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DPw) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%. We conclude that, overall, the results indicate a strong influence of lignin content on cellulose ultrastructural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of

  15. Bioinformatic and functional characterization of the basic peroxidase 72 from Arabidopsis thaliana involved in lignin biosynthesis.

    PubMed

    Herrero, Joaquín; Fernández-Pérez, Francisco; Yebra, Tatiana; Novo-Uzal, Esther; Pomar, Federico; Pedreño, Ma Ángeles; Cuello, Juan; Guéra, Alfredo; Esteban-Carrasco, Alberto; Zapata, José Miguel

    2013-06-01

    Lignins result from the oxidative polymerization of three hydroxycinnamyl (p-coumaryl, coniferyl, and sinapyl) alcohols in a reaction mediated by peroxidases. The most important of these is the cationic peroxidase from Zinnia elegans (ZePrx), an enzyme considered to be responsible for the last step of lignification in this plant. Bibliographical evidence indicates that the arabidopsis peroxidase 72 (AtPrx72), which is homolog to ZePrx, could have an important role in lignification. For this reason, we performed a bioinformatic, histochemical, photosynthetic, and phenotypical and lignin composition analysis of an arabidopsis knock-out mutant of AtPrx72 with the aim of characterizing the effects that occurred due to the absence of expression of this peroxidase from the aspects of plant physiology such as vascular development, lignification, and photosynthesis. In silico analyses indicated a high homology between AtPrx72 and ZePrx, cell wall localization and probably optimal levels of translation of AtPrx72. The histochemical study revealed a low content in syringyl units and a decrease in the amount of lignin in the atprx72 mutant plants compared to WT. The atprx72 mutant plants grew more slowly than WT plants, with both smaller rosette and principal stem, and with fewer branches and siliques than the WT plants. Lastly, chlorophyll a fluorescence revealed a significant decrease in ΦPSII and q L in atprx72 mutant plants that could be related to changes in carbon partitioning and/or utilization of redox equivalents in arabidopsis metabolism. The results suggest an important role of AtPrx72 in lignin biosynthesis. In addition, knock-out plants were able to respond and adapt to an insufficiency of lignification.

  16. Purification and Characterization of a Thermostable Laccase from Trametes trogii and Its Ability in Modification of Kraft Lignin.

    PubMed

    Ai, Ming-Qiang; Wang, Fang-Fang; Huang, Feng

    2015-08-01

    A blue laccase was purified from a white rot fungus of Trametes trogii, which was a monomeric protein of 64 kDa as determined by SDS-PAGE. The enzyme acted optimally at a pH of 2.2 to 4.5 and a temperature of 70°C and showed high thermal stability, with a half-life of 1.6 h at 60°C. A broad range of substrates, including the non-phenolic azo dye methyl red, was oxidized by the laccase, and the laccase exhibited high affinity towards ABTS and syringaldazine. Moreover, the laccase was fairly metal-tolerant. A high-molecular-weight kraft lignin was effectively polymerized by the laccase, with a maximum of 6.4-fold increase in weight-average molecular weight, as demonstrated by gel permeation chromatography. Notable structural changes in the polymerized lignin were detected by Fourier transform infrared spectroscopy and 1H NMR spectroscopy. This revealed an increase in condensed structures as well as carbonyl and aliphatic hydroxyl groups. Simultaneously, phenolic hydroxyl and methoxy groups decreased. These results suggested the potential use of the laccase in lignin modification. PMID:25876603

  17. Purification and Characterization of a Thermostable Laccase from Trametes trogii and Its Ability in Modification of Kraft Lignin.

    PubMed

    Ai, Ming-Qiang; Wang, Fang-Fang; Huang, Feng

    2015-08-01

    A blue laccase was purified from a white rot fungus of Trametes trogii, which was a monomeric protein of 64 kDa as determined by SDS-PAGE. The enzyme acted optimally at a pH of 2.2 to 4.5 and a temperature of 70°C and showed high thermal stability, with a half-life of 1.6 h at 60°C. A broad range of substrates, including the non-phenolic azo dye methyl red, was oxidized by the laccase, and the laccase exhibited high affinity towards ABTS and syringaldazine. Moreover, the laccase was fairly metal-tolerant. A high-molecular-weight kraft lignin was effectively polymerized by the laccase, with a maximum of 6.4-fold increase in weight-average molecular weight, as demonstrated by gel permeation chromatography. Notable structural changes in the polymerized lignin were detected by Fourier transform infrared spectroscopy and 1H NMR spectroscopy. This revealed an increase in condensed structures as well as carbonyl and aliphatic hydroxyl groups. Simultaneously, phenolic hydroxyl and methoxy groups decreased. These results suggested the potential use of the laccase in lignin modification.

  18. Analytical pyrolysis of hardwood and softwood lignins and its use in lignin-type determination of hardwood vessel elements

    SciTech Connect

    Obst, J.R.

    1983-01-01

    Pyrolysis, GC and mass spectrometry were performed on milled wood lignins and wood samples. Among the major pyrolysis products identified from loblolly pine lignin were: guaiacol, 4-methylguaiacol, 4-vinylguaiacol, vanillin, coniferaldehyde and coniferyl alcohol. White oak lignin pyrolysis products included: guaiacol, 4-methylguaiacol, vanillin, 2,6-dimethoxyphenol, 4-methyl-2,6-dimethoxyphenol, syringaldehyde and sinapaldehyde. By the identification of pyrolysis products it is thus possible to classify lignins as either guaiacyl-type or syringyl/guaiacyl-type. Pyrolysis of isolated vessel elements from white oak, white birch (Betula papyrifera) and American elm (Ulmus americana) indicated that vessel lignin is of the syringyl/guaiacyl type. 14 references.

  19. Benzoxazolin-2(3H)-one inhibits soybean growth and alters the monomeric composition of lignin.

    PubMed

    Parizotto, Angela Valderrama; Bubna, Gisele Adriana; Marchiosi, Rogério; Soares, Anderson Ricardo; Ferrarese, Maria de Lourdes Lucio; Ferrarese-Filho, Osvaldo

    2015-01-01

    The effects of the allelochemical benzoxazolin-2-(3H)-one (BOA) were evaluated on growth, lignin content and its monomers p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) in roots, stems and leaves of soybean. BOA decreased the lengths and fresh weights of roots and stems, and the fresh weights and areas of leaves. Reductions in the growth were accompanied by enhanced lignin content in all tissues. In roots, the allelochemical increased the content of H, G and S monomers as well as the overall amount of lignin (referred to as the sum of H+G+S), but did not alter the S/G ratio. In stems and leaves, BOA increased the H, G, S and H+G+S contents while decreasing the S/G ratio. In brief, BOA-induced inhibition of soybean may be due to excessive production of monomers that increase the degree of polymerization of lignin, limit cell expansion, solidify the cell wall and restrict plant growth.

  20. Identifying new lignin bioengineering targets: impact of epicatechin, quercetin glycoside, and gallate derivatives on the lignification and fermentation of maize cell walls.

    PubMed

    Grabber, John H; Ress, Dino; Ralph, John

    2012-05-23

    Apoplastic targeting of secondary metabolites compatible with monolignol polymerization may provide new avenues for designing lignins that are less inhibitory toward fiber fermentation. To identify suitable monolignol substitutes, primary maize cell walls were artificially lignified with normal monolignols plus various epicatechin, quercetin glycoside, and gallate derivatives added as 0 or 45% by weight of the precursor mixture. The flavonoids and gallates had variable effects on peroxidase activity, but all dropped lignification pH. Epigallocatechin gallate, epicatechin gallate, epicatechin vanillate, epigallocatechin, galloylhyperin, and pentagalloylglucose formed wall-bound lignin at moderate to high concentrations, and their incorporation increased 48 h in vitro ruminal fiber fermentability by 20-33% relative to lignified controls. By contrast, ethyl gallate and corilagin severely depressed lignification and increased 48 h fermentability by about 50%. The results suggest several flavonoid and gallate derivatives are promising lignin bioengineering targets for improving the inherent fermentability of nonpretreated cell walls.

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

    PubMed

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

    2013-01-01

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

  2. Lignin down-regulation of Zea mays via dsRNAi and klason lignin analysis.

    PubMed

    Park, Sang-Hyuck; Ong, Rebecca Garlock; Mei, Chuansheng; Sticklen, Mariam

    2014-07-23

    To facilitate the use of lignocellulosic biomass as an alternative bioenergy resource, during biological conversion processes, a pretreatment step is needed to open up the structure of the plant cell wall, increasing the accessibility of the cell wall carbohydrates. Lignin, a polyphenolic material present in many cell wall types, is known to be a significant hindrance to enzyme access. Reduction in lignin content to a level that does not interfere with the structural integrity and defense system of the plant might be a valuable step to reduce the costs of bioethanol production. In this study, we have genetically down-regulated one of the lignin biosynthesis-related genes, cinnamoyl-CoA reductase (ZmCCR1) via a double stranded RNA interference technique. The ZmCCR1_RNAi construct was integrated into the maize genome using the particle bombardment method. Transgenic maize plants grew normally as compared to the wild-type control plants without interfering with biomass growth or defense mechanisms, with the exception of displaying of brown-coloration in transgenic plants leaf mid-ribs, husks, and stems. The microscopic analyses, in conjunction with the histological assay, revealed that the leaf sclerenchyma fibers were thinned but the structure and size of other major vascular system components was not altered. The lignin content in the transgenic maize was reduced by 7-8.7%, the crystalline cellulose content was increased in response to lignin reduction, and hemicelluloses remained unchanged. The analyses may indicate that carbon flow might have been shifted from lignin biosynthesis to cellulose biosynthesis. This article delineates the procedures used to down-regulate the lignin content in maize via RNAi technology, and the cell wall compositional analyses used to verify the effect of the modifications on the cell wall structure.

  3. Lignin Down-regulation of Zea mays via dsRNAi and Klason Lignin Analysis

    PubMed Central

    Park, Sang-Hyuck; Ong, Rebecca Garlock; Mei, Chuansheng; Sticklen, Mariam

    2014-01-01

    To facilitate the use of lignocellulosic biomass as an alternative bioenergy resource, during biological conversion processes, a pretreatment step is needed to open up the structure of the plant cell wall, increasing the accessibility of the cell wall carbohydrates. Lignin, a polyphenolic material present in many cell wall types, is known to be a significant hindrance to enzyme access. Reduction in lignin content to a level that does not interfere with the structural integrity and defense system of the plant might be a valuable step to reduce the costs of bioethanol production. In this study, we have genetically down-regulated one of the lignin biosynthesis-related genes, cinnamoyl-CoA reductase (ZmCCR1) via a double stranded RNA interference technique. The ZmCCR1_RNAi construct was integrated into the maize genome using the particle bombardment method. Transgenic maize plants grew normally as compared to the wild-type control plants without interfering with biomass growth or defense mechanisms, with the exception of displaying of brown-coloration in transgenic plants leaf mid-ribs, husks, and stems. The microscopic analyses, in conjunction with the histological assay, revealed that the leaf sclerenchyma fibers were thinned but the structure and size of other major vascular system components was not altered. The lignin content in the transgenic maize was reduced by 7-8.7%, the crystalline cellulose content was increased in response to lignin reduction, and hemicelluloses remained unchanged. The analyses may indicate that carbon flow might have been shifted from lignin biosynthesis to cellulose biosynthesis. This article delineates the procedures used to down-regulate the lignin content in maize via RNAi technology, and the cell wall compositional analyses used to verify the effect of the modifications on the cell wall structure. PMID:25080235

  4. Gene Silencing of BnTT10 Family Genes Causes Retarded Pigmentation and Lignin Reduction in the Seed Coat of Brassica napus

    PubMed Central

    Zhang, Kai; Lu, Kun; Qu, Cunmin; Liang, Ying; Wang, Rui; Chai, Yourong; Li, Jiana

    2013-01-01

    Yellow-seed (i.e., yellow seed coat) is one of the most important agronomic traits of Brassica plants, which is correlated with seed oil and meal qualities. Previous studies on the Brassicaceae, including Arabidopsis and Brassica species, proposed that the seed-color trait is correlative to flavonoid and lignin biosynthesis, at the molecular level. In Arabidopsis thaliana, the oxidative polymerization of flavonoid and biosynthesis of lignin has been demonstrated to be catalyzed by laccase 15, a functional enzyme encoded by the AtTT10 gene. In this study, eight Brassica TT10 genes (three from B. napus, three from B. rapa and two from B. oleracea) were isolated and their roles in flavonoid oxidation/polymerization and lignin biosynthesis were investigated. Based on our phylogenetic analysis, these genes could be divided into two groups with obvious structural and functional differentiation. Expression studies showed that Brassica TT10 genes are active in developing seeds, but with differential expression patterns in yellow- and black-seeded near-isogenic lines. For functional analyses, three black-seeded B. napus cultivars were chosen for transgenic studies. Transgenic B. napus plants expressing antisense TT10 constructs exhibited retarded pigmentation in the seed coat. Chemical composition analysis revealed increased levels of soluble proanthocyanidins, and decreased extractable lignin in the seed coats of these transgenic plants compared with that of the controls. These findings indicate a role for the Brassica TT10 genes in proanthocyanidin polymerization and lignin biosynthesis, as well as seed coat pigmentation in B. napus. PMID:23613820

  5. Trends in lignin modification: a comprehensive analysis of the effects of genetic manipulations/mutations on lignification and vascular integrity

    NASA Technical Reports Server (NTRS)

    Anterola, Aldwin M.; Lewis, Norman G.

    2002-01-01

    /mutations also established that a depletion in monolignol supply reduced both lignin contents supply reduced both lignin contents and vascular integrity, with a concomitant shift towards (upstream) metabolite build-up and/or shunting.The extraordinary claims of involvement of surrogate monomers (2-methoxybenzaldehyde, feruloyl tyramine, vanillic acid, etc.) in lignification were fully disproven and put to rest, with the investigators themselves having largely retracted former claims. Furthermore analysis of the well-known bm1 mutation, a presumed CAD disrupted system, apparently revealed that both G and S lignin components were reduced. This seems to imply that there is no monolignol specific dehydrogenase, such as the recently described sinapyl alcohol dehydrogenase (SAD) for sinapyl alcohol formation. Nevertheless, different CAD isoforms of differing homology seem to be operative in different lignifying cell types, thereby giving the G-enriched and G/S-enriched lignin biopolymers, respectively. For the G-lignin forming network, however, the CAD isoform is apparently catalytically less efficient with all three monolignols than that additionally associated with the corresponding G/S lignin forming network(s), which can more efficiently use all three monolignols. However, since CAD does not determine either H, G, or S designation, it again serves in a subsidiary role-albeit using different isoforms for different cell wall developmental and cell wall type responses.The results from this analysis contrasts further with speculations of some early investigators, who had viewed lignin assembly as resulting from non-specific oxidative coupling of monolignols and subsequent random polymerization. At that time, though, the study of the complex biological (biochemical) process of lignin assembly had begun without any of the (bio)chemical tools to either address or answer the questions posed as to how its formation might actually occur. Today, by contrast, there is growing recognition of

  6. Systems biology-guided biodesign of consolidated lignin conversion

    DOE PAGES

    Lin, Lu; Cheng, Yanbing; Pu, Yunqiao; Sun, Su; Li, Xiao; Jin, Mingjie; Pierson, Elizabeth A.; Gross, Dennis C.; Dale, Bruce E.; Dai, Susie Y.; et al

    2016-07-12

    Lignin is the second most abundant biopolymer on the earth, yet its utilization for fungible products is complicated by its recalcitrant nature and remains a major challenge for sustainable lignocellulosic biorefineries. In this study, we used a systems biology approach to reveal the carbon utilization pattern and lignin degradation mechanisms in a unique lignin-utilizing Pseudomonas putida strain (A514). The mechanistic study further guided the design of three functional modules to enable a consolidated lignin bioconversion route. First, P. putida A514 mobilized a dye peroxidase-based enzymatic system for lignin depolymerization. This system could be enhanced by overexpressing a secreted multifunctional dyemore » peroxidase to promote a two-fold enhancement of cell growth on insoluble kraft lignin. Second, A514 employed a variety of peripheral and central catabolism pathways to metabolize aromatic compounds, which can be optimized by overexpressing key enzymes. Third, the β-oxidation of fatty acid was up-regulated, whereas fatty acid synthesis was down-regulated when A514 was grown on lignin and vanillic acid. Therefore, the functional module for polyhydroxyalkanoate (PHA) production was designed to rechannel β-oxidation products. As a result, PHA content reached 73% per cell dry weight (CDW). Further integrating the three functional modules enhanced the production of PHA from kraft lignin and biorefinery waste. Furthermore, this study elucidated lignin conversion mechanisms in bacteria with potential industrial implications and laid out the concept for engineering a consolidated lignin conversion route.« less

  7. Modulation of mutagenicity of various mutagens by lignin derivatives.

    PubMed

    Mikulásová, Mária; Kosíková, Bozena

    2003-03-01

    The effect of lignin on cytotoxicity, mutagenicity and SOS response induced by 4-nitroquinoline-N-oxide (4NQO), 3-(5-nitro-2-furyl)acrylic acid (5NFAA), 2-nitrofluorene (2NF) as well as hydrogen peroxide was investigated in bacterial assay systems, i.e. the Ames test with Salmonella typhimurium TA98, TA100, TA102 and the SOS chromotest with Escherichia coli PQ37. Lignin preparations obtained from beech wood significantly decreased the mutagenicity induced by 4NQO, 2NF and H(2)O(2). In the case of mutagenicity induced by 5NFAA the effect was lower. Antimutagenic properties of lignin samples tested were shown also by SOS chromotest where lignin inhibited the ability of both 4NQO and H(2)O(2) to induce the SOS response. Derivatives of lignin including those from soft and hard wood, as well as from annual plants differ in their efficiency to inhibit the induction of the SOS response. The modified lignins isolated from beech and spruce wood exhibit a high level of protection. Lignins from annual plants-corn cobs and straw-only marginally evoked an antimutagenic response, but their effect was increased by hydrothermic treatment of both annual plants. The results obtained indicate the prospective utilization of lignin preparations as additive in chemo-prevention. The antimutagenic effect of lignin samples varies with the method of isolation and modification, as well as with the genetic origin of the lignin. PMID:12581535

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    Lignins are amongst the most studied bio-macromolecules in natural environments, for their properties as biomarkers and their suggested influence on soil organic carbon dynamics. A large number of methods exists to characterize lignins, but the alkaline CuO oxidation is the most used for determining lignin fate in soils. The CuO oxidation products of lignins yield quantitative information (sum of V, S and C monomers) as well as qualitative information on the degradation of lignins (S/V, C/V, (Ad/Al)V,S…). The CuO-lignin products provide information on lignins but also on the environment and particularly on the present and past vegetation. Data from several studies were compiled in order to evaluate the relations between lignins in soils and various environmental parameters. The results of the multiple correspondence analysis (MCA) performed suggest that the lignin content in soils is directly related to the C and N contents, confirming its contribution to the pool of organic carbon. The lignin distribution appears also related to the climate and to the soil texture, which suggests the impact of these parameters on the lignin degradation and retention in soils, as observed for organic carbon (Burke et al., 1989). The total lignin content generally decreases with the soil depth and with the decreasing size of the granulometric fractions. Hence, the more lignins are degraded, the more they are associated with the finest fractions. In addition, it appears that lignin contents are linked to land-use. Thus, in accordance with the land cover, management type and amount of annual input, the forest soils are described by high contents of VSC, C and N, in contrast with the arable land. Lignins were often considered to greatly participate to the stock of slowly degradable and stable carbon in soils. However, several studies suggest that lignin turnover can be more rapid than that of the bulk soil organic carbon (SOC), suggesting that they are not stabilized in soil. On the

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

    PubMed

    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.

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

    PubMed

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

    2015-01-01

    Celery of the family Apiaceae is a biennial herb that is cultivated and consumed worldwide. Lignin is essential for cell wall structural integrity, stem strength, water transport, mechanical support, and plant pathogen defense. This study discussed the mechanism of lignin formation at different stages of celery development. The transcriptome profile, lignin distribution, anatomical characteristics, and expression profile of leaves at three stages were analyzed. Regulating lignin synthesis in celery growth development has a significant economic value. Celery leaves at three stages were collected, and Illumina paired-end sequencing technology was used to analyze large-scale transcriptome sequences. From Stage 1 to 3, the collenchyma and vascular bundles in the petioles and leaf blades thickened and expanded, whereas the phloem and the xylem extensively developed. Spongy and palisade mesophyll tissues further developed and were tightly arranged. Lignin accumulation increased in the petioles and the mesophyll (palisade and spongy), and the xylem showed strong lignification. Lignin accumulation in different tissues and at different stages of celery development coincides with the anatomic characteristics and transcript levels of genes involved in lignin biosynthesis. Identifying the genes that encode lignin biosynthesis-related enzymes accompanied by lignin distribution may help elucidate the regulatory mechanisms of lignin biosynthesis in celery. PMID:25651889

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

    PubMed Central

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

    2015-01-01

    Celery of the family Apiaceae is a biennial herb that is cultivated and consumed worldwide. Lignin is essential for cell wall structural integrity, stem strength, water transport, mechanical support, and plant pathogen defense. This study discussed the mechanism of lignin formation at different stages of celery development. The transcriptome profile, lignin distribution, anatomical characteristics, and expression profile of leaves at three stages were analyzed. Regulating lignin synthesis in celery growth development has a significant economic value. Celery leaves at three stages were collected, and Illumina paired-end sequencing technology was used to analyze large-scale transcriptome sequences. From Stage 1 to 3, the collenchyma and vascular bundles in the petioles and leaf blades thickened and expanded, whereas the phloem and the xylem extensively developed. Spongy and palisade mesophyll tissues further developed and were tightly arranged. Lignin accumulation increased in the petioles and the mesophyll (palisade and spongy), and the xylem showed strong lignification. Lignin accumulation in different tissues and at different stages of celery development coincides with the anatomic characteristics and transcript levels of genes involved in lignin biosynthesis. Identifying the genes that encode lignin biosynthesis-related enzymes accompanied by lignin distribution may help elucidate the regulatory mechanisms of lignin biosynthesis in celery. PMID:25651889

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    A chitosan biopolymer microfibre—reinforced by lignin—has been processed by a wet-spinning method. To optimise the fibre mechanical and structural properties two types of lignin, with molecular weights 28 000 g mol-1 and 60 000 g mol-1, were examined and the chitosan fibre was blended with the respective lignin type at 1, 3, 5, 7 and 8 wt% lignin concentrations. The main effects of lignin type and concentration, as well as the interaction between the two parameters, on the fibre tensile stiffness, extensibility, strength and toughness were evaluated using the two-factor analysis of variance. Significant variations in the respective mechanical properties were observed with varying lignin concentrations (P < 0.05). The magnitude of the respective mechanical properties is low at 1 wt% but peaks at 3 wt% before decreasing steadily with increasing lignin concentration. Except for extensibility, significant variations in the strength and toughness were observed with respect to lignin type (P < 0.05) variations in the stiffness were masked by interactions between lignin type and concentration. These results were related to the dispersion of lignin in the fibre and the nature of the bonds between lignin and chitosan, based on findings from scanning electron microscopy and Fourier transform infrared spectroscopy. This new method for the fabrication of chitosan biopolymer microfibre is inexpensive and versatile and could lend itself to the production of high performance biocomposite structures.

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

    PubMed

    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.

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

    PubMed

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

    2015-02-05

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

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

    PubMed

    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. PMID:27310182

  16. Enzymatic synthesis of lignin-siloxane hybrid functional polymers.

    PubMed

    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.

  17. Mechanism of lignin inhibition of enzymatic biomass deconstruction

    DOE PAGES

    Vermaas, Josh V.; Petridis, Loukas; Qi, Xianghong; Schulz, Roland; Lindner, Benjamin; Smith, Jeremy. C.

    2015-12-01

    The conversion of plant biomass to ethanol via enzymatic cellulose hydrolysis offers a potentially sustainable route to biofuel production. However, the inhibition of enzymatic activity in pretreated biomass by lignin severely limits the efficiency of this process. By performing atomic-detail molecular dynamics simulation of a biomass model containing cellulose, lignin, and cellulases (TrCel7A), we elucidate detailed lignin inhibition mechanisms. We find that lignin binds preferentially both to the elements of cellulose to which the cellulases also preferentially bind (the hydrophobic faces) and also to the specific residues on the cellulose-binding module of the cellulase that are critical for cellulose bindingmore » of TrCel7A (Y466, Y492, and Y493). In conclusion, lignin thus binds exactly where for industrial purposes it is least desired, providing a simple explanation of why hydrolysis yields increase with lignin removal.« less

  18. Directional synthesis of ethylbenzene through catalytic transformation of lignin.

    PubMed

    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.

  19. Comparison of lignin extraction processes: Economic and environmental assessment.

    PubMed

    Carvajal, Juan C; Gómez, Álvaro; Cardona, Carlos A

    2016-08-01

    This paper presents the technical-economic and environmental assessment of four lignin extraction processes from two different raw materials (sugarcane bagasse and rice husks). The processes are divided into two categories, the first processes evaluates lignin extraction with prior acid hydrolysis step, while in the second case the extraction processes are evaluated standalone for a total analysis of 16 scenarios. Profitability indicators as the net present value (NPV) and environmental indicators as the potential environmental impact (PEI) are used through a process engineering approach to understand and select the best lignin extraction process. The results show that both economically and environmentally process with sulfites and soda from rice husk presents the best results; however the quality of lignin obtained with sulfites is not suitable for high value-added products. Then, the soda is an interesting option for the extraction of lignin if high quality lignin is required for high value-added products at low costs.

  20. Redistribution of Lignin Caused by Dilute Acid Pretreatment of Biomass

    SciTech Connect

    Johnson, D. K.; Donohoe, B. S.; Katahira, R.; Tucker, M. P.; Vinzant, T. B.; Himmel, M. E.

    2012-01-01

    Research conducted at NREL has shown that lignin undergoes a phase transition during thermochemical pretreatments conducted above its glass transition temperature. The lignin coalesces within the plant cell wall and appears as microscopic droplets on cell surfaces. It is clear that pretreatment causes significant changes in lignin distribution in pretreatments at all scales from small laboratory reactors to pilot scale reactors. A method for selectively extracting lignin droplets from the surfaces of pretreated cell walls has allowed us to characterize the chemical nature and molecular weight distribution of this fraction. The effect of lignin redistribution on the digestibility of pretreated solids has also been tested. It is clear that removal of the droplets increases the digestibility of pretreated corn stover. The improved digestibility could be due to decreased non-specific binding of enzymes to lignin in the droplets, or because the droplets no longer block access to cellulose.

  1. Mechanism of lignin inhibition of enzymatic biomass deconstruction

    SciTech Connect

    Vermaas, Josh V.; Petridis, Loukas; Qi, Xianghong; Schulz, Roland; Lindner, Benjamin; Smith, Jeremy. C.

    2015-12-01

    The conversion of plant biomass to ethanol via enzymatic cellulose hydrolysis offers a potentially sustainable route to biofuel production. However, the inhibition of enzymatic activity in pretreated biomass by lignin severely limits the efficiency of this process. By performing atomic-detail molecular dynamics simulation of a biomass model containing cellulose, lignin, and cellulases (TrCel7A), we elucidate detailed lignin inhibition mechanisms. We find that lignin binds preferentially both to the elements of cellulose to which the cellulases also preferentially bind (the hydrophobic faces) and also to the specific residues on the cellulose-binding module of the cellulase that are critical for cellulose binding of TrCel7A (Y466, Y492, and Y493). In conclusion, lignin thus binds exactly where for industrial purposes it is least desired, providing a simple explanation of why hydrolysis yields increase with lignin removal.

  2. Comparison of lignin extraction processes: Economic and environmental assessment.

    PubMed

    Carvajal, Juan C; Gómez, Álvaro; Cardona, Carlos A

    2016-08-01

    This paper presents the technical-economic and environmental assessment of four lignin extraction processes from two different raw materials (sugarcane bagasse and rice husks). The processes are divided into two categories, the first processes evaluates lignin extraction with prior acid hydrolysis step, while in the second case the extraction processes are evaluated standalone for a total analysis of 16 scenarios. Profitability indicators as the net present value (NPV) and environmental indicators as the potential environmental impact (PEI) are used through a process engineering approach to understand and select the best lignin extraction process. The results show that both economically and environmentally process with sulfites and soda from rice husk presents the best results; however the quality of lignin obtained with sulfites is not suitable for high value-added products. Then, the soda is an interesting option for the extraction of lignin if high quality lignin is required for high value-added products at low costs. PMID:27174614

  3. Green Diesel from Kraft Lignin in Three Steps.

    PubMed

    Löfstedt, Joakim; Dahlstrand, Christian; Orebom, Alexander; Meuzelaar, Gerrit; Sawadjoon, Supaporn; Galkin, Maxim V; Agback, Peter; Wimby, Martin; Corresa, Elena; Mathieu, Yannick; Sauvanaud, Laurent; Eriksson, Sören; Corma, Avelino; Samec, Joseph S M

    2016-06-22

    Precipitated kraft lignin from black liquor was converted into green diesel in three steps. A mild Ni-catalyzed transfer hydrogenation/hydrogenolysis using 2-propanol generated a lignin residue in which the ethers, carbonyls, and olefins were reduced. An organocatalyzed esterification of the lignin residue with an in situ prepared tall oil fatty acid anhydride gave an esterified lignin residue that was soluble in light gas oil. The esterified lignin residue was coprocessed with light gas oil in a continous hydrotreater to produce a green diesel. This approach will enable the development of new techniques to process commercial lignin in existing oil refinery infrastructures to standardized transportation fuels in the future. PMID:27246391

  4. Modeling lignin liquefaction: 1. Catalytic hydroprocessing of lignin-related methoxyphenols and interaromatic unit linkages

    SciTech Connect

    Petrocelli, F.P.; Klein, M.T.

    1987-01-01

    The reactions of two sets of lignin model compounds over a sulfided CoOMoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst were studied. The first set mimicked lignin methoxyphenol residues and comprised 4-methyl-guaiacol, 4-methylcatechol, eugenol and vanillin. Deoxygenation and hydrogenation were facile and led to ultimate molar yields of single-ring products as high as 0.70. The selectivity to single-ring products increased with increases in temperature. o-hydroxydiphenylmethane, phenyl ether and o,o'-biphenol constituted the second set that mimicked thermally stable lignin bonds. Fragmentation of o-hydroxydiphenylmethane and phenyl ether occurred readily; o,o'-biphenol reacted to dibenzofuran.

  5. Step-Growth Polymerization.

    ERIC Educational Resources Information Center

    Stille, J. K.

    1981-01-01

    Following a comparison of chain-growth and step-growth polymerization, focuses on the latter process by describing requirements for high molecular weight, step-growth polymerization kinetics, synthesis and molecular weight distribution of some linear step-growth polymers, and three-dimensional network step-growth polymers. (JN)

  6. Halley's polymeric organic molecules

    NASA Technical Reports Server (NTRS)

    Huebner, W. F.; Boice, D. C.; Korth, A.

    1989-01-01

    The detection of polymeric organic compounds in the mass spectrum of Comet Halley obtained with the Positive Ion Cluster Composition analyzer on Giotto are examined. It is found that, in addition to polyoxymethylene, other polymers and complex molecules may exist in the comet. It is suggested that polymerized hydrogen cyanide may be a source for the observed CN and NH2 jets.

  7. Evidence for lignin oxidation by the giant panda fecal microbiome.

    PubMed

    Fang, Wei; Fang, Zemin; Zhou, Peng; Chang, Fei; Hong, Yuzhi; Zhang, Xuecheng; Peng, Hui; Xiao, Yazhong

    2012-01-01

    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 of bamboo lignin

  8. Lignin transformations and reactivity upon ozonation in aqueous media

    NASA Astrophysics Data System (ADS)

    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.

  9. Evidence for Lignin Oxidation by the Giant Panda Fecal Microbiome

    PubMed Central

    Zhou, Peng; Chang, Fei; Hong, Yuzhi; Zhang, Xuecheng; Peng, Hui; Xiao, Yazhong

    2012-01-01

    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 of bamboo

  10. Polymeric Carbon Dioxide

    SciTech Connect

    Yoo, C-S.

    1999-11-02

    Synthesis of polymeric carbon dioxide has long been of interest to many chemists and materials scientists. Very recently we discovered the polymeric phase of carbon dioxide (called CO{sub 2}-V) at high pressures and temperatures. Our optical and x-ray results indicate that CO{sub 2}-V is optically non-linear, generating the second harmonic of Nd: YLF laser at 527 nm and is also likely superhard similar to cubic-boron nitride or diamond. CO{sub 2}-V is made of CO{sub 4} tetrahedra, analogous to SiO{sub 2} polymorphs, and is quenchable at ambient temperature at pressures above 1 GPa. In this paper, we describe the pressure-induced polymerization of carbon dioxide together with the stability, structure, and mechanical and optical properties of polymeric CO{sub 2}-V. We also present some implications of polymeric CO{sub 2} for high-pressure chemistry and new materials synthesis.

  11. Experimental Study of Mechanistic Acid Deconstruction of Lignin

    SciTech Connect

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

    2012-01-01

    Lignin is a major component of biomass, which remains highly underutilized in selective biomass conversion strategies to renewable fuels and chemicals. Here we are interested in studying the mechanisms related to the acid deconstruction of lignin with a combined theoretical and experimental approach. Quantum mechanical calculations were employed to elucidate possible deconstruction mechanisms with transition state theory. Model dimers, imitating H, S, and G lignins, were synthesized with the most abundant {beta} - O - 4 linkage in lignin. These compounds were then depolymerized using various acids and at different operating conditions. The deconstruction products were analyzed to complement the QM studies and investigate proposed mechanisms.

  12. Acid precipitation and food quality: Effects of dietary Al, Ca and P on bone and liver characteristics in American black ducks and mallards

    USGS Publications Warehouse

    Sparling, D.W.

    1991-01-01

    American black ducks (Anas rubripes) and mallards (A. platyrhynchos) were fed diets varying in concentrations of aluminum (Al). calcium (Ca), and phosphorus (P) for 10 weeks to identify toxic effects of Al under conditions representative of areas with acid precipitation. Femur and liver tissues were analyzed for Al. Ca, and P concentrations and structural characteristics. At two weeks of age, both species demonstrated pronounced differences in femur Al and P concentrations and femur mass from dietary Al and interaction between Ca:P regimen and Al:Low Ca:Low P enhanced Al storage and decreased P and mass in femurs. Femur Ca was lowest in the Low Ca:Low P regimen but was not affected by dietary Al. At 10 weeks, femur and liver Al continued to vary with dietary Al. Elevated Al and reduced Ca lowered modulus of elasticity. Femur P increased with elevated dietary P in black ducks. Elevated dietary P negated some of the effects of dietary A! on femur mass in black ducks. Reduced Ca concentrations weakened bones of both species and lowered both Ca and P. An array of clinical signs including lameness, discoloration of the upper mandible, complete and greenstick fractures, and death were responses to elevated Al and Ca:P regimen. Black ducks seemed to display these signs over a wider range of diets than mallards. Diets of 1,000 mg/kg Al had toxic effects on both species, particularly when combined with diets low in Ca and P.

  13. Effects of acidic precipitation on the water quality of streams in the Laurel Hill area, Somerset County, Pennsylvania, 1983-86

    USGS Publications Warehouse

    Barker, J.L.; Witt, E. C.

    1990-01-01

    Five headwater streams in the Laurel Hill area in southwestern Pennsylvania were investigated from September 1983 through February 1986 to determine possible effects of acidic precipitation on water quality. Precipitation in the Laurel Hill area is among the most acidic in the Nation, with a mean volume-weighted pH of 4.06. Sulfate is the dominant acid-forming anion, averaging 3.6 milligrams per liter or about 50 kilograms per hectare in wet deposition alone. Nitrate averages about 2 milligrams per liter or 7 kilograms per hectare in the study area. Stream chemistry in the five streams is quite variable and apparently is influenced to a large degree by the bedrock geology and by small amounts of alkaline material in watershed soils. Three of the five streams with no or little acid-neutralizing capacity presently are devoid of fish because of low pH and elevated aluminum concentrations. Aluminum concentrations increase in the other two streams during rainfall and snowmelt despite comparatively higher base flow and acid-neutralizing capacities. Comparison of the chemistry of streamflow during 14 storm events at South Fork Bens Creek and North Fork Bens Creek reveals similar chemical responses when discharge suddenly increases. Concentrations of dissolved metals and sulfate increased during stormflow and snowmelt runoff, whereas concentrations of base cations, silica, and chloride decreased. Nitrate concentrations were not affected by rainfall runoff by tended to increase with snowmelt runoff.

  14. Acid precipitation and food quality: Inhibition of growth and survival in black ducks and mallards by dietary aluminum, calcium and phosphorus

    USGS Publications Warehouse

    Sparling, D.W.

    1990-01-01

    In areas impacted by acid precipitation, water chemistry of acidic ponds and streams often changes, resulting in increased mobilization of aluminum and decreased concentration of calcium carbonate. Aluminum binds with phosphorus and inhibits its uptake by organisms. Thus, invertebrate food organisms used by waterfowl may have inadequate Ca and P or elevated Al for normal growth and development. Acid rain and its effects may be one of the factors negatively impacting American black ducks (Anas rubripes) in eastern North America. One-day old mallards (A. platyrhynchos) and black ducks were placed on one of three Ca:P regimens: low:low (LL), normal:normal (NN), and low:high (LH) with each regimen divided further into three or four Al levels for 10 weeks. Forty-five % of the black ducks died on nine different diets whereas only 28% of the mallards died on three different diets. Mortality was significantly related to diet in both species. Growth rates for body weight, culmens, wings, and tarsi of both species on control diets exceeded those on many treatment diets but the differences were less apparent for mallards than for black ducks. Differences among treatments were due to both Ca:P and Al levels.

  15. Acid precipitation and food quality: inhibition of growth and survival in black ducks and mallards by dietary aluminum, calcium, and phosphorus.

    PubMed

    Sparling, D W

    1990-01-01

    In areas impacted by acid precipitation, water chemistry of acidic ponds and streams often changes, resulting in increased mobilization of aluminum and decreased concentration of calcium carbonate. Aluminum binds with phosphorus and inhibits its uptake by organisms. Thus, invertebrate food organisms used by waterfowl may have inadequate Ca and P or elevated Al for normal growth and development. Acid rain and its effects may be one of the factors negatively impacting American black ducks (Anas rubripes) in eastern North America. One-day old mallards (A. platyrhynchos) and black ducks were placed on one of three Ca:P regimens: low:low (LL), normal:normal (NN), and low:high (LH) with each regimen divided further into three or four Al levels for 10 weeks. Forty-five % of the black ducks died on nine different diets whereas only 28% of the mallards died on three different diets. Mortality was significantly related to diet in both species. Growth rates for body weight, culmens, wings, and tarsi of both species on control diets exceeded those on many treatment diets but the differences were less apparent for mallards than for black ducks. Differences among treatments were due to both Ca:P and Al levels.

  16. [High aluminum concentrations in well water of southern Lower Saxony sandy soil areas caused by acid precipitation--evaluation from the public health and ecologic viewpoint].

    PubMed

    Mühlenberg, W

    1990-01-01

    Decades of acid precipitation have caused soil acidification in regions with low neutralizing capacity of industrial countries, thus mobilizing aluminium from clay minerals into soil solution and ground water. In the southern sandy heath-land of Lower Saxony all the wells with pH values lower than 4.5 showed aluminium contents higher than 2.0 mg/l. 66.7% of the specimens within the pH-range 4.5 to 5.0 and 20% of the specimens within the pH-range 5.0 to 5.5 had aluminium levels of more than 0.2 mg/l, that is the maximum permissible limit value of the drinking water regulation. High contents of aluminium in drinking water are objectionable from the hygienic point of view, as they may cause intoxications in infants and patients with impaired renal function. In addition to this, the involvement of aluminium in the pathogenesis of severe degenerative disorders of the central nervous system cannot be excluded, such as Alzheimers disease, amyotrophic lateral sclerosis and Parkinsons dementia.

  17. Effects of acidic precipitation on the water quality of streams in the Larel Hill area, Somerset County, Pennsylvania, 1983-86

    SciTech Connect

    Barker, J.L.; Witt, E.C.

    1990-01-01

    Five headwater streams in the Laurel Hill area in southwestern Pennsylvania were investigated from September 1983 through February 1986 to determine possible effects of acidic precipitation on water quality. Precipitation in the Larel Hill area is among the most acidic in the Nation, with a mean volume-weighted pH of 4.06. Sulfate is the dominant acid-forming anion, averaging 3.6 mg/L or about 50 kg/hectare in wet deposition alone. Nitrate averages about 2 mg/L or 7 kg/hectare in the study area. Stream chemistry in the five streams is quite variable and apparently is influenced to a large degree by the bedrock geology and by small amounts of alkaline material in watershed soils. Three of the five streams with no or little acid-neutralizing capacity present are devoid of fish because of low pH and elevated aluminum concentrations. Aluminum concentrations increase in the other two streams during rainfall and snowmelt despite comparatively higher base flow and acid-neutralizing capacities. Comparison of the chemistry of streamflow during 14 storm events at South Fork Bens Creek and North Bens creek reveals similar chemical responses when discharge suddenly increases. concentrations of dissolved metals and sulfate increased during stormflow and snowmelt runoff, whereas concentrations of base cations, silica, and chloride decreased. Nitrate concentrations were not affected by rainfall runoff, but tended to increase with snowmelt runoff. 36 refs., 19 figs., 15 tabs.

  18. Growth response of four species of Eastern hardwood tree seedlings exposed to ozone, acidic precipitation, and sulfur dioxide. [Prunus serotina, Acer rubrum, Quercus rubra, Liriodendron tulipifera

    SciTech Connect

    Davis, D.D. Skelly, J.M. )

    1992-03-01

    In 1987 a study was conducted in controlled environment chambers to determine the foliar sensitivity of tree seedlings of eight species to ozone and acidic precipitation, and to determine the influence of leaf position on symptom severity. Jensen and Dochinger conducted concurrent similar studies in Continuously Stirred Tank Reactor (CSTR) chambers with ten species of forest trees. Based on the results of these initial studies, four species representing a range in foliar sensitivity to ozone were chosen: black cherry (Prunus serotina Ehrh.), red maple (Acer rubrum L.), northern red oak (Quercus rubra L.) and yellow-poplar (Liriodendron tulipifera L.). These species were also chosen because of their ecological and/or commercial importance in Pennsylvania. Seedlings were exposed in growth chambers simulated acid rain. In addition acute exposures to sulfur dioxide were conducted in a regime based on unpublished monitoring data collected near coal-fired power plants. The objective of this study was to determine if the pollutant treatments influenced the growth and productivity of seedlings of these four species. This information will help researchers and foresters understand the role of air pollution in productivity of eastern forests.

  19. In situ lignocellulosic unlocking mechanism for carbohydrate hydrolysis in termites: crucial lignin modification

    PubMed Central

    2011-01-01

    Background Termites are highly effective at degrading lignocelluloses, and thus can be used as a model for studying plant cell-wall degradation in biological systems. However, the process of lignin deconstruction and/or degradation in termites is still not well understood. Methods We investigated the associated structural modification caused by termites in the lignin biomolecular assembly in softwood tissues crucial for cell-wall degradation. We conducted comparative studies on the termite-digested (i.e. termite feces) and native (control) softwood tissues with the aid of advanced analytical techniques: 13C crosspolarization magic angle spinning and nuclear magnetic resonance (CP-MAS-NMR) spectroscopy, flash pyrolysis with gas chromatography mass spectrometry (Py-GC/MS), and Py-GC-MS in the presence of tetramethylammonium hydroxide (Py-TMAH)-GC/MS. Results The 13C CP/MAS NMR spectroscopic analysis revealed an increased level of guaiacyl-derived (G unit) polymeric framework in the termite-digested softwood (feces), while providing specific evidence of cellulose degradation. The Py-GC/MS data were in agreement with the 13C CP/MAS NMR spectroscopic studies, thus indicating dehydroxylation and modification of selective intermonomer side-chain linkages in the lignin in the termite feces. Moreover, Py-TMAH-GC/MS analysis showed significant differences in the product distribution between control and termite feces. This strongly suggests that the structural modification in lignin could be associated with the formation of additional condensed interunit linkages. Conclusion Collectively, these data further establish: 1) that the major β-O-4' (β-aryl ether) was conserved, albeit with substructure degeneracy, and 2) that the nature of the resulting polymer in termite feces retained most of its original aromatic moieties (G unit-derived). Overall, these results provide insight into lignin-unlocking mechanisms for understanding plant cell-wall deconstruction, which could be

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

    PubMed

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

    2014-11-13

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

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Obtainment of chelating agents through the enzymatic oxidation of lignins by phenol oxidase.

    PubMed

    Calabria, Gabriela M M; Gonçalves, Adilson R

    2006-01-01

    Oxidation of lignin obtained from acetosolv and ethanol/water pulping of sugarcane bagasse was performed by phenol oxidases: tyrosinase (TYR) and laccase (LAC), to increase the number of carbonyl and hydroxyl groups in lignin, and to improve its chelating capacity. The chelating properties of the original and oxidized lignins were compared by monitoring the amount of Cu2+ bound to lignin by gel permeation chromatography. The Acetosolv lignin oxidized with TYR was 16.8% and with LAC 21% higher than that of the original lignin. For ethanol/water lignin oxidized with TYR was 17.2% and with LAC 18% higher than that of the original lignin. PMID:16915650

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

    DOEpatents

    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.

  4. Acid precipitation; an annotated bibliography

    USGS Publications Warehouse

    Wiltshire, Denise A.; Evans, Margaret L.

    1984-01-01

    This collection of 1660 bibliographies references on the causes and environmental effects of acidic atmospheric deposition was compiled from computerized literature searches of earth-science and chemistry data bases. Categories of information are (1) atmospheric chemistry (gases and aerosols), (2) precipitation chemistry, (3) transport and deposition (wet and dry), (4) aquatic environments (biological and hydrological), (5) terrestrial environments, (6) effects on materials and structures, (7) air and precipitation monitoring and data collection, and (8) modeling studies. References date from the late 1800 's through December 1981. The bibliography includes short summaries of most documents. Omitted are unpublished manuscripts, publications in press, master 's theses and doctoral dissertations, newspaper articles, and book reviews. Coauthors and subject indexes are included. (USGS)

  5. [Characterization of lignin and Mn peroxidases from Phanerochaete chrysosporium

    SciTech Connect

    Not Available

    1992-01-01

    Lignin peroxidases were investigated with respect to enzyme kinetics and NMR spectroscopy of the heme domain. MN peroxidases were studied with respect to the role of oxalate in enzyme activity, the NMR spectroscopy of the heme domain. Gene expression of both lignin and MN peroxidases were examined as well as expression of site-directed mutants aimed at scale up production of these enzymes.

  6. Modification of lignin content and composition in plants

    DOEpatents

    Ye, Zheng-Hua

    2002-01-01

    Plants and methods of preparing plants having reduced lignin content and/or altered lignin composition are provided. The activities of caffeoyl-CoA O-methyltransferase and/or caffeic acid O-methyltransferase enzymes in the modified plants are reduced.

  7. Flocculation of high purity wheat straw soda lignin.

    PubMed

    Piazza, G J; Lora, J H; Garcia, R A

    2014-01-01

    In industrial process, acidification causes non-sulfonated lignin insolubility. The flocculants poly(diallyldimethylammonium chloride) (pDADMAC) and bovine blood (BB) also caused lignin insolubility while cationic polyacrylamide, chitosan, and soy protein PF 974 were ineffective. Turbidity determined optimal flocculant, but turbidity magnitude with BB was greater than expected. pDADMAC caused negative lignin Zeta potential to became positive, but BB-lignin Zeta potential was always negative. Insoluble lignin did not gravity sediment, and flocculant-lignin mixtures were centrifuged. Pellet and supernatant dry mass and corrected spectroscopic results were in good agreement for optimal pDADMAC and BB. Spectroscopy showed 87-92% loss of supernatant lignin. Nitrogen analysis showed BB concentrated in the pellet until the pellet became saturated with BB. Subtracting ash and BB mass from pellet and supernatant mass confirmed optimal BB. Low levels of alum caused increased lignin flocculation at lower levels of pDADMAC and BB, but alum did not affect optimal flocculant.

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

    PubMed

    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.

  9. Concise polymeric materials encyclopedia

    SciTech Connect

    Salamone, J.C.

    1999-01-01

    This comprehensive, accessible resource abridges the ``Polymeric Materials Encyclopedia'', presenting more than 1,100 articles and featuring contributions from more than 1,800 scientists from all over the world. The text discusses a vast array of subjects related to the: (1) synthesis, properties, and applications of polymeric materials; (2) development of modern catalysts in preparing new or modified polymers; (3) modification of existing polymers by chemical and physical processes; and (4) biologically oriented polymers.

  10. Catalytic Hydrolytic Cleavage and Oxy-Cleavage of Lignin Linkages

    SciTech Connect

    Xia, Guanguang; Chen, Baowei; Zhang, Rui; Zhang, Z. Conrad

    2014-07-26

    In this work, new strategies involving organic bases were evaluated to depolymerize lignin to reduced molecular fragments in aqueous medium. NaOH as an inorganic base was also investigated as a reference. Full nature lignin samples are used for the study. As research tools to unravel the complexity of the macro lignin structure and bulky molecular size under this study, size exclusion chromatography and high resolution mass spectrometric analysis, typically used for protein characterizations, were used to follow the progress of lignin depolymerisation by measuring the molecular weight distribution of the products and determining the key molecular fingerprints, respectively. The results show that sodium phenoxide and guanidine carbonate are effective catalysts for lignin depolymerization. It is observed that there exists a synergism between H2O2 and the organic base, which is strongest with guanidine carbonate.

  11. Altered lignin biosynthesis using biotechnology to improve lignocellulosic biofuel feedstocks.

    PubMed

    Poovaiah, Charleson R; Nageswara-Rao, Madhugiri; Soneji, Jaya R; Baxter, Holly L; Stewart, Charles N

    2014-12-01

    Lignocellulosic feedstocks can be converted to biofuels, which can conceivably replace a large fraction of fossil fuels currently used for transformation. However, lignin, a prominent constituent of secondary cell walls, is an impediment to the conversion of cell walls to fuel: the recalcitrance problem. Biomass pretreatment for removing lignin is the most expensive step in the production of lignocellulosic biofuels. Even though we have learned a great deal about the biosynthesis of lignin, we do not fully understand its role in plant biology, which is needed for the rational design of engineered cell walls for lignocellulosic feedstocks. This review will recapitulate our knowledge of lignin biosynthesis and discuss how lignin has been modified and the consequences for the host plant.

  12. Process for conversion of lignin to reformulated hydrocarbon gasoline

    DOEpatents

    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.

  13. The graft polymers from different species of lignin and acrylic acid: synthesis and mechanism study.

    PubMed

    Ye, De zhan; Jiang, Li; Ma, Chao; Zhang, Ming-hua; Zhang, Xi

    2014-02-01

    The influence of lignin species on the grafting mechanism of lignosulfonate (from eucalyptus and pine, recorded as HLS and SLS, respectively) with acrylic acid (AA) was investigated. The graft polymers were confirmed by the absorption of carbonyl groups in the FTIR spectra. The decreasing phenolic group's content (Ph-OH) is not only due to its participation as grafting site but also to the negative effect of initiator. In the initial period (0-60 min), HLS and SLS both accelerate the polymerization of AA. Additionally, Ph-OH group's content is proportional to product yield (Y%), monomer conversion (C%) and grafting efficiency (GE%), strongly indicating that it acts as active center. Nevertheless, compared with HLS, Y% and C% in SLS grafting system are lower though it has higher Ph-OH group's content, which is due to the quinonoid structure formed by the self-conjugated of phenoxy radical in Guaiacyl unit. Finally, the lignosulfonate grafting mechanism was proposed. PMID:24076194

  14. Heterogeneous and Photochemical Reactions Involving Surface Adsorbed Organics: Common Lignin Pyrolysis Products With Nitrogen Dioxide.

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.; Nichols, B. R.; Rapa, C.; Costa, V.

    2009-05-01

    Solid-air interfaces, such as airborne particulate matter and ground level surfaces, provide unique supports for tropospheric heterogeneous chemistry. These interfaces commonly contain surface adsorbed organics, such as lignin pyrolysis products, that can significantly alter their physical and chemical properties. Attenuated total reflectance infrared spectroscopy (ATR-FTIR) provides an ideal tool for monitoring chemical changes in thin organic films during heterogeneous and photochemical reactions. Phenolic compounds, with and without co- adsorbed photosensitizers, were exposed to NO2 concentrations in the parts-per-billion range at 300 K and 20% relative humidity. Catechol, when mixed with benzophenone or dicyclohexylketone, formed 4- nitrocatechol as the dominant product under dark conditions. Deuterating the catechol alcohol groups caused the initial rate of reaction to decrease by a factor of 3.3±0.5, consistent with formation of the ortho- semiquinone radical as the rate determining step. The rate of 4-nitrocatechol formation did not increase under illuminated conditions, even with the presence of benzophenone a well known photosensitizer. UV-A/visible radiation did, however, initiate a photochemical reaction between benzophenone and 4-nitrocatechol, likely forming high molecular weight polymerization products. In contrast, 2-ethoxyphenol displayed no reactivity with NO2, even under illuminated conditions with a photosensitizer. Implications for the fate of lignin pyrolysis products, which are prevalent in biomass combustion smoke, will be discussed.

  15. Radical-Mediated Enzymatic Polymerizations.

    PubMed

    Zavada, Scott R; Battsengel, Tsatsral; Scott, Timothy F

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes--catalytic proteins--owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol-ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  16. Radical-Mediated Enzymatic Polymerizations

    PubMed Central

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  17. Development of a prototype lignin concentration sensor

    SciTech Connect

    Malito, M.L.; Jeffers, L.A.

    1993-01-01

    The US Department of Energy, Office of Industrial Technologies, is sponsoring a research and development program for the development of a real-time, in-situ sensor to measure the concentration of lignin in wood pulp. The program is composed of phase I showing feasibility which is now complete, phase II for development and testing of a Field Prototype, in progress, Phase III commercialization. Phase I work (funded entirely by B W) demonstrated a correlation between the fluorescence intensity and lignin concentration (as measured by TAPPI procedure, T 236 hm-85 Kappa Number of Pulp) for undiluted wood pulp samples. In Phase II, a laboratory test program directed at characterizing the fluorescence of wood pulp has been conducted as a prelude to the design of a prototype sensor. The current report summarizes the testing completed in Phase I and documents the Phase II laboratory testing completed through December 1991. Future Phase II efforts include additional laboratory testing, design and fabrication of a prototype sensor, and field testing of the prototype sensor. Phase III of the program will concentrate on the incorporation of the sensor into a control system and commercialization of the sensor.

  18. Development of a prototype lignin concentration sensor

    SciTech Connect

    Malito, M.L.; Jeffers, L.A.

    1993-01-01

    The US Department of Energy, Office of Industrial Technologies, is sponsoring a research and development program for the development of a real-time, in-situ sensor to measure the concentration of lignin in wood pulp. The program is composed of phase I showing feasibility which is now complete, phase II for development and testing of a Field Prototype, in progress, Phase III commercialization. Phase I work (funded entirely by B&W) demonstrated a correlation between the fluorescence intensity and lignin concentration (as measured by TAPPI procedure, T 236 hm-85 Kappa Number of Pulp) for undiluted wood pulp samples. In Phase II, a laboratory test program directed at characterizing the fluorescence of wood pulp has been conducted as a prelude to the design of a prototype sensor. The current report summarizes the testing completed in Phase I and documents the Phase II laboratory testing completed through December 1991. Future Phase II efforts include additional laboratory testing, design and fabrication of a prototype sensor, and field testing of the prototype sensor. Phase III of the program will concentrate on the incorporation of the sensor into a control system and commercialization of the sensor.

  19. Lignin biodegradation and the production of ethyl alcohol from cellulose

    SciTech Connect

    Rosenberg, S.L.; Wilke, C.R.

    1981-02-01

    During the last few years our group has been engaged in developing a biochemical process for the conversion of lignocellulosic materials to ethyl alcohol. Lignin is a barrier to complete cellulose saccharification in this process, but chemical and physical delignification steps are too expensive to be used at the present time. An enzymatic delignification process might be attractive for several reasons: little energy would be expected to be needed, enzymes could be recovered and reused, and useful chemicals might be produced from dissolved lignin. A number of thermophilic and thermotolerant fungi were examined for the ability to rapidly degrade lignocellulose in order to find an organism whcih produced an active lignin-degrading enzyme system. Chryosporium pruinosum and Sporotrichum pulverulentum were found to be active lignocellulose degraders, and C. pruinosum was chosen for further study. Lignin and carbohydrate were degraded when the substrate remained moistened by, but not submerged in, the liquid medium. Attempts were made to demonstrate a cell-free lignin degrading system by both extraction and pressing of cultures grown on moist lignocellulose. Carbohydrate-degrading activity was found but not lignin-degrading activity. This led us to ask whether diffusible lignin-degrading activity could be demonstrated in this organism. The data indicate that the lignin degradation system, or one or more of its components, produced by this organism is either unstable, non-diffusible, or inactive at small distances (about 1 mm) from growing hyphae. At present, studies are being conducted using diffusion cultures to select mutants of C. pruinosum that do produce a diffusible lignin degradation system. We are also examining a number of mesophilic lignin-degrading molds for this ability.

  20. ATP-binding cassette-like transporters are involved in the transport of lignin precursors across plasma and vacuolar membranes

    SciTech Connect

    Miao, Y.C.; Liu, C.

    2010-12-28

    Lignin is a complex biopolymer derived primarily from the condensation of three monomeric precursors, the monolignols. The synthesis of monolignols occurs in the cytoplasm. To reach the cell wall where they are oxidized and polymerized, they must be transported across the cell membrane. However, the molecular mechanisms underlying the transport process are unclear. There are conflicting views about whether the transport of these precursors occurs by passive diffusion or is an energized active process; further, we know little about what chemical forms are required. Using isolated plasma and vacuolar membrane vesicles prepared from Arabidopsis, together with applying different transporter inhibitors in the assays, we examined the uptake of monolignols and their derivatives by these native membrane vesicles. We demonstrate that the transport of lignin precursors across plasmalemma and their sequestration into vacuoles are ATP-dependent primary-transport processes, involving ATP-binding cassette-like transporters. Moreover, we show that both plasma and vacuolar membrane vesicles selectively transport different forms of lignin precursors. In the presence of ATP, the inverted plasma membrane vesicles preferentially take up monolignol aglycones, whereas the vacuolar vesicles are more specific for glucoconjugates, suggesting that the different ATP-binding cassette-like transporters recognize different chemical forms in conveying them to distinct sites, and that glucosylation of monolignols is necessary for their vacuolar storage but not required for direct transport into the cell wall in Arabidopsis.

  1. Preparation and characterization of Lignin-graft-poly (ɛ-caprolactone) copolymers based on lignocellulosic butanol residue.

    PubMed

    Liu, Xiaohuan; Zong, Enmin; Jiang, Jinhua; Fu, Shenyuan; Wang, Jifu; Xu, Binbin; Li, Wenhuan; Lin, Xianzhi; Xu, Yuzhi; Wang, Chunpeng; Chu, Fuxiang

    2015-11-01

    In this paper, a "graft from" Ring-Opening Polymerization (ROP) technique was used to synthesize a lignin-graft-poly (ɛ-caprolactone) copolymer (BBL-g-PCL) using biobutanol lignin (BBL) as raw material recovered from lignocellulosic butanol residue. Polymerizations were carried out with various mass ratios of BBL and CL monomer ([BBL]/([BBL]+[CL])=1.0%, 5.0%, 10%, 20% and 40% (w/w)) to obtain BBL-g-PCL copolymers with different molecular weights, ranging from 367 to 8163gmol(-1). The grafting efficiency was preliminary evidenced by the long-term stability of dissolution of BBL-g-PCL in toluene. FT-IR and NMR analysis provided the further evidences for successful formation of BBL-g-PCL copolymer. The thermal properties of BBL-g-PCL copolymers were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). These results indicated that BBL-g-PCL copolymer had relatively good thermal stability. The static contact angle of BBL-g-PCL coating film reached to 80°. The surface functional groups and chemical composition of BBL-g-PCL copolymer was investigated in detail by X-ray photoelectron spectroscopy (XPS). The surface morphology of BBL-g-PCL copolymer was studied by Atomic force microscopy (AFM). Additionally, BBL-g-PCL coating film exhibited high absorption in the ultraviolet (UV) range, which could allow for applications in UV-blocking coatings, as well as the extents for the utilization of lignocellulosic butanol residue.

  2. The role of lignin and lignin-like materials during wood hydrolysis

    SciTech Connect

    Zaher, F.A.

    1981-01-01

    The nature of the material precipitating from the acid prehydrolysates and hydrolysates of wood upon storage has been investigated. This material was analyzed for its sugar content, ultraviolet spectra, elemental composition, molecular weight distribution, and thermogravimetric behavior. All the results indicate that this material has the same properties as lignin. The results suggest also that this material is neither a resinification product from sugar decomposition nor extraneous materials of wood (resins, tannins, etc.). It is suggested, too, that the extraction of this material along with sugar during hydrolysis and prehydrolysis causes a considerable error in the results of wood analysis using standard methods based on weight loss. The actual percentages of lignin in the wood samples tested appear to vary from two to four times their values measured by standard methods. Consequently, the actual cellulose content of these materials may be far lower than has been reported. This has serious implications for schemes based on biomass conversion.

  3. Azo Dye Biodecolorization Enhanced by Echinodontium taxodii Cultured with Lignin

    PubMed Central

    Meng, Jing; Yu, Hongbo; Zhang, Xiaoyu

    2014-01-01

    Lignocellulose facilitates the fungal oxidization of recalcitrant organic pollutants through the extracellular ligninolytic enzymes induced by lignin in wood or other plant tissues. However, available information on this phenomenon is insufficient. Free radical chain reactions during lignin metabolism are important in xenobiotic removal. Thus, the effect of lignin on azo dye decolorization in vivo by Echinodontium taxodii was evaluated. In the presence of lignin, optimum decolorization percentages for Remazol Brilliant Violet 5R, Direct Red 5B, Direct Black 38, and Direct Black 22 were 91.75% (control, 65.96%), 76.89% (control, 43.78%), 43.44% (control, 17.02%), and 44.75% (control, 12.16%), respectively, in the submerged cultures. Laccase was the most important enzyme during biodecolorization. Aside from the stimulating of laccase activity, lignin might be degraded by E. taxodii, and then these degraded low-molecular-weight metabolites could act as redox mediators promoting decolorization of azo dyes. The relationship between laccase and lignin degradation was investigated through decolorization tests in vitro with purified enzyme and dozens of aromatics, which can be derivatives of lignin and can function as laccase mediators or inducers. Dyes were decolorized at triple or even higher rates in certain laccase–aromatic systems at chemical concentrations as low as 10 µM. PMID:25285777

  4. Producing a True Lignin Depolymerase for Biobleaching Softwood Kraft Pulp

    SciTech Connect

    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

  5. Recent advances in green hydrogels from lignin: a review.

    PubMed

    Thakur, Vijay Kumar; Thakur, Manju Kumari

    2015-01-01

    Recently, biorenewable polymers from different natural resources have attracted a greater attention of the research community for different applications starting from biomedical to automotive. Lignin is the second most abundant non-food biomass next to cellulose in the category of biorenewable polymers and is abundantly available as byproduct of several industries involved in paper making, ethanol production, etc. The development of various green materials from lignin, which is most often considered as waste, is therefore of prime interest from environmental and economic points of view. Over the last few years, little studies have been made into the use of lignin as an indispensable component in the hydrogels. This article provides an overview of the research work carried out in the last few years on lignin based hydrogels. This article comprehensively reviews the potential efficacy of lignin in biopolymer based green hydrogels with particular emphasis on synthesis, characterization and applications. In this article, several examples of hydrogels synthesized using different types of lignin are discussed to illustrate the state of the art in the use of lignin.

  6. Oxidation in Acidic Medium of Lignins from Agricultural Residues

    NASA Astrophysics Data System (ADS)

    Labat, Gisele Aparecida Amaral; Gonçalves, Adilson Roberto

    Agricultural residues as sugarcane straw and bagasse are burned in boilers for generation of energy in sugar and alcohol industries. However, excess of those by-products could be used to obtain products with higher value. Pulping process generates cellulosic pulps and lignin. The lignin could be oxidized and applied in effluent treatments for heavy metal removal. Oxidized lignin presents very strong chelating properties. Lignins from sugarcane straw and bagasse were obtained by ethanol-water pulping. Oxidation of lignins was carried out using acetic acid and Co/Mn/Br catalytical system at 50, 80, and 115 °C for 5 h. Kinetics of the reaction was accomplished by measuring the UV-visible region. Activation energy was calculated for lignins from sugarcane straw and bagasse (34.2 and 23.4 kJ mol-1, respectively). The first value indicates higher cross-linked formation. Fourier-transformed infrared spectroscopy data of samples collected during oxidation are very similar. Principal component analysis applied to spectra shows only slight structure modifications in lignins after oxidation reaction.

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

    PubMed

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

    2014-11-01

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

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

    PubMed

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

    2014-11-01

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

  9. Organocatalyzed Group Transfer Polymerization.

    PubMed

    Chen, Yougen; Kakuchi, Toyoji

    2016-08-01

    In contrast to the conventional group transfer polymerization (GTP) using a catalyst of either an anionic nucleophile or a transition-metal compound, the organocatalyzed GTP has to a great extent improved the living characteristics of the polymerization from the viewpoints of synthesizing structurally well-defined acrylic polymers and constructing defect-free polymer architectures. In this article, we describe the organocatalyzed GTP from a relatively personal perspective to provide our colleagues with a perspicuous and systematic overview on its recent progress as well as a reply to the curiosity of how excellently the organocatalysts have performed in this field. The stated perspectives of this review mainly cover five aspects, in terms of the assessment of the livingness of the polymerization, limit and scope of applicable monomers, mechanistic studies, control of the polymer structure, and a new GTP methodology involving the use of tris(pentafluorophenyl)borane and hydrosilane. PMID:27427399

  10. Polymerization of vegetable oils

    SciTech Connect

    Korus, R.A.; Mousetis, T.L.; Lloyd, L.

    1982-01-01

    The addition of antioxidants and dispersants is not sufficient to eliminate gum formation in vegetable oils. Even with relatively unsaturated oils like rapeseed the extent of unsaturation overwhelms these additives. Fuel deterioration during storage will be minimized in an anaerobic storage environment and, to a lesser extent, with a lower degree of oil unsaturation. Gum formation and carbon coking can also occur immediately preceding and during combustion. Thermal polymerization may be the dominant gum forming reaction under combustion conditions since thermal polymerization has a higher activation energy than oxidative polymerization and anaerobic conditions can occur within atomized fuel droplets. Carbon coking can be reduced with a lower degree of oil unsaturation and with better atomization of the fuel. 4 figures, 1 table.

  11. Preparation of different carbon materials by thermochemical conversion of Lignin

    NASA Astrophysics Data System (ADS)

    Rosas, Juana; Berenguer, Raul; Valero-Romero, Maria; Rodriguez-Mirasol, Jose; Cordero, Tomás

    2014-12-01

    Lignin valorization plays a crucial role within the modern biorefinery scheme from both the economic and environmental points of view; and the structure and composition of lignin becomes it an ideal precursor for the preparation of advanced carbon materials with high added-value. This review provides an overview of the different carbonaceous materials obtained by thermochemical conversion of lignin, such as activated carbons, carbon fibers, template carbons; high ordered carbons; giving information about the new strategies in terms of the preparation method and their possible applications.

  12. Preparation of lignopolyols from wheat straw soda lignin.

    PubMed

    Ahvazi, Behzad; Wojciechowicz, Olivia; Ton-That, Tan-Minh; Hawari, Jalal

    2011-10-12

    Wheat straw soda lignin was modified and characterized by several qualitative and quantitative methods such as (31)P NMR spectroscopy to evaluate its potential as a substitute for polyols in view of polyurethane applications. Chemical modification of the lignin was achieved with propylene oxide to form lignopolyol derivatives. This was performed by a two-step reaction of lignin with maleic anhydride followed by propylene oxide and by direct oxyalkylation under acidic and alkaline conditions. The physical and chemical properties of lignopolyols from each method and the subsequent chain-extended hydroxyl groups were evaluated. Direct oxyalkylation of lignin under alkaline conditions was found to be more efficient than acidic conditions and more effective than the two-step process for preparing lignopolyol with higher aliphatic hydroxyl contents. PMID:21854019

  13. Hydrothermal fractionation of woody biomass: Lignin effect on sugars recovery.

    PubMed

    Yedro, Florencia M; Cantero, Danilo A; Pascual, Marcos; García-Serna, Juan; Cocero, M José

    2015-09-01

    Subcritical water was employed to fractionate woody biomass into carbohydrates and lignin. Nine urban trees species (hardwood and softwood) from Spain were studied. The experiments were carried out in a semi-continuous reactor at 250 °C for 64 min. The hemicellulose and cellulose recovery yields were between 30%wt. and 80%wt. while the lignin content in the solid product ranged between 32%wt. and 92%wt. It was observed that an increment of solubilized lignin disfavored the hydrolysis of hemicelluloses. It was determined that the maximum extraction of hemicellulose was achieved at 20 min of solid reaction time while the extraction of celluloses not exhibited a maximum value. The hydrolysis of hemicellulose and cellulose would be governed by the hydrolysis kinetic and the polymers accessibility. In addition, the extraction of hemicellulose was negatively affected by the lignin content in the raw material while cellulose hydrolysis was not affected by this parameter. PMID:25985415

  14. Molecular simulation as a tool for studying lignin

    SciTech Connect

    Sangha, Amandeep K; Petridis, Loukas; Smith, Jeremy C; Ziebell, Angela L; Parks, Jerry M

    2012-01-01

    Lignocellulosic biomass provides a sustainable source of sugars for biofuel and biomaterial production. However, biomass resistance to degradation imposes difficulties for economical conversion of plant carbohydrates to fermentable sugars. One of the key contributors to recalcitrance is lignin. Understanding the properties of lignin macromolecules in the cell wall matrix is useful for manipulating biomass structure to generate more easily degradable biomass. Along with experimental techniques such as 2D-NMR and mass spectrometry, computational techniques can be useful for characterizing the structural and energetic properties of the biomass assembly and its individual constituents. Here, we provide a brief introduction to lignin, review some of the recent, relevant scientific literature, and give our perspectives on the role of molecular simulation in understanding lignin structure.

  15. Hydrothermal fractionation of woody biomass: Lignin effect on sugars recovery.

    PubMed

    Yedro, Florencia M; Cantero, Danilo A; Pascual, Marcos; García-Serna, Juan; Cocero, M José

    2015-09-01

    Subcritical water was employed to fractionate woody biomass into carbohydrates and lignin. Nine urban trees species (hardwood and softwood) from Spain were studied. The experiments were carried out in a semi-continuous reactor at 250 °C for 64 min. The hemicellulose and cellulose recovery yields were between 30%wt. and 80%wt. while the lignin content in the solid product ranged between 32%wt. and 92%wt. It was observed that an increment of solubilized lignin disfavored the hydrolysis of hemicelluloses. It was determined that the maximum extraction of hemicellulose was achieved at 20 min of solid reaction time while the extraction of celluloses not exhibited a maximum value. The hydrolysis of hemicellulose and cellulose would be governed by the hydrolysis kinetic and the polymers accessibility. In addition, the extraction of hemicellulose was negatively affected by the lignin content in the raw material while cellulose hydrolysis was not affected by this parameter.

  16. Lignin in marine environment and its analysis—A review

    NASA Astrophysics Data System (ADS)

    Li, Xianguo; Zhang, Ting; Sun, Shuwen; Lan, Haiqing; Yu, Tao

    2012-12-01

    Lignin is a group of phenolic polymers which is abundant in the woody tissues of vascular plants, and is essentially absent from all other living organisms. It has therefore been accepted as a tracer for terrestrial organic carbon (TOC) in marine environment since the 1970s. Lignin polymers are not amenable to direct chemical analysis without prior isolation. This review focused on the methods of chemical decomposition, extraction, derivatization and detection of lignin in marine environment. We described and compared several chemical decomposition methods, including nitrobenzene oxidation, alkaline cupric oxide (CuO) oxidation and thermochemolysis, and detection methods such as gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), high performance liquid chromatography (HPLC) and so on. Possible improvement of lignin analysis and the application prospects of this tracer were also discussed.

  17. Membrane Technology for the Recovery of Lignin: A Review

    PubMed Central

    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

  18. Membrane Technology for the Recovery of Lignin: A Review.

    PubMed

    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

  19. Variable Effect during Polymerization

    ERIC Educational Resources Information Center

    Lunsford, S. K.

    2005-01-01

    An experiment performing the polymerization of 3-methylthiophene(P-3MT) onto the conditions for the selective electrode to determine the catechol by using cyclic voltammetry was performed. The P-3MT formed under optimized conditions improved electrochemical reversibility, selectivity and reproducibility for the detection of the catechol.

  20. Protein specific polymeric immunomicrospheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Dreyer, William J. (Inventor)

    1980-01-01

    Small, round, bio-compatible microspheres capable of covalently bonding proteins and having a uniform diameter below about 3500 A are prepared by substantially instantaneously initiating polymerization of an aqueous emulsion containing no more than 35% total monomer including an acrylic monomer substituted with a covalently bondable group such as hydroxyl, amino or carboxyl and a minor amount of a cross-linking agent.

  1. Programmable Supramolecular Polymerizations.

    PubMed

    van der Zwaag, Daan; de Greef, Tom F A; Meijer, E W

    2015-07-13

    Living large: Rational design of self-assembly pathways has been demonstrated in supramolecular polymers. By controlling the concentration of an aggregation-competent monomer through intramolecular interactions, living supramolecular polymerization conditions were achieved. This universal approach can be used to obtain aggregates of well-defined length and narrow dispersity, and allows access to new supramolecular polymer architectures. PMID:26095705

  2. Effective integrative supramolecular polymerization.

    PubMed

    Zhang, Qiwei; Tian, He

    2014-09-26

    Exercise control: By taking advantage of self-sorting processes among host-guest components, a controlled supramolecular polymerization can be realized, as demonstrated recently with the preparation of a cucurbit[n]uril-based supramolecular polymer. This method may be used for the design of more ordered supramolecular polymers from complex and discrete components. PMID:25080388

  3. Polymerized and functionalized triglycerides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plant oils are useful sustainable raw materials for the development of new chemical products. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a new method for polymerizing epoxidized triglycerides with the use of fluorosulfonic acid. Depending on the ...

  4. Plants with modified lignin content and methods for production thereof

    SciTech Connect

    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.

  5. Transcription factors for modification of lignin content in plants

    SciTech Connect

    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.

  6. Lignin nanotubes as vehicles for gene delivery into human cells.

    PubMed

    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.

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

    PubMed

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

    2009-11-11

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

  8. [Pretreatment of industrial lignin and catalytic conversion into phenol].

    PubMed

    Qu, Yongshui; Luo, Hao; Li, Hongqiang; Xu, Jian

    2014-05-01

    Recent concerns about the gradual depletion of conventional fossil resources and the pressure from global climate change have accentuated the need for new alternative feedstock. As one of the main components in biomass, lignin is the second most abundant natural polymer after cellulose, and has the potential to serve as a sustainable source of energy and organic carbon to replace petroleum-based chemicals. Efficient conversion of lignin into high value-added chemicals is crucial to improve the economic feasibility of biomass refinery. In the present study, several pretreatment technologies on industrial lignin were carried out to enhance phenol production. A microwave irradiation assisted biphasic reaction system was used to convert pretreated industrial lignin into phenolic compounds. Lignin conversion, reaction temperature, time and pretreatment method, were optimized. The highest phenol yield was 8.14% obtained from lignin pretreated by 1-ethyl-3-methylimidazolium acetate at 400 W for 60 min in a biophasic system catalyze by 1-aminoethyl-3-methylimidazolium tetrafluoroborate. PMID:25118400

  9. Solubilization and Mineralization of Lignin by White Rot Fungi

    PubMed Central

    Boyle, C. David; Kropp, Bradley R.; Reid, Ian D.

    1992-01-01

    The white rot fungi Lentinula edodes, Phanerochaete chrysosporium, Pleurotus sajor-caju, Flammulina velutipes, and Schizophyllum commune were grown in liquid media containing 14C-lignin-labelled wood, and the formation of water-soluble 14C-labelled products and 14CO2, the growth of the fungi, and the activities of extracellular lignin peroxidase, manganese peroxidase, and laccase were measured. Conditions that affect the rate of lignin degradation were imposed, and both long-term (0- to 16-day) and short-term (0- to 72-h) effects on the production of the two types of product and on the activities of the enzymes were monitored. The production of 14CO2-labelled products from the aqueous ones was also investigated. The short-term studies showed that the different conditions had different effects on the production of the two products and on the activities of the enzymes. Nitrogen sources inhibited the production of both products by all species when differences in growth could be discounted. Medium pH and manganese affected lignin degradation by the different species differently. With P. chrysosporium, the results were consistent, with lignin peroxidase playing a role in lignin solubilization and manganese peroxidase being important in subsequent CO2 production. PMID:16348781

  10. Lignin structural alterations in thermochemical pretreatments with limited delignification

    DOE PAGES

    Pu, Yunqiao; Hu, Fan; Huang, Fang; Ragauskas, Arthur J.

    2015-08-02

    Lignocellulosic biomass has a complex and rigid cell wall structure that makes biomass recalcitrant to biological and chemical degradation. Among the three major structural biopolymers (i.e., cellulose, hemicellulose and lignin) in plant cell walls, lignin is considered the most recalcitrant component and generally plays a negative role in the biochemical conversion of biomass to biofuels. The conversion of biomass to biofuels through a biochemical platform usually requires a pretreatment stage to reduce the recalcitrance. Pretreatment renders compositional and structural changes of biomass with these changes ultimately govern the efficiency of the subsequent enzymatic hydrolysis. Dilute acid, hot water, steam explosion,more » and ammonia fiber expansion pretreatments are among the leading thermochemical pretreatments with a limited delignification that can reduce biomass recalcitrance. Practical applications of these pretreatment are rapidly developing as illustrated by recent commercial scale cellulosic ethanol plants. While these thermochemical pretreatments generally lead to only a limited delignification and no significant change of lignin content in the pretreated biomass, the lignin transformations that occur during these pretreatments and the roles they play in recalcitrance reduction is an important research aspect. This review highlights recent advances in our understanding of lignin alterations during these limited delignification thermochemical pretreatments, with emphasis on lignin chemical structures, molecular weights, and redistributions in the pretreated biomass.« less

  11. Lignin structural alterations in thermochemical pretreatments with limited delignification

    SciTech Connect

    Pu, Yunqiao; Hu, Fan; Huang, Fang; Ragauskas, Arthur J.

    2015-08-02

    Lignocellulosic biomass has a complex and rigid cell wall structure that makes biomass recalcitrant to biological and chemical degradation. Among the three major structural biopolymers (i.e., cellulose, hemicellulose and lignin) in plant cell walls, lignin is considered the most recalcitrant component and generally plays a negative role in the biochemical conversion of biomass to biofuels. The conversion of biomass to biofuels through a biochemical platform usually requires a pretreatment stage to reduce the recalcitrance. Pretreatment renders compositional and structural changes of biomass with these changes ultimately govern the efficiency of the subsequent enzymatic hydrolysis. Dilute acid, hot water, steam explosion, and ammonia fiber expansion pretreatments are among the leading thermochemical pretreatments with a limited delignification that can reduce biomass recalcitrance. Practical applications of these pretreatment are rapidly developing as illustrated by recent commercial scale cellulosic ethanol plants. While these thermochemical pretreatments generally lead to only a limited delignification and no significant change of lignin content in the pretreated biomass, the lignin transformations that occur during these pretreatments and the roles they play in recalcitrance reduction is an important research aspect. This review highlights recent advances in our understanding of lignin alterations during these limited delignification thermochemical pretreatments, with emphasis on lignin chemical structures, molecular weights, and redistributions in the pretreated biomass.

  12. A radioimmunoassay for lignin in plant cell walls

    SciTech Connect

    Dawley, R.M.

    1989-01-01

    Lignin detection and determination in herbaceous tissue requires selective, specific assays which are not currently available. A radioimmunoassay (RIA) was developed to study lignin metabolism in these tissues. A {beta}-aryl ether lignin model compound was synthesized, linked to keyhole limpet hemocyanin using a water-soluble carbodiimide, and injected into rabbits. The highest titer of the antiserum obtained was 34 {eta}g/mL of model derivatized BSA. An in vitro system was developed to characterize the RIA. The model compound was linked to amino activated polyacrylamide beads to mimic lignin in the cell walls. {sup 125}I Radiolabelled protein A was used to detect IgG antibody binding. The RIA was shown in the in vitro system to exhibit saturable binding. The amount of antibody bound decreased when the serum was diluted. Immunoelectrophoresis and competitive binding experiments confirmed that both aromatic rings of the lignin model compound had been antigenic. Chlorogenic acid, a phenolic known to be present in plant cells, did not compete for antibody binding. The RIA was used to measure lignin in milled plant samples and barley seedlings. Antiserum binding to wheat cell walls and stressed barley segments was higher than preimmune serum binding. Antibody binding to stressed barley tissue decreased following NaClO{sub 2} delignification. The RIA was found to be less sensitive than expected, so several avenues for improving the method are discussed.

  13. Study on biodegradation process of lignin by FTIR and DSC.

    PubMed

    Liu, Yang; Hu, Tianjue; Wu, Zhengping; Zeng, Guangming; Huang, Danlian; Shen, Ying; He, Xiaoxiao; Lai, Mingyong; He, Yibin

    2014-12-01

    The biodegradation process of lignin by Penicillium simplicissimum was studied to reveal the lignin biodegradation mechanisms. The biodegradation products of lignin were detected using Fourier transform infrared spectroscopy (FTIR), UV-Vis spectrophotometer, different scanning calorimeter (DSC), and stereoscopic microscope. The analysis of FTIR spectrum showed the cleavage of various ether linkages (1,365 and 1,110 cm(-1)), oxidation, and demethylation (2,847 cm(-1)) by comparing the different peak values in the corresponding curve of each sample. Moreover, the differences (Tm and ΔHm values) between the DSC curves indirectly verified the FTIR analysis of biodegradation process. In addition, the effects of adding hydrogen peroxide (H2O2) to lignin biodegradation process were analyzed, which indicated that H2O2 could accelerate the secretion of the MnP and LiP and improve the enzymes activity. What is more, lignin peroxidase and manganese peroxidase catalyzed the lignin degradation effectively only when H2O2 was presented.

  14. Evaluation of pristine lignin for hazardous-waste treatment

    SciTech Connect

    O'Neil, D.J.; Newman, C.J.; Chian, E.S.K.; Gao, H.

    1987-05-01

    A feasibility study was conducted to assess the utilization of lignin, isolated from a steam-exploded hardwood (Tulip poplar) with 95% ethanol and 0.1n NaOH, as a potential adsorbent for hazardous-waste treatment. Eight organic compounds and two heavy metals were selected to allow comparison of lignin isolates with activated carbon. It was found that the adsorption capacity of lignin for heavy metals (chromium and lead) is comparable to activated carbon, despite a huge divergence in surface area (0.1 mS/g vs. 1000 mS/g). The surface area discrepancy and the extensive aromatic substitution in lignin macromolecule impeded the achievement of an adsorption capacity of lignin for polar organic compounds which would allow it to be cost-competitive with activated carbon although results with phenol and, to a lesser degree, naphthalene indicate significant potential for achieving competitive capacities. A recommended plan for surface area and structural enhancement is presented on the basis that lignin can be developed as an effective and low-cost adsorbent for polar priority pollutants and/or as an ion-exchange resins for heavy-metal wastewater clean-up.

  15. Influence of lignin addition on the enzymatic digestibility of pretreated lignocellulosic biomasses.

    PubMed

    Wang, Wangxia; Zhu, Yangsu; Du, Jing; Yang, Yiqin; Jin, Yongcan

    2015-04-01

    The presence of lignin in lignocellulosic biomass is correlated with its enzymatic digestibility. Their correlation and mechanism have been investigated widely but have not been elucidated clearly. In this study, hydrophilic sulfonated lignin and hydrophobic kraft lignin were introduced into the enzymatic hydrolysis process to investigate their effects on the enzymatic digestibility of different pretreated lignocellulose. The influence of lignin addition on the enzymatic digestibility varied with both introduced lignin type and the pretreatment methods of substrates. Slight enhancement of enzymatic hydrolysis was observed for all substrates by adding kraft lignin. The addition of sulfonated lignin could effectively improve the enzymatic digestibility of green liquor and acidic bisulfite pretreated materials, but had little effect on sulfite-formaldehyde pretreated samples. The enzymatic digestibility of green liquor pretreated masson pine increased from 42% without lignin addition to 75% with 0.3g/g-substrate sulfonated lignin addition.

  16. Slow pyrolysis of prot, alkali and dealkaline lignins for production of chemicals.

    PubMed

    Biswas, Bijoy; Singh, Rawel; Kumar, Jitendra; Khan, Adnan Ali; Krishna, Bhavya B; Bhaskar, Thallada

    2016-08-01

    Effect of different lignins were studied during slow pyrolysis. Maximum bio-oil yield of 31.2, 34.1, and 29.5wt.% was obtained at 350, 450 and 350°C for prot lignin, alkali lignin and dealkaline lignin respectively. Maximum yield of phenolic compounds 78%, 80% and 92% from prot lignin, alkali and dealkaline lignin at 350, 450 and 350°C. The differences in the pyrolysis products indicated the source of lignins such as soft and hard wood lignins. The biochar characterisation revealed that the various ether linkages were broken during pyrolysis and lignin was converted into monomeric substituted phenols. Bio-oil showed that the relative contents of each phenolic compound changes significantly with pyrolysis temperature and also the relative contents of each compound changes with different samples. PMID:26873286

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

    SciTech Connect

    Paul, Ryan; Naskar, Amit; Gallego, Nidia; Dai, Xuliang; Hausner, Andrew

    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.

  18. [Molecular/polymeric magnetism

    SciTech Connect

    Not Available

    1993-01-01

    New materials were synthesized to test the generality of magnetism in molecular/polymeric systems. The first room temperature molecular based magnet V(TCNE)[sub x][center dot]y(solvent) (1) is disclosed. The ferromagnetic and related transitions were studied in decamethylferrocenium tetracyanoethanide (TCNE), (1), and related materials. Our and others' models were tested for ferromagnetic and antiferromagnetic exchange between local sites; models for control of [Tc] were also tested.

  19. Surface polymerization agents

    SciTech Connect

    Taylor, C.; Wilkerson, C.

    1996-12-01

    This is the final report of a 1-year, Laboratory-Directed R&D project at LANL. A joint technical demonstration was proposed between US Army Missile Command (Redstone Arsenal) and LANL. Objective was to demonstrate that an unmanned vehicle or missile could be used as a platform to deliver a surface polymerization agent in such a manner as to obstruct the filters of an air-breathing mechanism, resulting in operational failure.

  20. Polymeric Bicontinuous Microemulsions

    NASA Astrophysics Data System (ADS)

    Bates, Frank S.; Maurer, Wayne W.; Lipic, Paul M.; Hillmyer, Marc A.; Almdal, Kristoffer; Mortensen, Kell; Fredrickson, Glenn H.; Lodge, Timothy P.

    1997-08-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in mixtures containing a model diblock copolymer and two homopolymers. Although we attribute development of this equilibrium morphology to the effects of fluctuations, mean-field theory provides a quantitative strategy for preparing the bicontinuous state at blend compositions near an isotropic Lifshitz point.

  1. Flocculation of kaolin and lignin by bovine blood and hemoglobin

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Polymeric flocculants are used extensively for water purification, inhibition of soil erosion, and reduction in water leakage from unlined canals. Production of highly active, renewable polymeric flocculants to replace synthetic flocculants is a priority. Using suspensions of kaolin, flocculation ...

  2. Lignin content in natural Populus variants affects sugar release

    PubMed Central

    Studer, Michael H.; DeMartini, Jaclyn D.; Davis, Mark F.; Sykes, Robert W.; Davison, Brian; Keller, Martin; Tuskan, Gerald A.; Wyman, Charles E.

    2011-01-01

    The primary obstacle to producing renewable fuels from lignocellulosic biomass is a plant's recalcitrance to releasing sugars bound in the cell wall. From a sample set of wood cores representing 1,100 individual undomesticated Populus trichocarpa trees, 47 extreme phenotypes were selected across measured lignin content and ratio of syringyl and guaiacyl units (S/G ratio). This subset was tested for total sugar release through enzymatic hydrolysis alone as well as through combined hot-water pretreatment and enzymatic hydrolysis using a high-throughput screening method. The total amount of glucan and xylan released varied widely among samples, with total sugar yields of up to 92% of the theoretical maximum. A strong negative correlation between sugar release and lignin content was only found for pretreated samples with an S/G ratio < 2.0. For higher S/G ratios, sugar release was generally higher, and the negative influence of lignin was less pronounced. When examined separately, only glucose release was correlated with lignin content and S/G ratio in this manner, whereas xylose release depended on the S/G ratio alone. For enzymatic hydrolysis without pretreatment, sugar release increased significantly with decreasing lignin content below 20%, irrespective of the S/G ratio. Furthermore, certain samples featuring average lignin content and S/G ratios exhibited exceptional sugar release. These facts suggest that factors beyond lignin and S/G ratio influence recalcitrance to sugar release and point to a critical need for deeper understanding of cell-wall structure before plants can be rationally engineered for reduced recalcitrance and efficient biofuels production. PMID:21444820

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

    SciTech Connect

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

    1986-01-01

    The biodegradation of lignin by fungi was studied in shake flasks using /sup 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/sub 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, /sup 14/CO evolution, OCH/sub 3/ loss, OH loss, and monomer and dimer yield after permanganate oxidation.

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

    DOE PAGES

    da Costa Sousa, Leonardo; Foston, Marcus; Bokade, Vijay; Azarpira, Ali; Lu, Fachuang; Ragauskas, Arthur J.; Ralph, John; Dale, Bruce; Balan, Venkatesh

    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 fuelsmore » and chemicals using green processes. In this work, 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 summary, EA-derived lignins preserve much of lignin's functionality, including the sensitive β-aryl ether units. Furthermore, nitrogen incorporation was observed in the lignin-rich streams, notably due to the presence of hydroxycinnamoyl amides formed during ammonia pretreatment.« less

  5. Degradation of carbohydrates and lignins in buried woods

    USGS Publications Warehouse

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

    1985-01-01

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

  6. Small Glycosylated Lignin Oligomers Are Stored in Arabidopsis Leaf Vacuoles

    PubMed Central

    Dima, Oana; Morreel, Kris; Vanholme, Bartel; Kim, Hoon; Ralph, John; Boerjan, Wout

    2015-01-01

    Lignin is an aromatic polymer derived from the combinatorial coupling of monolignol radicals in the cell wall. Recently, various glycosylated lignin oligomers have been revealed in Arabidopsis thaliana. Given that monolignol oxidation and monolignol radical coupling are known to occur in the apoplast, and glycosylation in the cytoplasm, it raises questions about the subcellular localization of glycosylated lignin oligomer biosynthesis and their storage. By metabolite profiling of Arabidopsis leaf vacuoles, we show that the leaf vacuole stores a large number of these small glycosylated lignin oligomers. Their structural variety and the incorporation of alternative monomers, as observed in Arabidopsis mutants with altered monolignol biosynthesis, indicate that they are all formed by combinatorial radical coupling. In contrast to the common believe that combinatorial coupling is restricted to the apoplast, we hypothesized that the aglycones of these compounds are made within the cell. To investigate this, leaf protoplast cultures were cofed with 13C6-labeled coniferyl alcohol and a 13C4-labeled dimer of coniferyl alcohol. Metabolite profiling of the cofed protoplasts provided strong support for the occurrence of intracellular monolignol coupling. We therefore propose a metabolic pathway involving intracellular combinatorial coupling of monolignol radicals, followed by oligomer glycosylation and vacuolar import, which shares characteristics with both lignin and lignan biosynthesis. PMID:25700483

  7. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation.

    PubMed

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

    2016-06-15

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the α-O cleavage reaction is lower than that of the β-O reaction. The catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets. PMID:27236926

  8. Cinnamic acid increases lignin production and inhibits soybean root growth.

    PubMed

    Salvador, Victor Hugo; Lima, Rogério Barbosa; dos Santos, Wanderley Dantas; Soares, Anderson Ricardo; Böhm, Paulo Alfredo Feitoza; Marchiosi, Rogério; Ferrarese, Maria de Lourdes Lucio; Ferrarese-Filho, Osvaldo

    2013-01-01

    Cinnamic acid is a known allelochemical that affects seed germination and plant root growth and therefore influences several metabolic processes. In the present work, we evaluated its effects on growth, indole-3-acetic acid (IAA) oxidase and cinnamate 4-hydroxylase (C4H) activities and lignin monomer composition in soybean (Glycine max) roots. The results revealed that exogenously applied cinnamic acid inhibited root growth and increased IAA oxidase and C4H activities. The allelochemical increased the total lignin content, thus altering the sum and ratios of the p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) lignin monomers. When applied alone or with cinnamic acid, piperonylic acid (PIP, a quasi-irreversible inhibitor of C4H) reduced C4H activity, lignin and the H, G, S monomer content compared to the cinnamic acid treatment. Taken together, these results indicate that exogenously applied cinnamic acid can be channeled into the phenylpropanoid pathway via the C4H reaction, resulting in an increase in H lignin. In conjunction with enhanced IAA oxidase activity, these metabolic responses lead to the stiffening of the cell wall and are followed by a reduction in soybean root growth.

  9. Cinnamic acid increases lignin production and inhibits soybean root growth.

    PubMed

    Salvador, Victor Hugo; Lima, Rogério Barbosa; dos Santos, Wanderley Dantas; Soares, Anderson Ricardo; Böhm, Paulo Alfredo Feitoza; Marchiosi, Rogério; Ferrarese, Maria de Lourdes Lucio; Ferrarese-Filho, Osvaldo

    2013-01-01

    Cinnamic acid is a known allelochemical that affects seed germination and plant root growth and therefore influences several metabolic processes. In the present work, we evaluated its effects on growth, indole-3-acetic acid (IAA) oxidase and cinnamate 4-hydroxylase (C4H) activities and lignin monomer composition in soybean (Glycine max) roots. The results revealed that exogenously applied cinnamic acid inhibited root growth and increased IAA oxidase and C4H activities. The allelochemical increased the total lignin content, thus altering the sum and ratios of the p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) lignin monomers. When applied alone or with cinnamic acid, piperonylic acid (PIP, a quasi-irreversible inhibitor of C4H) reduced C4H activity, lignin and the H, G, S monomer content compared to the cinnamic acid treatment. Taken together, these results indicate that exogenously applied cinnamic acid can be channeled into the phenylpropanoid pathway via the C4H reaction, resulting in an increase in H lignin. In conjunction with enhanced IAA oxidase activity, these metabolic responses lead to the stiffening of the cell wall and are followed by a reduction in soybean root growth. PMID:23922685

  10. On the surface interactions of proteins with lignin.

    PubMed

    Salas, Carlos; Rojas, Orlando J; Lucia, Lucian A; Hubbe, Martin A; Genzer, Jan

    2013-01-01

    Lignins are used often in formulations involving proteins but little is known about the surface interactions between these important biomacromolecules. In this work, we investigate the interactions at the solid-liquid interface of lignin with the two main proteins in soy, glycinin (11S) and β-conglycinin (7S). The extent of adsorption of 11S and 7S onto lignin films and the degree of hydration of the interfacial layers is quantified via Quartz crystal microgravimetry (QCM) and surface plasmon resonance (SPR). Solution ionic strength and protein denaturation (2-mercaptoethanol and urea) critically affect the adsorption process as protein molecules undergo conformational changes and their hydrophobic or hydrophilic amino acid residues interact with the surrounding medium. In general, the adsorption of the undenatured proteins onto lignin is more extensive compared to that of the denatured biomolecules and a large amount of water is coupled to the adsorbed molecules. The reduction in water contact angle after protein adsorption (by ~40° and 35° for undenatured 11S and 7S, respectively) is explained by strong nonspecific interactions between soy proteins and lignin. PMID:23234476

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

    PubMed

    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.

  12. Lignin Modification for Biopolymer/Conjugated Polymer Hybrids as Renewable Energy Storage Materials.

    PubMed

    Nilsson, Ting Yang; Wagner, Michal; Inganäs, Olle

    2015-12-01

    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.

  13. Influence of TEMPO-mediated oxidation on the lignin of thermomechanical pulp.

    PubMed

    Ma, Pu; Fu, Shaoling; Zhai, Huamin; Law, Kweinam; Daneault, Claude

    2012-08-01

    The influences of various factors in 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation on delignification, lignin aromatic ring and side chain structures of thermomechanical pulp (TMP) were investigated. The results indicate neither TEMPO nor NaBr alone can provoke changes in lignin content or lignin structure under weakly alkaline conditions. However, NaClO and NaClO-NaBr were able to remove lignin effectively, causing remarkable changes in lignin structure. Delignification was promoted when TEMPO was used with NaBr and NaClO. In contrast to NaClO alone, an additional 15% lignin was removed when TEMPO-mediated oxidation system was used, but it did not induce further changes on lignin structure. Increased doses of oxidizing agent and reaction time also improved the oxidation of cellulose and delignification, but they did not have a significant impact on lignin aromatic and side chain structures.

  14. Bimorphic polymeric photomechanical actuator

    NASA Technical Reports Server (NTRS)

    Sarkisov, Sergey S. (Inventor); Curley, Michael J. (Inventor); Adamovsky, Grigory (Inventor); Sarkisov, Jr., Sergey S. (Inventor); Fields, Aisha B. (Inventor)

    2006-01-01

    A bimorphic polymeric photomechanical actuator, in one embodiment using polyvinylidene fluoride (PVDF) as a photosensitive body, transmitting light over fiber optic cables, and controlling the shape and pulse duration of the light pulse to control movement of the actuator. Multiple light beams are utilized to generate different ranges of motion for the actuator from a single photomechanical body and alternative designs use multiple light beams and multiple photomechanical bodies to provide controlled movement. Actuator movement using one or more ranges of motion is utilized to control motion to position an actuating element in three dimensional space.

  15. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    2003-08-26

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  16. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    1999-01-01

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  17. Living olefin polymerization processes

    DOEpatents

    Schrock, R.R.; Baumann, R.

    1999-03-30

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  18. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Bauman, Robert

    2006-11-14

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

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

    SciTech Connect

    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 {sup 14}CO{sub 2} from {sup 14}C-labeled dehydrogenative polymerizate lignin was likewise affected by Mn(II). The rate of {sup 14}CO{sub 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.

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

    PubMed

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

    2014-12-01

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

  1. Reductive Dealkylation of Anisole and Phenetole: Towards Practical Lignin Conversion

    PubMed Central

    Strassberger, Zea; Tanase, Stefania; Rothenberg, Gadi

    2011-01-01

    We present and develop alternative catalysts for biomass conversion and specifically lignin conversion into aromatics. Unlike the conventional CoMo and NiMo formulations, our catalysts can convert low-sulfur feedstocks. A set of five magnesia–alumina mixed oxides were screened in the hydrodealkylation of alkyl phenyl ethers as lignin model compounds. The typical selectivity to phenol is 30–75 %. Interestingly, we saw that the more basic the catalyst, the higher the selectivity for phenol. The results concur with the formation of phenoxide (PhO–) and RH3+ fragments on the catalyst surface. These can then react with H+ and H– species formed by the hydrogen dissociation on the MgO surface, giving phenol and hydrocarbons. We conclude that magnesia–alumina mixed oxides are attractive candidates for catalyzing lignin breakdown. These catalysts are highly stable, inexpensive, and readily available.

  2. Conversion of kraft lignin over hierarchical MFI zeolite.

    PubMed

    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.

  3. Monolignol ferulate conjugates are naturally incorporated into plant lignins

    PubMed Central

    Karlen, Steven D.; Zhang, Chengcheng; Peck, Matthew L.; Smith, Rebecca A.; Padmakshan, Dharshana; Helmich, Kate E.; Free, Heather C. A.; Lee, Seonghee; Smith, Bronwen G.; Lu, Fachuang; Sedbrook, John C.; Sibout, Richard; Grabber, John H.; Runge, Troy M.; Mysore, Kirankumar S.; Harris, Philip J.; Bartley, Laura E.; Ralph, John

    2016-01-01

    Angiosperms represent most of the terrestrial plants and are the primary research focus for the conversion of biomass to liquid fuels and coproducts. Lignin limits our access to fibers and represents a large fraction of the chemical energy stored in plant cell walls. Recently, the incorporation of monolignol ferulates into lignin polymers was accomplished via the engineering of an exotic transferase into commercially relevant poplar. We report that various angiosperm species might have convergently evolved to natively produce lignins that incorporate monolignol ferulate conjugates. We show that this activity may be accomplished by a BAHD feruloyl–coenzyme A monolignol transferase, OsFMT1 (AT5), in rice and its orthologs in other monocots. PMID:27757415

  4. Sustainable polymerizations in recoverable microemulsions.

    PubMed

    Chen, Zhenzhen; Yan, Feng; Qiu, Lihua; Lu, Jianmei; Zhou, Yinxia; Chen, Jiaxin; Tang, Yishan; Texter, John

    2010-03-16

    Free radical and atom-transfer radical polymerizations were conducted in monomer/ionic liquid microemulsions. After the polymerization and isolation of the resultant polymers, the mixture of the catalyst and ionic liquids (surfactant and continuous phase) can be recovered and reused, thereby dramatically improving the environmental sustainability of such chemical processing. The addition of monomer to recovered ionic liquid mixtures regenerates transparent, stable microemulsions that are ready for the next polymerization cycle upon addition of initiator. The method combines the advantages of IL recycling and microemulsion polymerization and minimizes environmental disposable effects from surfactants and heavy metal ions. PMID:20170175

  5. Polymerization Evaluation by Spectrophotometric Measurements.

    ERIC Educational Resources Information Center

    Dunach, Jaume

    1985-01-01

    Discusses polymerization evaluation by spectrophotometric measurements by considering: (1) association degrees and molar absorptivities; (2) association degrees and equilibrium constants; and (3) absorbance and equilibrium constants. (JN)

  6. Efficient cobalt-catalyzed oxidative conversion of lignin models to benzoquinones.

    PubMed

    Biannic, Berenger; Bozell, Joseph J

    2013-06-01

    Phenolic lignin model monomers and dimers representing the primary substructural units of lignin were successfully oxidized to benzoquinones in high yield with molecular oxygen using new Co-Schiff base catalysts bearing a bulky heterocyclic nitrogen base as a substituent. This is the first example of a catalytic system able to convert both S and G lignin model phenols in high yield, a process necessary for effective use of lignin as a chemical feedstock. PMID:23679189

  7. In situ micro-spectroscopic investigation of lignin in poplar cell walls pretreated by maleic acid

    DOE PAGES

    Zeng, Yining; Zhao, Shuai; Wei, Hui; Tucker, Melvin P.; Himmel, Michael E.; Mosier, Nathan S.; Meilan, Richard; Ding, Shi -You

    2015-08-27

    In higher plant cells, lignin provides necessary physical support for plant growth and resistance to attack by microorganisms. For the same reason, lignin is considered to be a major impediment to the process of deconstructing biomass to simple sugars by hydrolytic enzymes. Furthermore, the in situ variation of lignin in plant cell walls is important for better understanding of the roles lignin play in biomass recalcitrance.

  8. Characterization of lignin and Mn peroxidases from Phanerochaete chrysosporium

    SciTech Connect

    Not Available

    1991-01-01

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

  9. Alcohol adsorption on softwood lignin from aqueous solutions.

    PubMed

    Yang, Y; Ladisch, M R; Ladisch, C M

    1990-02-01

    Lignin prepared by acid and enzyme hydrolysis of a softwood mixture adsorbs acetone, butanol, and other alcohols while showing only a slight uptake of glucose. Adsorption of butanol is independent of temperature in the range of 30-65 degrees C. The Polanyi theory fits adsorption for the linear alcohols methanol through hexanol with values of DeltaS and Delta(mu) ranging from 2.6 to 26 J mol(-1) K(-1)and -0.8 to -8 kJ/mol. The adsorption capacity is given by Q (g alcohol/g lignin) = KC(*). Where C(*) is the equilibrium alcohol concentration (g/mL), K = epsilon(W)exp (Delta/R), and epsilon(w) is the porosity of the lignin (0.23-0.42 mL/g). The value of the adsorption capacity constant K for n-butanol ranges from 1.3 to 2.7 mL/g on sorbent containing 26-72% lignin, while ethanol is 0.5-0.73, acetone is 0.62-1.0, and glucose is 0.35. Adsorption is shown to occur through combined hydrophobic and hydrophilic interactions of the alkyl and hydroxyl groups, respectively, of the adsorbate with the lignin. Consequently, for the alcohols methanol to hexanol, we present the capacity constant K[=K(R) + K(OH)] as a sum of an alky! adsorption constant (0.1-9.5 mL/g) and a hydrophilic (0.40-0.50 mL/g) contribution. This approach may be applicable to organic acids. Lignin's sorbent properties have potential to moderate product inhibition in the anaerobic acetone-butanol-ethanol (ABE) fermentation. PMID:18592519

  10. Comparative geochemistries of lignins and carbohydrates in an anoxic fjord

    SciTech Connect

    Hamilton, S.E.; Hedges, J.I.

    1988-01-01

    A reducing, varved sediment core and monthly (May-September) plankton and sediment trap samples from Saanich Inlet, B.C., Canada, were analyzed for their elemental, lignin and neutral sugar compositions. Total yields of lignin-derived phenols from both the sediment trap and core samples indicated less than 15% and 30%, respectively, of chemically recognizable vascular plant remains, derived predominantly from gymnosperm wood and nonwoody angiosperm tissues. The elevated vanillyl and syringyl acid/aldehyde ratios of this material compared to fresh plant material indicated that it suffered mild aerobic decomposition prior to introduction to the Inlet. Organic carbon, total nitrogen, and total neutral sugars and lignin phenols all exhibited decreasing concentrations with depth in a region of uniform varving (upper 15 cm) in the sediment core. Neutral sugars were consistently the most reactive chemical class, accounting for roughly 15% of the total organic carbon turnover. Although lignin appeared to be degraded within the sediment core, this degradation was nonselective for different lignin types and did not lead to increased acid/aldehyde ratios as occur during aerobic lignin decomposition. Comparisons of the yields of individual neutral sugars from the sediment and sediment trap samples to those expected from the vascular plant component alone indicated that the vascular plant debris in the upper portion of the sediment core had lost a portion of its initial glucose, lyxose, and mannose. In contrast, rhamnose and fucose were produced by all samples in large excess of total yields expected for chemically intact vascular plant and plankton components and must have additional sources.

  11. Demonstration of Lignin-to-Peroxidase Direct Electron Transfer

    PubMed Central

    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

  12. Genetic mapping in the lignin-degrading basidiomycete Phanerochaete chrysosporium

    SciTech Connect

    Krejci, R. ); Homolka, L. )

    1991-01-01

    The basidiomycete Phanerochaete chrysosporium is commonly used as a model organism in studies concerned with lignin biodegradation. In further investigations of the enzymology and regulation of ligninolytic activity as well as the construction of industrially applicable strains for biotechnological processing of lignin and lignocellulose, the genetics of this fungus is of great interest. A method of meiotic segregation analysis based on recombinant selection in the homothallic basidiomycete Phanerochaete chrysosporium was developed. Using this method, we were able to reveal linkage relationships and to estimate recombination frequencies between seven mutations to auxotrophy. We detected two linkage groups, the first containing four and the second three of the seven mapped mutations.

  13. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. The highest conductivities reported (approximately 4/Scm) were achieved with polythiophene in a polystyrene host polymer. The best films using a polyamide as base polymer were four orders of magnitude less conductive than the polystyrene films. The authors suggested that this was because polyimides were unable to swell sufficiently for infiltration of monomer as in the polystyrene. It was not clear, however, if the different conductivities obtained were merely the result of differing oxidation conditions. Oxidation time, temperature and oxidant concentration varied widely among the studies.

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

    PubMed

    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.

  15. Structural Insights into the Affinity of Cel7A Carbohydrate-binding Module for Lignin*

    PubMed Central

    Strobel, Kathryn L.; Pfeiffer, Katherine A.; Blanch, Harvey W.; Clark, Douglas S.

    2015-01-01

    The high cost of hydrolytic enzymes impedes the commercial production of lignocellulosic biofuels. High enzyme loadings are required in part due to their non-productive adsorption to lignin, a major component of biomass. Despite numerous studies documenting cellulase adsorption to lignin, few attempts have been made to engineer enzymes to reduce lignin binding. In this work, we used alanine-scanning mutagenesis to elucidate the structural basis for the lignin affinity of Trichoderma reesei Cel7A carbohydrate binding module (CBM). T. reesei Cel7A CBM mutants were produced with a Talaromyces emersonii Cel7A catalytic domain and screened for their binding to cellulose and lignin. Mutation of aromatic and polar residues on the planar face of the CBM greatly decreased binding to both cellulose and lignin, supporting the hypothesis that the cellulose-binding face is also responsible for lignin affinity. Cellulose and lignin affinity of the 31 mutants were highly correlated, although several mutants displayed selective reductions in lignin or cellulose affinity. Four mutants with increased cellulose selectivity (Q2A, H4A, V18A, and P30A) did not exhibit improved hydrolysis of cellulose in the presence of lignin. Further reduction in lignin affinity while maintaining a high level of cellulose affinity is thus necessary to generate an enzyme with improved hydrolysis capability. This work provides insights into the structural underpinnings of lignin affinity, identifies residues amenable to mutation without compromising cellulose affinity, and informs engineering strategies for family one CBMs. PMID:26209638

  16. Visualizing Lignin Coalescence and Migration Through Maize Cell Walls Following Thermochemical Pretreatment

    SciTech Connect

    Donohoe, B. S.; Decker, S. R.; Tucker, M. P.; Himmel, M. E.; Vinzant, T. B.

    2008-12-01

    Plant cell walls are composed primarily of cellulose, hemicelluloses, lignins, and pectins. Of these components, lignins exhibit unique chemistry and physiological functions. Although lignins can be used as a product feedstock or as a fuel, lignins are also generally seen as a barrier to efficient enzymatic breakdown of biomass to sugars. Indeed, many pretreatment strategies focus on removing a significant fraction of lignin from biomass to better enable saccharification. In order to better understand the fate of biomass lignins that remain with the solids following dilute acid pretreatment, we undertook a structural investigation to track lignins on and in biomass cell walls. SEM and TEM imaging revealed a range of droplet morphologies that appear on and within cell walls of pretreated biomass; as well as the specific ultrastructural regions that accumulate the droplets. These droplets were shown to contain lignin by FTIR, NMR, antibody labeling, and cytochemical staining. We provide evidence supporting the idea that thermochemical pretreatments reaching temperatures above the range for lignin phase transition cause lignins to coalesce into larger molten bodies that migrate within and out of the cell wall, and can redeposit on the surface of plant cell walls. This decompartmentalization and relocalization of lignins is likely to be at least as important as lignin removal in the quest to improve the digestibility of biomass for sugars and fuels production.

  17. Structural insights into the affinity of Cel7A carbohydrate-binding module for lignin.

    PubMed

    Strobel, Kathryn L; Pfeiffer, Katherine A; Blanch, Harvey W; Clark, Douglas S

    2015-09-11

    The high cost of hydrolytic enzymes impedes the commercial production of lignocellulosic biofuels. High enzyme loadings are required in part due to their non-productive adsorption to lignin, a major component of biomass. Despite numerous studies documenting cellulase adsorption to lignin, few attempts have been made to engineer enzymes to reduce lignin binding. In this work, we used alanine-scanning mutagenesis to elucidate the structural basis for the lignin affinity of Trichoderma reesei Cel7A carbohydrate binding module (CBM). T. reesei Cel7A CBM mutants were produced with a Talaromyces emersonii Cel7A catalytic domain and screened for their binding to cellulose and lignin. Mutation of aromatic and polar residues on the planar face of the CBM greatly decreased binding to both cellulose and lignin, supporting the hypothesis that the cellulose-binding face is also responsible for lignin affinity. Cellulose and lignin affinity of the 31 mutants were highly correlated, although several mutants displayed selective reductions in lignin or cellulose affinity. Four mutants with increased cellulose selectivity (Q2A, H4A, V18A, and P30A) did not exhibit improved hydrolysis of cellulose in the presence of lignin. Further reduction in lignin affinity while maintaining a high level of cellulose affinity is thus necessary to generate an enzyme with improved hydrolysis capability. This work provides insights into the structural underpinnings of lignin affinity, identifies residues amenable to mutation without compromising cellulose affinity, and informs engineering strategies for family one CBMs. PMID:26209638

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

    PubMed

    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. PMID:25453284

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

    NASA Astrophysics Data System (ADS)

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

    1999-11-01

    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.

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

    SciTech Connect

    Crawford, D.L.

    1992-12-31

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

  1. Structural insights into the affinity of Cel7A carbohydrate-binding module for lignin.

    PubMed

    Strobel, Kathryn L; Pfeiffer, Katherine A; Blanch, Harvey W; Clark, Douglas S

    2015-09-11

    The high cost of hydrolytic enzymes impedes the commercial production of lignocellulosic biofuels. High enzyme loadings are required in part due to their non-productive adsorption to lignin, a major component of biomass. Despite numerous studies documenting cellulase adsorption to lignin, few attempts have been made to engineer enzymes to reduce lignin binding. In this work, we used alanine-scanning mutagenesis to elucidate the structural basis for the lignin affinity of Trichoderma reesei Cel7A carbohydrate binding module (CBM). T. reesei Cel7A CBM mutants were produced with a Talaromyces emersonii Cel7A catalytic domain and screened for their binding to cellulose and lignin. Mutation of aromatic and polar residues on the planar face of the CBM greatly decreased binding to both cellulose and lignin, supporting the hypothesis that the cellulose-binding face is also responsible for lignin affinity. Cellulose and lignin affinity of the 31 mutants were highly correlated, although several mutants displayed selective reductions in lignin or cellulose affinity. Four mutants with increased cellulose selectivity (Q2A, H4A, V18A, and P30A) did not exhibit improved hydrolysis of cellulose in the presence of lignin. Further reduction in lignin affinity while maintaining a high level of cellulose affinity is thus necessary to generate an enzyme with improved hydrolysis capability. This work provides insights into the structural underpinnings of lignin affinity, identifies residues amenable to mutation without compromising cellulose affinity, and informs engineering strategies for family one CBMs.

  2. Antimicrobial and antioxidant activities of lignin from residue of corn stover to ethanol production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To improve the economic viability of the biofuel production from biomass resource, a value-added lignin byproduct from this process is increasingly interested. Antioxidant and antimicrobial activities of lignin extracted from residue of corn stover to ethanol production were investigated. The lignin...

  3. Preparation and characterization of Lignin-graft-poly (ɛ-caprolactone) copolymers based on lignocellulosic butanol residue.

    PubMed

    Liu, Xiaohuan; Zong, Enmin; Jiang, Jinhua; Fu, Shenyuan; Wang, Jifu; Xu, Binbin; Li, Wenhuan; Lin, Xianzhi; Xu, Yuzhi; Wang, Chunpeng; Chu, Fuxiang

    2015-11-01

    In this paper, a "graft from" Ring-Opening Polymerization (ROP) technique was used to synthesize a lignin-graft-poly (ɛ-caprolactone) copolymer (BBL-g-PCL) using biobutanol lignin (BBL) as raw material recovered from lignocellulosic butanol residue. Polymerizations were carried out with various mass ratios of BBL and CL monomer ([BBL]/([BBL]+[CL])=1.0%, 5.0%, 10%, 20% and 40% (w/w)) to obtain BBL-g-PCL copolymers with different molecular weights, ranging from 367 to 8163gmol(-1). The grafting efficiency was preliminary evidenced by the long-term stability of dissolution of BBL-g-PCL in toluene. FT-IR and NMR analysis provided the further evidences for successful formation of BBL-g-PCL copolymer. The thermal properties of BBL-g-PCL copolymers were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). These results indicated that BBL-g-PCL copolymer had relatively good thermal stability. The static contact angle of BBL-g-PCL coating film reached to 80°. The surface functional groups and chemical composition of BBL-g-PCL copolymer was investigated in detail by X-ray photoelectron spectroscopy (XPS). The surface morphology of BBL-g-PCL copolymer was studied by Atomic force microscopy (AFM). Additionally, BBL-g-PCL coating film exhibited high absorption in the ultraviolet (UV) range, which could allow for applications in UV-blocking coatings, as well as the extents for the utilization of lignocellulosic butanol residue. PMID:26306414

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

    PubMed Central

    2010-01-01

    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 of ester group hydroxylation

  5. Amplification of actin polymerization forces

    PubMed Central

    Dmitrieff, Serge; Nédélec, François

    2016-01-01

    The actin cytoskeleton drives many essential processes in vivo, using molecular motors and actin assembly as force generators. We discuss here the propagation of forces caused by actin polymerization, highlighting simple configurations where the force developed by the network can exceed the sum of the polymerization forces from all filaments. PMID:27002174

  6. Coating of plasma polymerized film

    NASA Technical Reports Server (NTRS)

    Morita, S.; Ishibashi, S.

    1980-01-01

    Plasma polymerized thin film coating and the use of other coatings is suggested for passivation film, thin film used for conducting light, and solid body lubrication film of dielectrics of ultra insulators for electrical conduction, electron accessories, etc. The special features of flow discharge development and the polymerized film growth mechanism are discussed.

  7. Gold-promoted styrene polymerization.

    PubMed

    Urbano, Juan; Hormigo, A Jesús; de Frémont, Pierre; Nolan, Steven P; Díaz-Requejo, M Mar; Pérez, Pedro J

    2008-02-14

    Styrene can be polymerized at room temperature in the presence of equimolar mixtures of the gold(III) complexes (NHC)AuBr3 (NHC = N-heterocyclic carbene ligand) and NaBAr'4, in the first example of a gold-induced olefin polymerization reaction.

  8. Quantitative investigation of free radicals in bio-oil and their potential role in condensed-phase polymerization.

    PubMed

    Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah; Gable, Preston; Brown, Robert C

    2015-03-01

    We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20)  spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable.

  9. Solvent-Driven Preferential Association of Lignin with Regions of Crystalline Cellulose in Molecular Dynamics Simulation

    SciTech Connect

    Lindner, Benjamin; Petridis, Loukas; Schulz, Roland; Smith, Jeremy C

    2013-01-01

    The precipitation of lignin onto cellulose after pretreatment of lignocellulosic biomass is an obstacle to economically viable cellulosic ethanol production. Here, 750 ns nonequilibrium molecular dynamics simulations are reported of a system of lignin and cellulose in aqueous solution. Lignin is found to strongly associate with itself and the cellulose. However, noncrystalline regions of cellulose are observed to have a lower tendency to associate with lignin than crystalline regions, and this is found to arise from stronger hydration of the noncrystalline chains. The results suggest that the recalcitrance of crystalline cellulose to hydrolysis arises not only from the inaccessibility of inner fibers but also due to the promotion of lignin adhesion.

  10. Access of cellulase to cellulose and lignin for poplar solids produced by leading pretreatment technologies.

    PubMed

    Kumar, Rajeev; Wyman, Charles E

    2009-01-01

    Adsorption of cellulase on solids resulting from pretreatment of poplar wood by ammonia fiber expansion (AFEX), ammonia recycled percolation (ARP), controlled pH, dilute acid (DA), flowthrough (FT), lime, and sulfur dioxide (SO(2)) and pure Avicel glucan was measured at 4 degrees C, as were adsorption and desorption of cellulase and adsorption of beta-glucosidase for lignin left after enzymatic digestion of the solids from these pretreatments. From this, Langmuir adsorption parameters, cellulose accessibility to cellulase, and the effectiveness of cellulase adsorbed on poplar solids were estimated, and the effect of delignification on cellulase effectiveness was determined. Furthermore, Avicel hydrolysis inhibition by enzymatic and acid lignin of poplar solids was studied. Flowthrough pretreated solids showed the highest maximum cellulase adsorption capacity (sigma(solids) = 195 mg/g solid) followed by dilute acid (sigma(solids) = 170.0 mg/g solid) and lime pretreated solids (sigma(solids) = 150.8 mg/g solid), whereas controlled pH pretreated solids had the lowest (sigma(solids) = 56 mg/g solid). Lime pretreated solids also had the highest cellulose accessibility (sigma(cellulose) = 241 mg/g cellulose) followed by FT and DA. AFEX lignin had the lowest cellulase adsorption capacity (sigma(lignin) = 57 mg/g lignin) followed by dilute acid lignin (sigma(lignin) = 74 mg/g lignin). AFEX lignin also had the lowest beta-glucosidase capacity (sigma(lignin) = 66.6 mg/g lignin), while lignin from SO(2) (sigma(lignin) = 320 mg/g lignin) followed by dilute acid had the highest (301 mg/g lignin). Furthermore, SO(2) followed by dilute acid pretreated solids gave the highest cellulase effectiveness, but delignification enhanced cellulase effectiveness more for high pH than low pH pretreatments, suggesting that lignin impedes access of enzymes to xylan more than to glucan, which in turn affects glucan accessibility. In addition, lignin from enzymatic digestion of AFEX and dilute

  11. Chemicals from Lignin by Catalytic Fast Pyrolysis, from Product Control to Reaction Mechanism.

    PubMed

    Ma, Zhiqiang; Custodis, Victoria; Hemberger, Patrick; Bährle, Christian; Vogel, Frédéric; Jeschk, Gunnar; van Bokhoven, Jeroen A

    2015-01-01

    Conversion of lignin into renewable and value-added chemicals by thermal processes, especially pyrolysis, receives great attention. The products may serve as feedstock for chemicals and fuels and contribute to the development of a sustainable society. However, the application of lignin conversion is limited by the low selectivity from lignin to the desired products. The opportunities for catalysis to selectively convert lignin into useful chemicals by catalytic fast pyrolysis and our efforts to elucidate the mechanism of lignin pyrolysis are discussed. Possible research directions will be identified. PMID:26598403

  12. Rapid and accurate determination of the lignin content of lignocellulosic biomass by solid-state NMR.

    PubMed

    Fu, Li; McCallum, Scott A; Miao, Jianjun; Hart, Courtney; Tudryn, Gregory J; Zhang, Fuming; Linhardt, Robert J

    2015-02-01

    Biofuels and biomaterials, produced from lignocellulosic feedstock, require facile access to cellulose and hemicellulose to be competitive with petroleum processing and sugar-based fermentation. Physical-chemical barriers resulting from lignin complicates the hydrolysis biomass into fermentable sugars. Thus, the amount of lignin within a substrate is critical in determining biomass processing. The application of (13)C cross-polarization, magic-angle spinning, and solid-state nuclear magnetic resonance for the direct quantification of lignin content in biomass is examined. Using a standard curve constructed from pristine lignin and cellulose, the lignin content of a biomass sample is accurately determined through direct measurement without chemical or enzymatic pre-treatment.

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

    DOEpatents

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

    2014-06-10

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

  14. Interference of peptone and tyrosine with the lignin peroxidase assay.

    PubMed Central

    ten Have, R; Hartmans, S; Field, J A

    1997-01-01

    The N-unregulated white rot fungus Bjerkandera sp. strain BOS55 was cultured in 1 liter of peptone-yeast extract medium to produce lignin peroxidase (LiP). During the LiP assay, the oxidation of veratryl alcohol to veratraldehyde was inhibited due to tyrosine present in the peptone and the yeast extract. PMID:9251220

  15. Catalytic pyrolysis-GC/MS of lignin from several sources

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lignin from four different sources extracted by various methods were pyrolyzed at 650 degree C using analytical pyrolysis methods, py-GC/MS. Pyrolysis was carried out in the absence and presence of two heterogeneous catalysts , an acidic zeolite (HZSM-5) catalyst and a mixed metal oxide catalyst (Co...

  16. Graphitic biocarbon from metal-catalyzed hydrothermal carbonization of lignin

    SciTech Connect

    Demir, Muslum; Kahveci, Zafer; Aksoy, Burak; Palapati, Naveen K. R.; Subramanian, Arunkumar; Cullinan, Harry T.; El-Kaderi, Hani M.; Harris, Charles T.; Gupta, Ram B.

    2015-10-09

    Lignin is a high-volume byproduct from the pulp and paper industry and is currently burned to generate electricity and process heat. Moreover, the industry has been searching for high value-added uses of lignin to improve the process economics. In addition, battery manufacturers are seeking nonfossil sources of graphitic carbon for environmental sustainability. In our work, lignin (which is a cross-linked polymer of phenols, a component of biomass) is converted into graphitic porous carbon using a two-step conversion. Lignin is first carbonized in water at 300 °C and 1500 psi to produce biochar, which is then graphitized using a metal nitrate catalyst at 900–1100 °C in an inert gas at 15 psi. Graphitization effectiveness of three different catalysts—iron, cobalt, and manganese nitrates—is examined. The product is analyzed for morphology, thermal stability, surface properties, and electrical conductivity. Both temperature and catalyst type influenced the degree of graphitization. A good quality graphitic carbon was obtained using catalysis by Mn(NO3)2 at 900 °C and Co(NO3)2 at 1100 °C.

  17. Graphitic biocarbon from metal-catalyzed hydrothermal carbonization of lignin

    DOE PAGES

    Demir, Muslum; Kahveci, Zafer; Aksoy, Burak; Palapati, Naveen K. R.; Subramanian, Arunkumar; Cullinan, Harry T.; El-Kaderi, Hani M.; Harris, Charles T.; Gupta, Ram B.

    2015-10-09

    Lignin is a high-volume byproduct from the pulp and paper industry and is currently burned to generate electricity and process heat. Moreover, the industry has been searching for high value-added uses of lignin to improve the process economics. In addition, battery manufacturers are seeking nonfossil sources of graphitic carbon for environmental sustainability. In our work, lignin (which is a cross-linked polymer of phenols, a component of biomass) is converted into graphitic porous carbon using a two-step conversion. Lignin is first carbonized in water at 300 °C and 1500 psi to produce biochar, which is then graphitized using a metal nitratemore » catalyst at 900–1100 °C in an inert gas at 15 psi. Graphitization effectiveness of three different catalysts—iron, cobalt, and manganese nitrates—is examined. The product is analyzed for morphology, thermal stability, surface properties, and electrical conductivity. Both temperature and catalyst type influenced the degree of graphitization. A good quality graphitic carbon was obtained using catalysis by Mn(NO3)2 at 900 °C and Co(NO3)2 at 1100 °C.« less

  18. Recent Development in Chemical Depolymerization of Lignin: A Review

    DOE PAGES

    Wang, Hai; Tucker, Melvin; Ji, Yun

    2013-01-01

    This article reviewed recent development of chemical depolymerization of lignins. There were five types of treatment discussed, including base-catalyzed, acid-catalyzed, metallic catalyzed, ionic liquids-assisted, and supercritical fluids-assisted lignin depolymerizations. The methods employed in this research were described, and the important results were marked. Generally, base-catalyzed and acid-catalyzed methods were straightforward, but the selectivity was low. The severe reaction conditions (high pressure, high temperature, and extreme pH) resulted in requirement of specially designed reactors, which led to high costs of facility and handling. Ionic liquids, and supercritical fluids-assisted lignin depolymerizations had high selectivity, but the high costs of ionic liquids recyclingmore » and supercritical fluid facility limited their applications on commercial scale biomass treatment. Metallic catalyzed depolymerization had great advantages because of its high selectivity to certain monomeric compounds and much milder reaction condition than base-catalyzed or acid-catalyzed depolymerizations. It would be a great contribution to lignin conversion if appropriate catalysts were synthesized.« less

  19. Rigid Polyurethane Foams from Lignin Based-Polyols

    NASA Astrophysics Data System (ADS)

    Cateto, Carolina; Barreiro, Filomena; Rodrigues, Alírio; Belgacem, Naceur

    2008-08-01

    Rigid polyurethane (RPU) foams were synthesized using lignin-based polyols obtained by an oxypropylation process. Alcell, Indulin AT, Curan 27-11P and Sarkanda lignins have been oxypropylated using formulations deduced from an optimization study with Alcell. L/PO/C (ratio between lignin, PO and catalyst content) of 30/70/2 and 20/80/5 were used to obtain the desired polyols. The resulting RPU foams were characterized in terms of density, mechanical properties, conductivity and morphology. All Sarkanda lignin based polyols and the 30/70/2 Curan 27-11P polyol were found inadequate for RPU formulations. Alcell and Indulin AT based polyols and the 20/80/5 Curan 27-11P polyol resulted in RPU foams with properties very similar to those obtained from conventional commercial polyols. RPU foams produced with the 30/70/2 Alcell and the 30/70/2 Indulin AT polyols exhibited improved properties compared with those from 20/80/5 based formulations.

  20. Laccase-mediator catalyzed conversion of model lignin compounds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Laccases play an important role in the biological breakdown of lignin and have great potential in the deconstruction of lignocellulosic feedstocks. We examined a variety of laccases, both commercially prepared and crude extracts, for their ability to oxidize three model lignol compounds (p-coumaryl...

  1. Process for conversion of lignin to reformulated, partially oxygenated gasoline

    DOEpatents

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

    2001-01-09

    A high-yield process for converting lignin into reformulated, partially oxygenated gasoline compositions of high quality is provided. The process is a two-stage catalytic reaction process that produces a reformulated, partially oxygenated gasoline product with a controlled amount of aromatics. In the first stage of the process, a lignin feed material is subjected to a base-catalyzed depolymerization reaction, followed by a selective hydrocracking reaction which utilizes a superacid catalyst to produce a high oxygen-content depolymerized lignin product mainly composed of alkylated phenols, alkylated alkoxyphenols, and alkylbenzenes. In the second stage of the process, the depolymerized lignin product is subjected to an exhaustive etherification reaction, optionally followed by a partial ring hydrogenation reaction, to produce a reformulated, partially oxygenated/etherified gasoline product, which includes a mixture of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C.sub.7 -C.sub.10 alkylbenzenes, C.sub.6 -C.sub.10 branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.

  2. Laccase-mediator catalyzed conversion of model lignin compounds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Identifying suitable reaction conditions remains an important task in the development of practical enzyme catalysts. Laccases play an important role in the biological break down of lignin and have great potential in the deconstruction of lignocellulosic feedstocks. We examined 16 laccases, both comm...

  3. Hydrotreating Pyrolytic Lignin to Produce a Refinery Feedstock (Poster)

    SciTech Connect

    French, R. J.

    2013-09-01

    Fast pyrolysis of biomass followed by water separation to produce pyrolytic lignin and hydrotreating of the lignin could be used to produce a stable volatile low-oxygen intermediate liquid. Such a liquid could be converted into a finished motor-fuel in a refinery, taking advantage of the existing infrastructure and economies of scale of refineries. Hydrotreating just the lignin would consume less hydrogen while preserving about half of the energy of the original oil. The aqueous by-products could be reformed to produce the needed hydrogen and would contain much of the unwanted acids and unstable oxygenates. To assess such intermediate liquids, several pyrolytic lignins were prepared by mixing pyrolysis oil with water at 1:1 and 3:1 ratios. The carboxylic acidity in the pyrolytic lignin was reduced to 24 and 10 mg-KOH/g-lignin compared to 81 in the whole oil. These lignins were hydrotreated using Ni-Mo(S)/alumina, Pt/char, or Pd/C(activated) in a semi-batch 1 L stirred autoclave. The oil was stabilized under hydrogen at 150-280 degrees C, then water and light organics were removed by partial depressurization. Hydrodeoxygenation was then performed at 340-400 degrees C. Total pressure was controlled at 70 or 170 bar with hydrogen gas. Organic liquid yields of 39-56% were obtained. For many experiments the organic oxygen content was <7%, acidity was < 7 mg-KOH/g-oil, the volatility was greater than or equal to 94% and, on a carbon basis, the total yield of organic products miscible in hydrocarbons at a 1:10 ratio was over 50%. These properties are probably acceptable to a refinery.The residual liquids left in the reactor at the end of the experiment comprised 60-85% of the organic-phase product while the rest was condensate. 13C-NMR of the residual liquids showed that they were 50-80% aliphatic. 13C-NMR coupled with GC-MS identified phenolic compounds as the main oxygenates in most residual liquids.

  4. Bio-inspired MOF-based Catalysts for Lignin Valorization.

    SciTech Connect

    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

  5. Flocculation of wheat straw soda lignin by hemoglobin and chicken blood: Effects of cationic polymer or calcium chloride

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flocculation can be used to separate non-sulfonated lignin from base hydrolyzed biomass. In the industrial process, the lignin is isolated by filtration and washed with water. Some of the lignin is lost in the wash water, and flocculation can be used to recover this lignin. Several ways of enhanc...

  6. Effect of different isolation methods on structure and properties of lignin from valonea of Quercus variabilis.

    PubMed

    Yang, Lina; Wang, Dongmei; Zhou, Dan; Zhang, Yawei

    2016-04-01

    Valonea of Quercus variabilis Blume, an abundant feedstock in China, can be used for tannin. However, there are little studies about lignin from this material. The present study aimed at lignin from the valonea: (1) Ethanol lignin (EL), alkali lignin (AL), milled wood lignin (MWL) and enzyme hydrolysis lignin (EHL) were prepared from the valonea of Q.variabilis Blume. (2) The effect of different isolation processes on the lignin chemical and physical features were studied by UV-vis, FT-IR, GPC, TG and (1)H NMR. (3) Antioxidant activities of four lignin preparations were evaluated by DPPH, ABTS and FRAP assays. The results showed that the valonea of Q. variabilis contained mass lignin and four lignin preparations were GSH-type with little differences. The MWL contained the least functional groups (1.75 mmol/g MeO, 0.87 mmol/g ArOH and 1.27 mmol/g AlkOH), the poorest thermostability (onset degradation temperature=111°C, maximum rate of degradation=268°C) and the highest antioxidant activity. The EHL had the highest molecular weight (Mw=1,429 g/mol; Mn=746.18 g/mol). This study provided a theoretical basis for the development and utilization of lignin from the valonea of Q. variabilis.

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

    PubMed

    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. PMID:25212007

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

    PubMed

    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.

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

    PubMed

    Wang, Wen; Zhuang, Xinshu; Yuan, Zhenhong; Qi, Wei; Yu, Qiang; Wang, Qiong

    2016-01-01

    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. PMID:27563678

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

    PubMed Central

    Zhuang, Xinshu; Qi, Wei; Yu, Qiang; Wang, Qiong

    2016-01-01

    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. PMID:27563678

  11. Peroxidase 4 is involved in syringyl lignin formation in Arabidopsis thaliana.

    PubMed

    Fernández-Pérez, Francisco; Vivar, Tamara; Pomar, Federico; Pedreño, María A; Novo-Uzal, Esther

    2015-03-01

    Syringyl lignins result from the oxidative polymerization of sinapyl alcohol in a reaction mediated by syringyl (basic) peroxidases. Several peroxidases have been identified in the genome of Arabidopsis thaliana as close homologues to ZePrx, the best characterized basic peroxidase so far, but none of these has been directly involved in lignification. We have used a knock-out mutant of AtPrx4, the closest homologue to ZePrx, to study the involvement of this basic peroxidase in the physiology of the plant under both long- and short-day light conditions. Our results suggest that AtPrx4 is involved in cell wall lignification, especially in syringyl monomer formation. The disruption of AtPrx4 causes a decrease in syringyl units proportion, but only when light conditions are optimal. Moreover, the effect of AtPrx4 disruption is age-dependent, and it is only significant when the elongation process of the stem has ceased and lignification becomes active. In conclusion, AtPrx4 emerges as a basic peroxidase regulated by day length with an important role in lignification.

  12. Peroxidase 4 is involved in syringyl lignin formation in Arabidopsis thaliana.

    PubMed

    Fernández-Pérez, Francisco; Vivar, Tamara; Pomar, Federico; Pedreño, María A; Novo-Uzal, Esther

    2015-03-01

    Syringyl lignins result from the oxidative polymerization of sinapyl alcohol in a reaction mediated by syringyl (basic) peroxidases. Several peroxidases have been identified in the genome of Arabidopsis thaliana as close homologues to ZePrx, the best characterized basic peroxidase so far, but none of these has been directly involved in lignification. We have used a knock-out mutant of AtPrx4, the closest homologue to ZePrx, to study the involvement of this basic peroxidase in the physiology of the plant under both long- and short-day light conditions. Our results suggest that AtPrx4 is involved in cell wall lignification, especially in syringyl monomer formation. The disruption of AtPrx4 causes a decrease in syringyl units proportion, but only when light conditions are optimal. Moreover, the effect of AtPrx4 disruption is age-dependent, and it is only significant when the elongation process of the stem has ceased and lignification becomes active. In conclusion, AtPrx4 emerges as a basic peroxidase regulated by day length with an important role in lignification. PMID:25506770

  13. Characterization of carbon nanofiber mats produced from electrospun lignin-g-polyacrylonitrile copolymer.

    PubMed

    Youe, Won-Jae; Lee, Soo-Min; Lee, Sung-Suk; Lee, Seung-Hwan; Kim, Yong Sik

    2016-01-01

    The graft copolymerization of acrylonitrile (AN) onto methanol-soluble kraft lignin (ML) was achieved through a two-step process in which AN was first polymerized with an α,α'-azobisisobutyronitrile initiator, followed by radical coupling with activated ML. A carbon nanofiber material was obtained by electrospinning a solution of this copolymer in N,N-dimethylformamide, then subjecting it to a heat treatment including thermostabilization at 250°C and subsequent carbonization at 600-1400°C. Increasing the carbonization temperature was found to increase the carbon content of the resulting carbon nanofibers from 70.5 to 97.1%, which had the effect of increasing their tensile strength from 35.2 to 89.4 MPa, their crystallite size from 13.2 to 19.1 nm, and their electrical conductivity from ∼0 to 21.3 Scm(-1). The morphology of the mats, in terms of whether they experienced beading or not, was found to be dependent on the concentration of the initial electrospinning solution. From these results, it is proposed that these mats could provide the basis for a new class of carbon fiber material.

  14. Characterization of carbon nanofiber mats produced from electrospun lignin-g-polyacrylonitrile copolymer.

    PubMed

    Youe, Won-Jae; Lee, Soo-Min; Lee, Sung-Suk; Lee, Seung-Hwan; Kim, Yong Sik

    2016-01-01

    The graft copolymerization of acrylonitrile (AN) onto methanol-soluble kraft lignin (ML) was achieved through a two-step process in which AN was first polymerized with an α,α'-azobisisobutyronitrile initiator, followed by radical coupling with activated ML. A carbon nanofiber material was obtained by electrospinning a solution of this copolymer in N,N-dimethylformamide, then subjecting it to a heat treatment including thermostabilization at 250°C and subsequent carbonization at 600-1400°C. Increasing the carbonization temperature was found to increase the carbon content of the resulting carbon nanofibers from 70.5 to 97.1%, which had the effect of increasing their tensile strength from 35.2 to 89.4 MPa, their crystallite size from 13.2 to 19.1 nm, and their electrical conductivity from ∼0 to 21.3 Scm(-1). The morphology of the mats, in terms of whether they experienced beading or not, was found to be dependent on the concentration of the initial electrospinning solution. From these results, it is proposed that these mats could provide the basis for a new class of carbon fiber material. PMID:26459170

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

    PubMed

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

    2012-12-14

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

  16. Lignin valorization through integrated biological funneling and chemical catalysis.

    PubMed

    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

    2014-08-19

    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

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

    PubMed

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

    2012-12-14

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

  18. Lignin valorization through integrated biological funneling and chemical catalysis

    PubMed Central

    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

  19. Consolidated bioprocessing of Populus using Clostridium (Ruminiclostridium) thermocellum: a case study on the impact of lignin composition and structure

    DOE PAGES

    Dumitrache, Alexandru; Akinosho, Hannah; Rodriguez, Miguel; Meng, Xianzhi; Yoo, Chang Geun; Natzke, Jace; Engle, Nancy L.; Sykes, Robert W.; Tschaplinski, Timothy J.; Muchero, Wellington; et al

    2016-02-04

    Background: Higher ratios of syringyl-to-guaiacyl (S/G) lignin components of Populus were shown to improve sugar release by enzymatic hydrolysis using commercial blends. Cellulolytic microbes are often robust biomass hydrolyzers and may offer cost advantages; however, it is unknown whether their activity can also be significantly influenced by the ratio of different monolignol types in Populus biomass. Hydrolysis and fermentation of autoclaved, but otherwise not pretreated Populus trichocarpa by Clostridium thermocellum ATCC 27405 was compared using feedstocks that had similar carbohydrate and total lignin contents but differed in S/G ratios. Results: Populus with an S/G ratio of 2.1 was converted moremore » rapidly and to a greater extent compared to similar biomass that had a ratio of 1.2. For either microbes or commercial enzymes, an approximate 50% relative difference in total solids solubilization was measured for both biomasses, which suggests that the differences and limitations in the microbial breakdown of lignocellulose may be largely from the enzymatic hydrolytic process. Unexpectedly, the reduction in glucan content per gram solid in the residual microbially processed biomass was similar (17–18%) irrespective of S/G ratio, pointing to a similar mechanism of solubilization that proceeded at different rates. Fermentation metabolome testing did not reveal the release of known biomass-derived alcohol and aldehyde inhibitors that could explain observed differences in microbial hydrolytic activity. Biomass-derived p-hydroxybenzoic acid was up to ninefold higher in low S/G ratio biomass fermentations, but was not found to be inhibitory in subsequent test fermentations. Cellulose crystallinity and degree of polymerization did not vary between Populus lines and had minor changes after fermentation. However, lignin molecular weights and cellulose accessibility determined by Simons’ staining were positively correlated to the S/G content. Conclusions: Higher

  20. Biomimetic Fenton-catalyzed lignin depolymerization to high-value aromatics and dicarboxylic acids.

    PubMed

    Zeng, Jijiao; Yoo, Chang Geun; Wang, Fei; Pan, Xuejun; Vermerris, Wilfred; Tong, Zhaohui

    2015-03-01

    By mimicking natural lignin degradation systems, the Fenton catalyst (Fe(3+), H2O2) can effectively facilitate lignin depolymerization in supercritical ethanol (7 MPa, 250 °C) to give organic oils that consist of mono- and oligomeric aromatics, phenols, dicarboxylic acids, and their derivatives in yields up to (66.0±8.5) %. The thermal properties, functional groups, and surface chemistry of lignin before and after Fenton treatment were examined by thermogravimetric analysis, pyrolysis-gas chromatography-mass spectrometry, (31)P NMR spectroscopy, and X-ray photoelectron spectroscopy. The results suggest that the Fenton catalyst facilitates lignin depolymerization through cleavage of β-ether bonds between lignin residues. The formation of a lignin-iron chelating complex effectively depresses lignin recondensation; thus minimizing charcoal formation and enhancing the yield of liquid products.

  1. Predicting enzyme adsorption to lignin films by calculating enzyme surface hydrophobicity.

    PubMed

    Sammond, Deanne W; Yarbrough, John M; Mansfield, Elisabeth; Bomble, Yannick J; Hobdey, Sarah E; Decker, Stephen R; Taylor, Larry E; Resch, Michael G; Bozell, Joseph J; Himmel, Michael E; Vinzant, Todd B; Crowley, Michael F

    2014-07-25

    The inhibitory action of lignin on cellulase cocktails is a major challenge to the biological saccharification of plant cell wall polysaccharides. Although the mechanism remains unclear, hydrophobic interactions between enzymes and lignin are hypothesized to drive adsorption. Here we evaluate the role of hydrophobic interactions in enzyme-lignin binding. The hydrophobicity of the enzyme surface was quantified using an estimation of the clustering of nonpolar atoms, identifying potential interaction sites. The adsorption of enzymes to lignin surfaces, measured using the quartz crystal microbalance, correlates to the hydrophobic cluster scores. Further, these results suggest a minimum hydrophobic cluster size for a protein to preferentially adsorb to lignin. The impact of electrostatic contribution was ruled out by comparing the isoelectric point (pI) values to the adsorption of proteins to lignin surfaces. These results demonstrate the ability to predict enzyme-lignin adsorption and could potentially be used to design improved cellulase cocktails, thus lowering the overall cost of biofuel production. PMID:24876380

  2. Predicting Enzyme Adsorption to Lignin Films by Calculating Enzyme Surface Hydrophobicity*

    PubMed Central

    Sammond, Deanne W.; Yarbrough, John M.; Mansfield, Elisabeth; Bomble, Yannick J.; Hobdey, Sarah E.; Decker, Stephen R.; Taylor, Larry E.; Resch, Michael G.; Bozell, Joseph J.; Himmel, Michael E.; Vinzant, Todd B.; Crowley, Michael F.

    2014-01-01

    The inhibitory action of lignin on cellulase cocktails is a major challenge to the biological saccharification of plant cell wall polysaccharides. Although the mechanism remains unclear, hydrophobic interactions between enzymes and lignin are hypothesized to drive adsorption. Here we evaluate the role of hydrophobic interactions in enzyme-lignin binding. The hydrophobicity of the enzyme surface was quantified using an estimation of the clustering of nonpolar atoms, identifying potential interaction sites. The adsorption of enzymes to lignin surfaces, measured using the quartz crystal microbalance, correlates to the hydrophobic cluster scores. Further, these results suggest a minimum hydrophobic cluster size for a protein to preferentially adsorb to lignin. The impact of electrostatic contribution was ruled out by comparing the isoelectric point (pI) values to the adsorption of proteins to lignin surfaces. These results demonstrate the ability to predict enzyme-lignin adsorption and could potentially be used to design improved cellulase cocktails, thus lowering the overall cost of biofuel production. PMID:24876380

  3. Interpreting C-13 NMR spectra of technical lignins based on ionization chemical shifts

    SciTech Connect

    Akim, L.G.; Fedulina, T.G.; Shevchenko, S.M.

    1996-10-01

    Newly developed technique of C-13 NMR spectroscopy of ionized lignins in aqueous alkali has been applied to analysis of the chemical structure of technical lignins. Ionization of phenolic and carboxylic hydroxyl groups has a strong effect on the electronic structure of lignin and leads to significant changes in C-13 NMR spectra of the polymer. Comparative analysis of the spectra of organosolv and alkali lignins in neutral organic and aqueous alkaline media based on the data obtained for lignin model compounds demonstrated the usefulness and scope of applicability of the method. This method was especially useful when applied to a highly degraded alkaline lignin, enhancing our ability to analyze the poorly resolved spectrum. A technique is developed that permits the user to analyze a lignin spectrum in an aqueous alkaline solution without the accompanying spectrum in an organic solution. The research described was made possible by Grant No. NWFOOO from the International Science Foundation.

  4. A study of poplar organosolv lignin after melt rheology treatment as carbon fiber precursors

    DOE PAGES

    Sun, Qining; Khunsupat, Ratayakorn; Akato, Kokouvi; Tao, Jingming; Labbe, Nicole; Gallego, Nidia C.; Bozell, Joseph J.; Rials, Timothy G.; Tuskan, Gerald A.; Tschaplinski, Timothy J.; et al

    2016-06-16

    Lignins from various poplar genotypes were isolated by using organosolv fractionation and subjected to rheological treatment at various temperatures. Physicochemical characterization of the lignin variants shows a broad distribution of glass transition temperatures, melt viscosity, and pyrolysis char residues. Rheological treatment at 170 °C induces lignin repolymerization accompanied with an increase in condensed linkages, molecular weights, and viscosities. In contrast, rheology testing at 190 °C results in the decrease in lignin aliphatic and phenolic hydroxyl groups, β-O-aryl ether linkages, molecular weights, and viscosity values. Lignin under air cooling generates more oxygenated and condensed compounds, but lower amounts of ether linkagesmore » than lignin cooled under nitrogen. Here, lignin with a lower syringyl/guaiacyl ratio tends to form more cross-linkages along with higher viscosity values, higher molecular weight and larger amounts of condensed bonds.« less

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

    PubMed Central

    Sattler, Scott E.; Funnell-Harris, Deanna L.

    2013-01-01

    Lignin is a ubiquitous polymer present in cell walls of all vascular plants, where it rigidifies and strengthens the cell wall structure through covalent cross-linkages to cell wall polysaccharides. The presence of lignin makes the cell wall recalcitrant to conversion into fermentable sugars for bioenergy uses. Therefore, reducing lignin content and modifying its linkages have become major targets for bioenergy feedstock development through either biotechnology or traditional plant breeding. In addition, lignin synthesis has long been implicated as an important plant defense mechanism against pathogens, because lignin synthesis is often induced at the site of pathogen attack. This article explores the impact of lignin modifications on the susceptibility of a range of plant species to their associated pathogens, and the implications for development of feedstocks for the second-generation biofuels industry. Surprisingly, there are some instances where plants modified in lignin synthesis may display increased resistance to associated pathogens, which is explored in this article. PMID:23577013

  6. Singlet oxygen mediated degradation of lignin--isolation of oxidation products from steam-exploded lignin from pine.

    PubMed

    Bonini, Carlo; D'Auria, Maurizio; Ferri, Rachele

    2002-08-01

    Lignin obtained from steam explosion of pine was fully characterized. Elemental analysis, GPC, and ultraviolet and 1H and 13C NMR spectra revealed that the obtained lignin contains both guaiacyl and syringyl units. Lignin was dissolved in acetonitrile-ethanol and treated with visible light in the presence of both oxygen and Rose Bengal for different irradiation times. Column chromatography of the residue showed the presence of six compounds: trans-sinapyl alcohol, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethoxyphenylacetone, 4-hydroxy-3-methoxybenzaldehyde, cis-sinapyl alcohol, and sinapyl aldehyde. The total amount of fine chemicals increases with the irradiation time. However, it increases rapidly during the first eight hours, but increases slowly after this period. The most important compounds obtained were sinapyl alcohol and 4-hydroxy-3,5-dimethoxybenzaldehyde, but sinapyl alcohol was obtained in the highest amounts after eight hours' irradiation, while the highest amounts of 4-hydroxy-3,5-dimethoxybenzaldehyde were obtained after irradiation for 4 h. After 48 h irradiation comparable amounts of sinapyl aldehyde were obtained. We obtained only compounds derived from the syringyl units in lignin in agreement with the hypothesis that the guaiacyl units are more easily oxidised.

  7. Fate and transport of lignin in the soil-water continuum

    NASA Astrophysics Data System (ADS)

    Williams, J. S.; Dungait, J.; Bol, R.; Abbott, G. D.

    2011-12-01

    Soils have been identified as having the potential to store greater amounts of carbon (C) in soil organic matter (SOM) through appropriate land uses and management practices to increase the input of recalcitrant components of organic matter, such as lignin. Lignin is allocated to the 'slow' soil C pools with residence times between 15 - 100 yrs. Lignin is 30% of the C fixed by plants and is an important C input to soils. However, Recent research has shown that the configuration of lignin monomers within the lignin macromolecule is not random [1], that lignin degradation is monomer specific [2], and that lignin is preferentially degraded relative to the bulk SOM [3], thereby questioning the role of lignin in C sequestration. Although guaiacyl (G) and syringyl (S) lignin monomers have been identified in fresh, estuarine, and marine waters [4], the initial forms to which lignin is degraded into water-transportable products and lost from the soil C reservoir are not known. The aims of this project are to (i) identify and quantify the lignin-derived products entering the soluble phase in soils, and (ii) determine the rate of lignin degradation into water-soluble components, and their rate of transport through soil. In experiment 1 we tested the best approach to extract and analyse dissolved lignin from outflows from grassland and woodland sites. C18 solid phase extraction (SPE) or freeze-drying (FD) was used to isolate water-borne lignin monomers. Gas chromatography-mass spectrometry (GC-MS) of trimethylsilyl (TMS) derivatives or tetramethylammonium hydroxide (TMAH) thermochemolysis was used to analyse the samples. In a subsequent experiment, we allowed leaves from different vegetation types (Lolium perenne, Ranunculus repens, Fraxinus excelsior, Quercus robur), corresponding to the vegetation at our initial sites in Experiment 1, to degrade in soil lysimeters for 1.5 years to determine the rates of decomposition of different plant material and dominant form of lignin

  8. Production of monodisperse, polymeric microspheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chang, Manchium (Inventor)

    1990-01-01

    Very small, individual polymeric microspheres with very precise size and a wide variation in monomer type and properties are produced by deploying a precisely formed liquid monomer droplet, suitably an acrylic compound such as hydroxyethyl methacrylate into a containerless environment. The droplet which assumes a spheroid shape is subjected to polymerizing radiation such as ultraviolet or gamma radiation as it travels through the environment. Polymeric microspheres having precise diameters varying no more than plus or minus 5 percent from an average size are recovered. Many types of fillers including magnetic fillers may be dispersed in the liquid droplet.

  9. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for

  10. High temperature structural, polymeric foams from high internal emulsion polymerization

    SciTech Connect

    Hoisington, M.A.; Duke, J.R.; Apen, P.G.

    1996-02-01

    In 1982, a high internal phase emulsion (HIPE) polymerization process to manufacture microcellular, polymeric foam systems was patented by Unilever. This patent discloses a polymerization process that occurs in a water-in-oil emulsion in which the water represents at least 76% of the emulsion by volume. The oil phase consists of vinyl monomers such as styrene and acrylates that are crosslinked by divinyl monomers during polymerization. After polymerization and drying to remove the water phase, the result is a crosslinked polymer foam with an open cell microstructure that is homogeneous throughout in terms of morphology, density, and mechanical properties. Since 1982, numerous patents have examined various HIPE polymerized foam processing techniques and applications that include absorbents for body fluids, cleaning materials, and ion exchange systems. All the published HIPE polymerized foams have concentrated on materials for low temperature applications. Copolymerization of styrene with maleic anhydride and N-substituted maleimides to produce heat resistant thermoplastics has been studied extensively. These investigations have shown that styrene will free radically copolymerize with N-substituted maleimides to create an alternating thermoplastic copolymer with a Tg of approximately 200{degrees}C. However, there are many difficulties in attempting the maleimide styrene copolymerization in a HIPE such as lower polymerization temperatures, maleimide solubility difficulties in both styrene and water, and difficulty obtaining a stable HIPE with a styrene/maleimide oil phase. This work describes the preparation of copolymer foams from N-ethylmaleimide and Bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane with styrene based monomers and crosslinking agents.

  11. Comparison of XAD with other dissolved lignin isolation techniques and a compilation of analytical improvements for the analysis of lignin in aquatic settings

    USGS Publications Warehouse

    Spencer, R.G.M.; Aiken, G.R.; Dyda, R.Y.; Butler, K.D.; Bergamaschi, B.A.; Hernes, P.J.

    2010-01-01

    This manuscript highlights numerous incremental improvements in dissolved lignin measurements over the nearly three decades since CuO oxidation of lignin phenols was first adapted for environmental samples. Intercomparison of the recovery efficiency of three common lignin phenol concentration and isolation techniques, namely XAD, C18 with both CH3OH (C18M) and CH3CN (C18A) used independently for priming and elution steps, and tangential flow filtration (TFF) for a range of aquatic samples including fresh, estuarine and marine waters, was undertaken. With freshwater samples XAD8-1, C18M and TFF were all observed to recover ca. 80-90% of the lignin phenols and showed no fractionation effects with respect to diagnostic lignin parameters. With estuarine and marine samples more lignin phenols were recovered with C18M and XAD8-1 than TFF because of the increased prevalence of low molecular weight lignin phenols in marine influenced samples. For marine systems, differences were also observed between diagnostic lignin parameters isolated via TFF vs. C18M and XAD8-1 as a result of the high molecular weight lignin phenols being less degraded than the bulk. Therefore, it is recommended for future studies of marine systems that only one technique is utilized for ease of intercomparison within studies. It is suggested that for studies solely aimed at recovering bulk dissolved lignin in marine environments that C18M and XAD8-1 appear to be more suitable than TFF as they recover more lignin. Our results highlight that, for freshwater samples, all three common lignin phenol concentration and isolation techniques are comparable to whole water concentrated by rotary evaporation (i.e. not isolated) but, that for marine systems, the choice of concentration and isolation techniques needs to be taken into consideration with respect to both lignin concentration and diagnostic parameters. Finally, as the study highlights XAD8-1 to be a suitable method for the isolation of dissolved lignin

  12. Kinetics of silica polymerization

    SciTech Connect

    Weres, O.; Yee, A.; Tsao, L.

    1980-05-01

    The polymerization of silicic acid in geothermal brine-like aqueous solutions to produce amorphous silica in colloidal form has been studied experimentally and theoretically. A large amount of high quality experimental data has been generated over the temperature rang 23 to 100{sup 0}C. Wide ranges of dissolved silica concentration, pH, and sodium chloride concentration were covered. The catalytic effects of fluoride and the reaction inhibiting effects of aluminum and boron were studied also. Two basic processes have been separately studied: the formation of new colloidal particles by the homogeneous nucleation process and the deposition of dissolved silica on pre-existing colloidal particles. A rigorous theory of the formation of colloidal particles of amorphous silica by homogeneous nucleation was developed. This theory employs the Lothe-Pound formalism, and is embodied in the computer code SILNUC which quantitatively models the homogeneous nucleation and growth of colloidal silica particles in more than enough detail for practical application. The theory and code were extensively used in planning the experimental work and analyzing the data produced. The code is now complete and running in its final form. It is capable of reproducing most of the experimental results to within experimental error. It is also capable of extrapolation to experimentally inaccessible conditions, i.e., high temperatures, rapidly varying temperature and pH, etc.

  13. Some novel polymeric nanocomposites.

    PubMed

    Mark, James E

    2006-12-01

    The nanocomposites described here all involve polymers and were chosen because they are already of commercial importance, show some promise of becoming so, or simply seem interesting. The field is so broad that some topics are mentioned only very briefly, and there is considerable emphasis on the polysiloxane nanocomposites studied by the author's research group. Some are typically prepared using techniques very similar to those used in the new sol-gel approach to ceramics, with either the polymer or the ceramic being the continuous phase. Other dispersed phases include particles responsive to an applied magnetic field, intercalated or exfoliated platelets obtained from clays, mica, or graphite, silsesquioxane nanocages, nanotubes, dual fillers, porous particles, spherical and ellipsoidal polymeric particles, and nanocatalysts. Also described are some typical studies involving theory or simulations on such particle reinforcement. Experiments on ceramics modified by dispersed polymers are equally interesting, but there is less relevant theory. Many of the fields mentioned have become so vast that the approach taken here is simply to describe general approaches and characteristics of the composites, list some specific examples, and provide leading references (with some emphasis on studies that are relatively recent or in the nature of reviews).

  14. A novel and efficient polymerization of lignosulfonates by horseradish peroxidase/H(2)O(2) incubation.

    PubMed

    Zhou, Haifeng; Yang, Dongjie; Qiu, Xueqing; Wu, Xiaolei; Li, Yuan

    2013-12-01

    Lignosulfonates(LSs), by-products from chemical pulping processes, are low-value products with limited dispersion properties. The ability of commercially available horseradish peroxidase (HRP) to polymerize LS macromolecules and improve the dispersion properties of LSs was investigated. The polymerization of LSs proceeded efficiently under mild reaction conditions in an aqueous solution with HRP/H2O2. Gel permeation chromatography showed a significant increase in weight-average molecular weight (M w ) of sulfonated kraft lignin and sodium lignosulfonate (NaLS) by 8.5-fold and 4.7-fold, respectively. The mechanism of polymerization was investigated by elemental analysis, surface charge measurement, headspace gas chromatography, infrared spectroscopy (IR), and hydrogen nuclear magnetic resonance spectrometry ((1)H-NMR). The functional group measurements indicated that HRP incubation did not reduce the sulfonic group content. However, it decreased the phenolic and methoxyl group contents. As the phenolic group content decreased, M w increased as a power function. The polymerization was proposed to involve the random coupling of phenoxy radical intermediates. The radicals coupled with each other to form different inter-unit linkages, most of which were the β-O-4' type, as the (1)H-NMR spectra indicated. Moreover, the HRP/H2O2 incubation induced a significant improvement in the adsorption and dispersion properties of LSs. Therefore, the HRP/H2O2 incubation is a promising approach for industrial applications of LSs. PMID:24196582

  15. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

  16. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles. PMID:16430253

  17. Degradation and polymerization of monolignols by Abortiporus biennis, and induction of its degradation with a reducing agent.

    PubMed

    Hong, Chang-Young; Park, Se-Yeong; Kim, Seon-Hong; Lee, Su-Yeon; Choi, Won-Sil; Choi, In-Gyu

    2016-10-01

    This study was carried out to better understand the characteristic modification mechanisms of monolignols by enzyme system of Abortiporus biennis and to induce the degradation of monolignols. Degradation and polymerization of monolignols were simultaneously induced by A. biennis. Whole cells of A. biennis degraded coniferyl alcohol to vanillin and coniferyl aldehyde, and degraded sinapyl alcohol to 2,6-dimethoxybenzene- 1,4-diol, with the production of dimers. The molecular weight of monolignols treated with A. biennis increased drastically. The activities of lignin degrading enzymes were monitored for 24 h to determine whether there was any correlation between monolignol biomodification and ligninolytic enzymes. We concluded that complex enzyme systems were involved in the degradation and polymerization of monolignols. To degrade monolignols, ascorbic acid was added to the culture medium as a reducing agent. In the presence of ascorbic acid, the molecular weight was less increased in the case of coniferyl alcohol, while that of sinapyl alcohol was similar to that of the control. Furthermore, the addition of ascorbic acid led to the production of various degraded compounds: syringaldehyde and acid compounds. Accordingly, these results demonstrated that ascorbic acid prevented the rapid polymerization of monolignols, thus stabilizing radicals generated by enzymes of A. biennis. Thereafter, A. biennis catalyzed the oxidation of stable monolignols. As a result, ascorbic acid facilitated predominantly monolignols degradation by A. biennis through the stabilization of radicals. These findings showed outstanding ability of A. biennis to modify the lignin compounds rapidly and usefully. PMID:27687230

  18. An ab initio molecular dynamics analysis of lignin as a potential antioxidant for hydrocarbons.

    PubMed

    Pan, Tongyan; Cheng, Cheng

    2015-11-01

    Lignins are complex phenolic polymers with limited industrial uses. To identify new applications of lignins, this study aims to evaluate the conifer alcohol lignin as a potential antioxidant for hydrocarbons, using the petroleum asphalt as an example. Using the ab initio molecular dynamics (AIMD) method, the evaluation is accomplished by tracking the generation of critical species in a lignin-asphalt mixture under a simulated oxidative condition. The generation of new species was detected using nuclear magnetic resonance and four analytical methods including density of states analysis, highest occupied molecular orbital and lowest unoccupied molecular orbital analyses, bonding and energy level analysis, and electrostatic potential energy analysis. Results of the analyses show that the chemical radicals of carbon, nitrogen and sulfur generated in the oxidation process could enhance the agglomeration and/or decomposition tendency of asphalt. The effectiveness of lignins as an antioxidant depends on their chemical compositions. Lignins with a HOMO-LUMO gap larger than the HOMO-LUMO gap of the hydrocarbon system to be protected, such as the conifer alcohol lignin to protect petroleum asphalt as was studied in this work, do not demonstrate beneficial anti-oxidation capacity. Lignins, however, may be effective oxidants for hydrocarbon systems with a larger HOMO-LUMO gap. In addition, lignins may contain more polar sites than the hydrocarbons to be protected; thus the lignins' hydrophobicity and compatibility with the host hydrocarbons need to be well evaluated. The developed AIMD model provides a useful tool for developing antioxidants for generic hydrocarbons. PMID:26562413

  19. Characterization of dietary fiber lignins from fruits and vegetables using the DFRC method.

    PubMed

    Bunzel, Mirko; Seiler, Annika; Steinhart, Hans

    2005-11-30

    Insoluble fiber fractions from 11 fruits and vegetables were investigated for their lignin composition using the derivatization followed by reductive cleavage (DFRC) methodology. To enrich lignin contents and to minimize polysaccharide excess that led to nonanalyzable DFRC chromatograms, the insoluble fibers were degraded by a carbohydrolases mixture. The residues that were found to be representative for the insoluble fiber lignins were analyzed. The investigated fibers differ considerably in their lignin contents and also in their lignin compositions. With the exception of radish fiber, only trace amounts (or none) of the products resulting from p-hydroxyphenyl units were detected. Lignins noticeably differed in the ratio of the DFRC products resulting from syringyl units (S) and guaiacyl (G) units (G/S ratios ranged from approximately 39 to 0.2). The insoluble fiber lignins were classified as G-rich lignins (G/S ratio > 3; carrot, spinach, kiwi, curly kale, radish, and asparagus), S-rich lignins (S/G ratio > 3; rhubarb), or balanced lignins (0.3 < G/S ratio < 3; pear, apple, small radish, and kohlrabi). Information about further structural characteristics, for example, cinnamyl endgroups, was obtained from the analysis of DFRC minor products.

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

    PubMed

    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.

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

    PubMed

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

    2014-05-01

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

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

    PubMed

    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. PMID:27373451

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

    PubMed

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

    2014-05-01

    Milled wood lignin was subjected to heat treatment between 150 and 300°C to understand the pattern of its structural modification and thermal properties. When the temperature was elevated with interval of 50°C, the color of the lignin became dark brown and the lignin released various forms of phenols from terminal phenolic groups in the lignin, leading to two physical phenomena: (1) gradual weight loss of the lignin, up to 19% based on dry weight and (2) increase in the carbon content and decrease in the oxygen content. Nitrobenzene oxidation and (13)C NMR analyses confirmed a cleavage of β-O-4 linkage (depolymerization) and reduction of methoxyl as well as phenolic hydroxyl group were also characteristic in the lignin structure during heat treatment. Simultaneously with lignin depolymerization, GPC analysis provided a possibility that condensation between lignin fragments could also occur during heat treatment. TGA/DTG/DSC data revealed that thermal stability of lignin obviously increased after heat treatment, implicating the structural rearrangement of lignin to reduction of β-O-4 linkage as well as accumulation of CC bonds. PMID:24530642

  4. Lignin-assisted coal depolymerization. Technical report, December 1, 1991--February 29, 1992

    SciTech Connect

    Lalvani, S.B.

    1992-08-01

    Previous research has shown that addition of lignin and lignin-derived liquids to coal stirred in tetralin under mild reaction conditions (375{degrees}C and 300--500 psig) results in a marked enhancement in the rate of coal depolymerization. In this quarterly report, overall mass balances on experiments conducted with tetralin, coal, lignin and coal-lignin mixture are reported. Overall mass recoveries of 95--99% of the total mass charged to the reactor were obtained. A number of experiments were conducted on coal, lignin and coal-lignin depolymerization. A careful statistical analysis of the data shows that coal depolymerization is enhanced by 10.4%, due to the lignin addition. The liquids obtained are being examined for their elemental composition, and molecular weight determination by size exclusion chromatography. The stability of the liquid products is being examined in various environments. The gaseous product analyses show that the major gases produced during the course of depolymerization are CO, CH{sub 4}, and CO{sub 2}. When coal and lignin are reacted together, the amount of CO and CH{sub 4}produced respectively 12% and 38% greater than the corresponding amount of gases calculated, based on the weighted average of values obtained for coal and lignin alone. The data obtained show that lignin addition to coal is synergistic in that not only is the extent of coal depolymerization increased, but the gas produced contains higher concentrations of more desirable gaseous products.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Turning Renewable Resources into Recyclable Polymer: Development of Lignin-Based Thermoplastic

    SciTech Connect

    Saito, Tomonori; Brown, Rebecca H; Hunt, Marcus A; Pickel, Deanna L; Pickel, Joseph M; Messman, Jamie M; Baker, Frederick S; Keller, Martin; Naskar, Amit K

    2012-01-01

    Productive uses of lignin, the third most abundant natural polymer, have been sought for decades. One especially attractive possibility is that of developing value-added products including thermoplastics based on lignin. This possibility warrants special attention due to growth of the modern biofuel industries. However, the polydisperse molecular weight and hyper-branched structure of lignin has hindered the creation of high-performance biopolymers. Here, we report the preparation and characterization of novel lignin-based, partially carbon-neutral thermoplastics. We first altered the molecular weight of lignin, either by fractionation with methanol, or by formaldehyde crosslinking. A crosslinking of lignin increases the molecular weight, exhibiting Mn = 31000 g/mol, whereas that of native lignin is 1840 g/mol. Tuning the molecular weight of lignin enabled successful preparation of novel lignin-derived thermoplastics, when coupled with telechelic polybutadiene soft-segments at proper feed ratios. Characteristic to thermoplastic rubbers, free-standing films of the resulting copolymers exhibit two-phase morphology and associated relaxations in the dynamic mechanical loss spectrum. To our knowledge this article is the first report to demonstrate phase immiscibility, melt-processibility, and biphasic morphology of soft and hard segments in a lignin-based copolymer for all feed ratios of two macromolecular components. The use of higher molecular weight lignin enhanced the resulting shear modulus due to efficient network formation of telechelic polybutadiene bridges. The storage modulus in the rubbery plateau region increased with increasing lignin content. The successful synthesis of novel lignin-based thermoplastics will open a new pathway to biomass utilization and will help conserve petrochemicals.

  7. Lignin decomposition along an Alpine elevation gradient in relation to physicochemical and soil microbial parameters.

    PubMed

    Duboc, Olivier; Dignac, Marie-France; Djukic, Ika; Zehetner, Franz; Gerzabek, Martin H; Rumpel, Cornelia

    2014-07-01

    Lignin is an aromatic plant compound that decomposes more slowly than other organic matter compounds; however, it was recently shown that lignin could decompose as fast as litter bulk carbon in minerals soils. In alpine Histosols, where organic matter dynamics is largely unaffected by mineral constituents, lignin may be an important part of soil organic matter (SOM). These soils are expected to experience alterations in temperature and/or physicochemical parameters as a result of global climate change. The effect of these changes on lignin dynamics remains to be examined and the importance of lignin as SOM compound in these soils evaluated. Here, we investigated the decomposition of individual lignin phenols of maize litter incubated for 2 years in-situ in Histosols on an Alpine elevation gradient (900, 1300, and 1900 m above sea level); to this end, we used the cupric oxide oxidation method and determined the phenols' (13) C signature. Maize lignin decomposed faster than bulk maize carbon in the first year (86 vs. 78% decomposed); however, after the second year, lignin and bulk C decomposition did not differ significantly. Lignin mass loss did not correlate with soil temperature after the first year, and even correlated negatively at the end of the second year. Lignin mass loss also correlated negatively with the remaining maize N at the end of the second year, and we interpreted this result as a possible negative influence of nitrogen on lignin degradation, although other factors (notably the depletion of easily degradable carbon sources) may also have played a role at this stage of decomposition. Microbial community composition did not correlate with lignin mass loss, but it did so with the lignin degradation indicators (Ac/Al)s and S/V after 2 years of decomposition. Progressing substrate decomposition toward the final stages thus appears to be linked with microbial community differentiation. PMID:24323640

  8. Lignin decomposition along an Alpine elevation gradient in relation to physicochemical and soil microbial parameters.

    PubMed

    Duboc, Olivier; Dignac, Marie-France; Djukic, Ika; Zehetner, Franz; Gerzabek, Martin H; Rumpel, Cornelia

    2014-07-01

    Lignin is an aromatic plant compound that decomposes more slowly than other organic matter compounds; however, it was recently shown that lignin could decompose as fast as litter bulk carbon in minerals soils. In alpine Histosols, where organic matter dynamics is largely unaffected by mineral constituents, lignin may be an important part of soil organic matter (SOM). These soils are expected to experience alterations in temperature and/or physicochemical parameters as a result of global climate change. The effect of these changes on lignin dynamics remains to be examined and the importance of lignin as SOM compound in these soils evaluated. Here, we investigated the decomposition of individual lignin phenols of maize litter incubated for 2 years in-situ in Histosols on an Alpine elevation gradient (900, 1300, and 1900 m above sea level); to this end, we used the cupric oxide oxidation method and determined the phenols' (13) C signature. Maize lignin decomposed faster than bulk maize carbon in the first year (86 vs. 78% decomposed); however, after the second year, lignin and bulk C decomposition did not differ significantly. Lignin mass loss did not correlate with soil temperature after the first year, and even correlated negatively at the end of the second year. Lignin mass loss also correlated negatively with the remaining maize N at the end of the second year, and we interpreted this result as a possible negative influence of nitrogen on lignin degradation, although other factors (notably the depletion of easily degradable carbon sources) may also have played a role at this stage of decomposition. Microbial community composition did not correlate with lignin mass loss, but it did so with the lignin degradation indicators (Ac/Al)s and S/V after 2 years of decomposition. Progressing substrate decomposition toward the final stages thus appears to be linked with microbial community differentiation.

  9. Performance of biofuel processes utilising separate lignin and carbohydrate processing.

    PubMed

    Melin, Kristian; Kohl, Thomas; Koskinen, Jukka; Hurme, Markku

    2015-09-01

    Novel biofuel pathways with increased product yields are evaluated against conventional lignocellulosic biofuel production processes: methanol or methane production via gasification and ethanol production via steam-explosion pre-treatment. The novel processes studied are ethanol production combined with methanol production by gasification, hydrocarbon fuel production with additional hydrogen produced from lignin residue gasification, methanol or methane synthesis using synthesis gas from lignin residue gasification and additional hydrogen obtained by aqueous phase reforming in synthesis gas production. The material and energy balances of the processes were calculated by Aspen flow sheet models and add on excel calculations applicable at the conceptual design stage to evaluate the pre-feasibility of the alternatives. The processes were compared using the following criteria: energy efficiency from biomass to products, primary energy efficiency, GHG reduction potential and economy (expressed as net present value: NPV). Several novel biorefinery concepts gave higher energy yields, GHG reduction potential and NPV. PMID:26056782

  10. Performance of biofuel processes utilising separate lignin and carbohydrate processing.

    PubMed

    Melin, Kristian; Kohl, Thomas; Koskinen, Jukka; Hurme, Markku

    2015-09-01

    Novel biofuel pathways with increased product yields are evaluated against conventional lignocellulosic biofuel production processes: methanol or methane production via gasification and ethanol production via steam-explosion pre-treatment. The novel processes studied are ethanol production combined with methanol production by gasification, hydrocarbon fuel production with additional hydrogen produced from lignin residue gasification, methanol or methane synthesis using synthesis gas from lignin residue gasification and additional hydrogen obtained by aqueous phase reforming in synthesis gas production. The material and energy balances of the processes were calculated by Aspen flow sheet models and add on excel calculations applicable at the conceptual design stage to evaluate the pre-feasibility of the alternatives. The processes were compared using the following criteria: energy efficiency from biomass to products, primary energy efficiency, GHG reduction potential and economy (expressed as net present value: NPV). Several novel biorefinery concepts gave higher energy yields, GHG reduction potential and NPV.

  11. Lignin Based Carbon Materials for Energy Storage Applications

    SciTech Connect

    Chatterjee, Sabornie; Saito, Tomonori; Rios, Orlando; Johs, Alexander

    2014-01-01

    The implementation of Li-ion battery technology into electric and hybrid electric vehicles and portable electronic devices such as smart phones, laptops and tablets, creates a demand for efficient, economic and sustainable materials for energy storage. However, the high cost and long processing time associated with manufacturing battery-grade anode and cathode materials are two big constraints for lowering the total cost of batteries and environmentally friendly electric vehicles. Lignin, a byproduct of the pulp and paper industry and biorefinery, is one of the most abundant and inexpensive natural biopolymers. It can be efficiently converted to low cost carbon fibers with optimal properties for use as anode materials. Recent developments in the preparation of lignin precursors and conversion to carbon fiber-based anode materials have created a new class of anode materials with excellent electrochemical characteristics suitable for immediate use in existing Li- or Na-ion battery technologies.

  12. Molecular Dynamics Simulations of Lignin Peroxidase in Solution

    PubMed Central

    Francesca Gerini, M.; Roccatano, Danilo; Baciocchi, Enrico; Nola, Alfredo Di

    2003-01-01

    The dynamical and structural properties of lignin peroxidase and its Trp171Ala mutant have been investigated in aqueous solution using molecular dynamics (MD) simulations. In both cases, the enzyme retained its overall backbone structure and all its noncovalent interactions in the course of the MD simulations. Very interestingly, the analysis of the MD trajectories showed the presence of large fluctuations in correspondence of the residues forming the heme access channel; these movements enlarge the opening and facilitate the access of substrates to the enzyme active site. Moreover, steered molecular dynamics docking simulations have shown that lignin peroxidase natural substrate (veratryl alcohol) can easily approach the heme edge through the access channel. PMID:12770894

  13. Polymeric materials in Space

    NASA Astrophysics Data System (ADS)

    Skurat, Vladimir

    Paper of short review type. It is the continuation of and addition to previous review papers "V. E. Skurat. Polymers in Space. In: Encyclopedia of aerospace engineering, vol. 4, Wiley and sons, 2010; Ibid., 2012 (on line)". Following topics are considered: (1) Destruction of polymers by solar radiation with various wavelengths in different spectral regions (visible-UV, vacuum UV (VUV), deep UV, soft and hard X-rays) are discussed. In difference with common polymer photochemistry induced by UV radiation, directions of various routs of polymer phototransformations and their relative yields are greatly dependent on wavelength of light (photon energy) during illuminations in VUV, deep UV and X-ray regions. During last twenty years, intensive spacecraft investigations of solar spectrum show great periodic and spontaneous variations of radiation intensities in short-wavelengths regions - up to one - two decimal orders of magnitude for X-rays. As a result, during solar flares the absorbed dose on the polymer surfaces from X-rays can be compared with absorbed dose from VUV radiation. (2) Some new approaches to predictions of reaction efficiencies of fast orbital atomic oxygen in their interaction with polymeric materials are considered. (3) Some aspects of photocatalitic destruction of polymers in vacuum conditions by full-spectrum solar radiation are discussed. This process can take place in enamels containing semiconducting particles (TiO2, ZnO) as pigments. (4) Contamination of spacecraft surfaces from intrinsic outer atmosphere play important role not only from the point of view of deterioration of optical and thermophysical properties. Layers of SiO2 contaminations with nanometer thicknesses can greatly diminish mass losses from perfluorinated polymers under VUV irradiation.

  14. Polymeric materials for neovascularization

    NASA Astrophysics Data System (ADS)

    DeVolder, Ross John

    Revascularization therapies have emerged as a promising strategy to treat various acute and chronic wounds, cardiovascular diseases, and tissue defects. It is common to either administer proangiogenic growth factors, such as vascular endothelial growth factor (VEGF), or transplant cells that endogenously express multiple proangiogenic factors. Additionally, these strategies utilize a wide variety of polymeric systems, including hydrogels and biodegradable plastics, to deliver proangiogenic factors in a sophisticated manner to maintain a sustained proangiogenic environment. Despite some impressive results in rebuilding vascular networks, it is still a challenging task to engineer mature and functional neovessels in target tissues, because of the increasing complexities involved with neovascularization applications. To resolve these challenges, this work aims to design a wide variety of proangiogenic biomaterial systems with tunable properties used for neovascularization therapies. This thesis describes the design of several biomaterial systems used for the delivery of proangiogenic factors in neovascularization therapies, including: an electrospun/electrosprayed biodegradable plastic patch used for directional blood vessel growth (Chapter 2), an alginate-g-pyrrole hydrogel system that biochemically stimulates cellular endogenous proangiogenic factor expression (Chapter 3), an enzyme-catalyzed alginate-g-pyrrole hydrogel system for VEGF delivery (Chapter 4), an enzyme-activated alginate-g-pyrrole hydrogel system with systematically controllable electrical and mechanical properties (Chapter 5), and an alginate-g-pyrrole hydrogel that enables the decoupled control of electrical conductivity and mechanical rigidity and is use to electrically stimulate cellular endogenous proangiogenic factor expression (Chapter 6). Overall, the biomaterial systems developed in this thesis will be broadly useful for improving the quality of a wide array of molecular and cellular based

  15. Countercurrent Process for Lignin Separation from Biomass Matrix

    SciTech Connect

    Kiran Kadam; Ed Lehrburger

    2006-03-31

    The overall goal of the project was to test the concept of using a twin-screw extruder to conduct autohydrolysis pretreatment of wheat straw in countercurrent fashion, demonstrate in situ solid/liquid separation, and produce a low-lignin cellulose product using ethanol as an extractant. The resultant solid product is suitable for sugar production through enzymatic hydrolysis and for pulp applications. Pilot-scale equipment was used to successfully demonstrate the process both for sugar and pulp applications.

  16. Phenolic compounds in ectomycorrhizal interaction of lignin modified silver birch

    PubMed Central

    Sutela, Suvi; Niemi, Karoliina; Edesi, Jaanika; Laakso, Tapio; Saranpää, Pekka; Vuosku, Jaana; Mäkelä, Riina; Tiimonen, Heidi; Chiang, Vincent L; Koskimäki, Janne; Suorsa, Marja; Julkunen-Tiitto, Riitta; Häggman, Hely

    2009-01-01

    Background The monolignol biosynthetic pathway interconnects with the biosynthesis of other secondary phenolic metabolites, such as cinnamic acid derivatives, flavonoids and condensed tannins. The objective of this study is to evaluate whether genetic modification of the monolignol pathway in silver birch (Betula pendula Roth.) would alter the metabolism of these phenolic compounds and how such alterations, if exist, would affect the ectomycorrhizal symbiosis. Results Silver birch lines expressing quaking aspen (Populus tremuloides L.) caffeate/5-hydroxyferulate O-methyltransferase (PtCOMT) under the 35S cauliflower mosaic virus (CaMV) promoter showed a reduction in the relative expression of a putative silver birch COMT (BpCOMT) gene and, consequently, a decrease in the lignin syringyl/guaiacyl composition ratio. Alterations were also detected in concentrations of certain phenolic compounds. All PtCOMT silver birch lines produced normal ectomycorrhizas with the ectomycorrhizal fungus Paxillus involutus (Batsch: Fr.), and the formation of symbiosis enhanced the growth of the transgenic plants. Conclusion The down-regulation of BpCOMT in the 35S-PtCOMT lines caused a reduction in the syringyl/guaiacyl ratio of lignin, but no significant effect was seen in the composition or quantity of phenolic compounds that would have been caused by the expression of PtCOMT under the 35S or UbB1 promoter. Moreover, the detected alterations in the composition of lignin and secondary phenolic compounds had no effect on the interaction between silver birch and P. involutus. PMID:19788757

  17. Development of a prototype lignin concentration sensor. Final report. Draft

    SciTech Connect

    Jeffers, L.A.

    1994-11-01

    The ultimate objective of the DOE-sponsored program discussed in this report is to commercialize an instrument for real-time, in-situ measurement of lignin in wood pulp at a variety of locations in the pulp process stream. The instrument will be used as a primary sensor for process control in the pulp and paper industry. Work done by B&W prior to the initiation of this program had shown: there is a functional relationship between the fluorescence intensity and the Kappa number as measured at the pulp mill laboratory. Kappa number is a standard wet chemical method for determination of the lignin concentration; the relationship is one of decreasing intensity with Kappa number, indicating operation in the quenched fluorescence regime; a great deal of scatter in the data. Because of the preliminary nature of the study, the origin of the scatter was not identified. This report documents the results of laboratory measurements made on a variety of well defined pulp samples to generate the data necessary to: determine the feasibility of an instrument for on-line lignin concentration measurement using laser fluorescence; identify the preferred measurement strategy; define the range of applicability of the instrument; and to provide background information to guide the design of a field-worthy prototype.

  18. Heterogeneous Ozonolysis of Surface Adsorbed Lignin Pyrolysis Products

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.

    2012-12-01

    Biomass combustion releases semi-volatile organic compounds into the troposphere, including many phenols and methoxyphenols as the result of lignin pyrolysis. Given their relatively low vapor pressures, these compounds readily adsorb on inorganic and organic aerosol substrates where they may alter aerosol properties and undergo heterogeneous chemistry. We use infrared spectroscopy (DRIFTS and ATR-FTIR) to monitor the adsorption and subsequent heterogeneous ozonolysis of model lignin pyrolysis products, including catechol, eugenol, and 4-propylguaiacol. Ozonolysis reaction kinetics were compared on various inorganic substrates - such as Al2O3 and NaCl, which serve as mineral and sea salt aerosol substrates, respectively - and as a function of ozone concentration and relative humidity. Following in situ FTIR analysis, the adsorbed organics were extracted and analyzed using gas chromatography-mass spectroscopy to identify reaction products and quantify product branching ratios. Ozonolysis of catechol and 4-propylguaiacol readily resulted in ring cleavage forming dicarboxylic acids (e.g., muconic acid). Eugenol ozonolysis proceeded rapidly at the alkene side chain producing homovanillic acid and homovanillin in an approximate 2:1 branching ratio at 0% RH; ring cleavage was also observed. For all lignin pyrolysis products, heterogeneous ozonolysis was faster on NaCl versus Al2O3. Implications for the atmospheric chemistry of semi-volatile methoxylphenols adsorbed on aerosol substrates will be discussed.

  19. Mechanistic Study of the Acid Degradation of Lignin Model Compounds

    SciTech Connect

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

    2012-01-01

    Lignin is a major constituent of biomass, which remains underutilized in selective biomass conversion strategies to renewable fuels and chemicals. Here we are interested in understanding the mechanisms related to the acid deconstruction of lignin with a combined theoretical and experimental approach. Two model dimers with a b-O-4 aryl ether linkage (2-phenoxy-1-phenethanol and 2-phenoxy-1-phenyl-1,3 propanediol) and model dimmers with an a-O-4 aryl ether linkage were synthesized and deconstructed in H2SO4. The major products of the acidolysis of the b-O-4 compounds consisted of phenol and two aldehydes, phenylacetaldehyde and benzaldehyde. Quantum mechanical calculations were employed to elucidate possible deconstruction mechanisms with transition state theory. To confirm proposed mechanisms several possible intermediates were studied under similar acidolysis conditions. Although the resonance time for cleavage was on the order several hours, we have shown that the cleavage of the aryl ether linkage affords phenol and aldehydes. We would next like to utilize our mechanism of aryl ether cleavage in actual lignin.

  20. Mechanochemical solid-state polymerization. VIII. Novel composite polymeric prodrugs prepared by mechanochemical polymerization in the presence of pharmaceutical aids.

    PubMed

    Kondo, S; Hosaka, S; Kuzuya, M

    1998-04-01

    We carried out the mechanochemical polymerization of methacryloyl derivatives of acetoaminophen and 5-fluorouracil in the presence of lactose. The reaction proceeded readily and the polymeric prodrugs were quantitatively produced. This method produces powdered polymeric prodrugs in which fine particles of lactose are homogeneously dispersed, since the reaction proceeds quantitatively through a totally dry process. It is difficult to prepare such a powdered polymeric prodrug by conventional solution polymerization. The rate of drug release of polymeric prodrugs increases with increasing content of lactose, as is shown to be true of the specific surface of polymeric prodrugs. These results suggest that lactose is homogeneously dispersed in powdered polymeric prodrugs. The present method seems applicable to a wide variety of pharmaceutical aids. If one takes the physiochemical property of pharmaceutical aids into consideration, novel polymeric prodrugs with a variety of drug release rates can be synthesized simultaneously with mixing. PMID:9579043

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

    PubMed

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

    2016-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

  3. Synthesis and properties of lignin peroxidase from Streptomyces viridosporus T7A

    SciTech Connect

    Lodha, S.J.; Korus, R.A.; Crawford, D.L.

    1991-12-31

    The production of lignin peroxidase by Streptomyces viridosporus T7A was studied in shake flasks and under aerobic conditions in a 7.5-L batch fermentor. Lignin peroxidase synthesis was found to be strongly affected by catabolite repression. Lignin peroxidase was a non-growth-associated, secondary metabolite. The maximum lignin peroxidase activity was 0.064 U/mL at 36 h. In order to maximize lignin peroxidase activity, optimal conditions were determined. The optimal incubation temperature, pH, and substrate (2,4-dichlorophenol) concentration for the enzyme assays were 45{degrees}C, 6, and 3 m-M, respectively. Stability of lignin peroxidase was determined at 37, 45, and 60{degrees}C, and over the pH range 4-9.

  4. Pyrolysis behaviors of four lignin polymers isolated from the same pine wood.

    PubMed

    Wang, Shurong; Ru, Bin; Lin, Haizhou; Sun, Wuxing; Luo, Zhongyang

    2015-04-01

    Four lignin polymers, alkali lignin (AL), klason lignin (KL), organosolv lignin (OL), and milled wood lignin (MWL), were isolated from the same pine wood. Structural characterization by FTIR and (13)C NMR indicated that the four lignins have different structural features. Their pyrolysis behaviors were analyzed by TG-FTIR and Py-GC/MS. Thermally unstable ether bonds and side branches were well-preserved in AL and MWL, but were broken in OL and KL. Pyrolysis of AL and KL produce more phenols at low temperature by the breakage of ether bonds. AL and KL show lower activation energies in the main degradation stage, quantified by a distribution activation energy model with two linearly combined Gaussian functions. The evolution behaviors of typical gaseous products, CH4, CO2, and CO, were analyzed, and insights about the correlation between chemical structure and pyrolysis behavior were obtained.

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

    PubMed

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

    2016-04-01

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

  6. Microwave-assisted oxidative digestion of lignin with hydrogen peroxide for TOC and color removal.

    PubMed

    Ouyang, Xinping; Huang, Xiangzhen; Ruan, Tao; Qiu, Xueqing

    2015-01-01

    Dilute lignin solution was successfully digested into colorless and clarified liquor under microwave-assisted oxidative digestion with hydrogen peroxide. High dosage of hydrogen peroxide is needed to effectively digest lignin, but excessive hydrogen peroxide may lead to recondensation of formed fragments in digested lignin. Microwave irradiation greatly facilitates the oxidative digestion of lignin. Compared with conventional heating technique, microwave-assisted digestion achieves the same or higher digestion rate within a shorter time and/or at lower temperature. After digestion, total organic carbon content of lignin solution decreases by 93.9%, and a small amount of aliphatic alkane, alcohol, acid and ester are formed via the cleavage of aromatic rings as well as the deprivation of side chains in original lignin. This work provides an alternative way to efficiently treat spent pulping liquor. PMID:25714638

  7. Tandem Catalytic Depolymerization of Lignin by Water-Tolerant Lewis Acids and Rhodium Complexes.

    PubMed

    Jastrzebski, Robin; Constant, Sandra; Lancefield, Christopher S; Westwood, Nicholas J; Weckhuysen, Bert M; Bruijnincx, Pieter C A

    2016-08-23

    Lignin is an attractive renewable feedstock for aromatic bulk and fine chemicals production, provided that suitable depolymerization procedures are developed. Here, we describe a tandem catalysis strategy for ether linkage cleavage within lignin, involving ether hydrolysis by water-tolerant Lewis acids followed by aldehyde decarbonylation by a Rh complex. In situ decarbonylation of the reactive aldehydes limits loss of monomers by recondensation, a major issue in acid-catalyzed lignin depolymerization. Rate of hydrolysis and decarbonylation were matched using lignin model compounds, allowing the method to be successfully applied to softwood, hardwood, and herbaceous dioxasolv lignins, as well as poplar sawdust, to give the anticipated decarbonylation products and, rather surprisingly, 4-(1-propenyl)phenols. Promisingly, product selectivity can be tuned by variation of the Lewis-acid strength and lignin source. PMID:27440544

  8. Approaches to the selective catalytic conversion of lignin: a grand challenge for biorefinery development.

    PubMed

    Bozell, Joseph J

    2014-01-01

    Lignin comprises 15-25% of terrestrial biomass and is the second most abundant source of renewable carbon after cellulose. However, its structural heterogeneity frustrates efforts for its selective conversion into biobased chemicals. Catalyst design for lignin transformation offers an opportunity to improve selectivity, and, hence, improve lignin's utility as a raw material in chemical production. Catalytic deconstruction and conversion of lignin has been examined using a variety of thermochemical treatments, analogous to those used in the petrochemical industry. However, the complex nature of these products limits their utility. More recently, greater focus has been given to an understanding of lignin's molecular level structure, and designing catalysts that can be targeted to key individual structural units within the biopolymer. This review gives a sense of the field by providing a representative description of recent developments in some of the primary technologies employed for lignin conversion and approaches that promise to improve selectivity. PMID:24696353

  9. The emerging role for bacteria in lignin degradation and bio-product formation.

    PubMed

    Bugg, Timothy D H; Ahmad, Mark; Hardiman, Elizabeth M; Singh, Rahul

    2011-06-01

    The microbial degradation of lignin has been well studied in white-rot and brown-rot fungi, but is much less well studied in bacteria. Recent published work suggests that a range of soil bacteria, often aromatic-degrading bacteria, are able to break down lignin. The enzymology of bacterial lignin breakdown is currently not well understood, but extracellular peroxidase and laccase enzymes appear to be involved. There are also reports of aromatic-degrading bacteria isolated from termite guts, though there are conflicting reports on the ability of termite gut micro-organisms to break down lignin. If biocatalytic routes for lignin breakdown could be developed, then lignin represents a potentially rich source of renewable aromatic chemicals.

  10. Microwave-assisted oxidative digestion of lignin with hydrogen peroxide for TOC and color removal.

    PubMed

    Ouyang, Xinping; Huang, Xiangzhen; Ruan, Tao; Qiu, Xueqing

    2015-01-01

    Dilute lignin solution was successfully digested into colorless and clarified liquor under microwave-assisted oxidative digestion with hydrogen peroxide. High dosage of hydrogen peroxide is needed to effectively digest lignin, but excessive hydrogen peroxide may lead to recondensation of formed fragments in digested lignin. Microwave irradiation greatly facilitates the oxidative digestion of lignin. Compared with conventional heating technique, microwave-assisted digestion achieves the same or higher digestion rate within a shorter time and/or at lower temperature. After digestion, total organic carbon content of lignin solution decreases by 93.9%, and a small amount of aliphatic alkane, alcohol, acid and ester are formed via the cleavage of aromatic rings as well as the deprivation of side chains in original lignin. This work provides an alternative way to efficiently treat spent pulping liquor.

  11. Free radical scavenging activity and reducing power of Acacia nilotica wood lignin.

    PubMed

    Aadil, Keshaw Ram; Barapatre, Anand; Sahu, Sudha; Jha, Harit; Tiwary, Bhupendra Nath

    2014-06-01

    Nine different fractions of lignin extracted by alkali, hot water and organosolv methods from Acacia wood powder were assessed for antioxidants activity. Results indicated that methanolic lignin fraction had highest polyphenol content of 393.30±9.2μg/ml (GAE). The oraganosolv lignin with total phenols and phenolic hydroxyl group content exhibited significant antioxidant activity as compared to other lignin fractions. Antioxidant properties of acetone fractions revealed a high antiradical scavenging activity (<90%) with a simultaneous high ferric and molybdate ion reducing capacity. The influence of extraction methods on functional groups of lignin fractions was confirmed by analytical methods and Fourier transform infrared spectroscopy (FTIR) analysis. Whereas the phenolic content showed strong correlation with reducing capacity, the antiradical activity was moderately correlated with phenolic content. A high phenolic hydroxyl groups content of organosolv lignin fractions provides evidence for the presence of active therapeutic antioxidant compounds for their testing as potential value added products for cosmetics and pharmaceutical industries.

  12. High-Strength Composite Fibers from Cellulose-Lignin Blends Regenerated from Ionic Liquid Solution.

    PubMed

    Ma, Yibo; Asaadi, Shirin; Johansson, Leena-Sisko; Ahvenainen, Patrik; Reza, Mehedi; Alekhina, Marina; Rautkari, Lauri; Michud, Anne; Hauru, Lauri; Hummel, Michael; Sixta, Herbert

    2015-12-01

    Composite fibres that contain cellulose and lignin were produced from ionic liquid solutions by dry-jet wet spinning. Eucalyptus dissolving pulp and organosolv/kraft lignin blends in different ratios were dissolved in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate to prepare a spinning dope from which composite fibres were spun successfully. The composite fibres had a high strength with slightly decreasing values for fibres with an increasing share of lignin, which is because of the reduction in crystallinity. The total orientation of composite fibres and SEM images show morphological changes caused by the presence of lignin. The hydrophobic contribution of lignin reduced the vapour adsorption in the fibre. Thermogravimetric analysis curves of the composite fibres reveal the positive effect of the lignin on the carbonisation yield. Finally, the composite fibre was found to be a potential raw material for textile manufacturing and as a precursor for carbon fibre production.

  13. Lignocellulose Nanofiber-Reinforced Polystyrene Produced from Composite Microspheres Obtained in Suspension Polymerization Shows Superior Mechanical Performance.

    PubMed

    Ballner, Daniel; Herzele, Sabine; Keckes, Jozef; Edler, Matthias; Griesser, Thomas; Saake, Bodo; Liebner, Falk; Potthast, Antje; Paulik, Christian; Gindl-Altmutter, Wolfgang

    2016-06-01

    A facile approach to obtaining cellulose nanofiber-reinforced polystyrene with greatly improved mechanical performance compared to unreinforced polystyrene is presented. Cellulose nanofibers were obtained by mechanical fibrillation of partially delignified wood (MFLC) and compared to nanofibers obtained from bleached pulp. Residual hemicellulose and lignin imparted amphiphilic surface chemical character to MFLC, which enabled the stabilization of emulsions of styrene in water. Upon suspension polymerization of styrene from the emulsion, polystyrene microspheres coated in MFLC were obtained. When processed into polymer sheets by hot-pressing, improved bending strength and superior impact toughness was observed for the polystyrene-MFLC composite compared to the un-reinforced polystyrene. PMID:27163488

  14. Lignocellulose Nanofiber-Reinforced Polystyrene Produced from Composite Microspheres Obtained in Suspension Polymerization Shows Superior Mechanical Performance.

    PubMed

    Ballner, Daniel; Herzele, Sabine; Keckes, Jozef; Edler, Matthias; Griesser, Thomas; Saake, Bodo; Liebner, Falk; Potthast, Antje; Paulik, Christian; Gindl-Altmutter, Wolfgang

    2016-06-01

    A facile approach to obtaining cellulose nanofiber-reinforced polystyrene with greatly improved mechanical performance compared to unreinforced polystyrene is presented. Cellulose nanofibers were obtained by mechanical fibrillation of partially delignified wood (MFLC) and compared to nanofibers obtained from bleached pulp. Residual hemicellulose and lignin imparted amphiphilic surface chemical character to MFLC, which enabled the stabilization of emulsions of styrene in water. Upon suspension polymerization of styrene from the emulsion, polystyrene microspheres coated in MFLC were obtained. When processed into polymer sheets by hot-pressing, improved bending strength and superior impact toughness was observed for the polystyrene-MFLC composite compared to the un-reinforced polystyrene.

  15. Tuning the lignin oil OH-content with Ru and Pd catalysts during lignin hydrogenolysis on birch wood.

    PubMed

    Van den Bosch, S; Schutyser, W; Koelewijn, S-F; Renders, T; Courtin, C M; Sels, B F

    2015-08-28

    Liquid reductive processing of birch wood in the presence of commercial Ru/C or Pd/C catalysts yields about 50% of a select set of phenolic monomers and a variety of phenolic di- and oligomers, next to a solid carbohydrate pulp. Changing the catalyst from Ru/C to Pd/C drastically increases the OH-content of the lignin-derived products, in particular for the phenolic monomers.

  16. Characterization of Trapped Lignin-Degrading Microbes in Tropical Forest Soil

    SciTech Connect

    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.

  17. Characterization of trapped lignin-degrading microbes in tropical forest soil

    SciTech Connect

    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.

  18. Characterization of Trapped Lignin-Degrading Microbes in Tropical Forest Soil

    SciTech Connect

    DeAngelis, Kristen M.; Allgaier, Martin; Chavarria, Yaucin; Fortney, Julian L.; Hugenholtz, Philip; Simmons, Blake A.; Sublette, Kerry; Silver, Whendee; Hazen, Terry C.

    2011-04-29

    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.

  19. On-line measurement of lignin in wood pulp by color shift of fluorescence

    DOEpatents

    Jeffers, Larry A.; Malito, Michael L.

    1996-01-01

    Lignin concentrations from wood pulp samples are measured by applying an excitation light at a selected wavelength to the samples in order to cause the lignin to emit fluorescence. A spectral distribution of the fluorescence emission is then determined. The lignin concentration is then calculated based on the spectral distribution signal. The spectral distribution is quantified by either a wavelength centroid method or a band ratio method.

  20. On-line measurement of lignin in wood pulp by color shift of fluorescence

    DOEpatents

    Jeffers, L.A.; Malito, M.L.

    1996-01-23

    Lignin concentrations from wood pulp samples are measured by applying an excitation light at a selected wavelength to the samples in order to cause the lignin to emit fluorescence. A spectral distribution of the fluorescence emission is then determined. The lignin concentration is then calculated based on the spectral distribution signal. The spectral distribution is quantified by either a wavelength centroid method or a band ratio method. 6 figs.