WorldWideScience

Sample records for oxidized lignin solubility

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

    OpenAIRE

    Joshua, CJ; Simmons, BA; Singer, SW

    2016-01-01

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

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

    DEFF Research Database (Denmark)

    2016-01-01

    Solvent consumption in supercritical ethanol, propanol or butanol treatment of either refined pre-extracted lignin or comparatively impure lignin-rich solid residual from hydrothermally pretreated lignocellulosic biomass can be minimized by conducting the reaction at very high loading of lignin...... to solvent. Comparatively impure, crude lignin- rich solid residual can be directly converted by supercritical alcohol treatment to significantly diesel-soluble lignin oil without requirement for pre-extraction or pre- solubilisation of lignin or for added reaction promoters such as catalysts, hydrogen donor...... co-solvents, acids, based or H2 gas. O:C ratio of product oil can readily be obtained using crude lignin residual in such a process at levels 0.20 or lower....

  3. Selective Oxidation of Lignin Model Compounds.

    Science.gov (United States)

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

    2018-05-02

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

  4. Catalytic hydrotreating of lignin with water-soluble molybdenum catalyst

    Energy Technology Data Exchange (ETDEWEB)

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

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

  5. Lignin Valorization using Heterogenous Catalytic Oxidation

    DEFF Research Database (Denmark)

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

    The research interests in biomass conversion to fuels and chemicals has increased significantly in the last decade in view of current problems such as global warming, high oil prices, food crisis and other geopolitical scenarios. Many different reactions and processes to convert biomass into high...... of the reaction conditions 4. Here, we therefore present an overview of the recent research about conversion of some lignin model compounds using heterogeneous catalysis in oxidation reactions....

  6. Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol

    DEFF Research Database (Denmark)

    Warner, Genoa; Hansen, Thomas Søndergaard; Riisager, Anders

    2014-01-01

    conversion to methanol-soluble products, without char formation, were based on copper in combination with other dopants based on relatively earth-abundant metals. Nearly complete conversion of lignin to bio-oil composed of monomers and low-mass oligomers with high aromatic content was obtained in 6. h at 310......An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin...

  7. Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

    International Nuclear Information System (INIS)

    Das, Lalitendu; Xu, Siquan; Shi, Jian

    2017-01-01

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

  8. Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-08-10

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

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  10. Nitroxyl-mediated oxidation of lignin and polycarboxylated products

    Energy Technology Data Exchange (ETDEWEB)

    Stahl, Shannon S.; Rafiee, Mohammad

    2018-02-27

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

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

    Directory of Open Access Journals (Sweden)

    Wei Fang

    Full Text Available The digestion of lignin and lignin-related phenolic compounds from bamboo by giant pandas has puzzled scientists because of the lack of lignin-degrading genes in the genome of the bamboo-feeding animals. We constructed a 16S rRNA gene library from the microorganisms derived from the giant panda feces to identify the possibility for the presence of potential lignin-degrading bacteria. Phylogenetic analysis showed that the phylotypes of the intestinal bacteria were affiliated with the phyla Proteobacteria (53% and Firmicutes (47%. Two phylotypes were affiliated with the known lignin-degrading bacterium Pseudomonas putida and the mangrove forest bacteria. To test the hypothesis that microbes in the giant panda gut help degrade lignin, a metagenomic library of the intestinal bacteria was constructed and screened for clones that contained genes encoding laccase, a lignin-degrading related enzyme. A multicopper oxidase gene, designated as lac51, was identified from a metagenomic clone. Sequence analysis and copper content determination indicated that Lac51 is a laccase rather than a metallo-oxidase and may work outside its original host cell because it has a TAT-type signal peptide and a transmembrane segment at its N-terminus. Lac51 oxidizes a variety of lignin-related phenolic compounds, including syringaldazine, 2,6-dimethoxyphenol, ferulic acid, veratryl alcohol, guaiacol, and sinapinic acid at conditions that simulate the physiologic environment in giant panda intestines. Furthermore, in the presence of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS, syringic acid, or ferulic acid as mediators, the oxidative ability of Lac51 on lignin was promoted. The absorbance of lignin at 445 nm decreased to 36% for ABTS, 51% for syringic acid, and 51% for ferulic acid after incubation for 10 h. Our findings demonstrate that the intestinal bacteria of giant pandas may facilitate the oxidation of lignin moieties, thereby clarifying the digestion

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

    African Journals Online (AJOL)

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

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

    Science.gov (United States)

    Stahl, Shannon S; Rahimi, Alireza

    2015-03-03

    Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

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

    Science.gov (United States)

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

    2014-11-01

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

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

    African Journals Online (AJOL)

    2011-01-11

    Jan 11, 2011 ... Oxygen oxidation has previously been shown to produce aldehyde-type compounds, and in this work has produced good yields of both vanillin and syringaldehyde compared to previous oxygen oxidation reac- tions. Hydrogen peroxide is a strong oxidising agent that tends to over-oxidise the lignin during ...

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

    International Nuclear Information System (INIS)

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

    1999-01-01

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

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

    Science.gov (United States)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2013-01-01

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

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

    Science.gov (United States)

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

    2018-03-14

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

  20. Enzymatically and chemically oxidized lignin nanoparticles for biomaterial applications.

    Science.gov (United States)

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

    2018-04-01

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

  1. AN OXIDANT TO REPLACE NITROBENZENE IN LIGNIN ANALYSIS

    Directory of Open Access Journals (Sweden)

    Michael P. Masingale

    2009-08-01

    Full Text Available Four metal organic frameworks (MOFs are being evaluated as possible catalysts for alkaline lignin oxidation. One aspect of the screening process is the oxidation of in-situ hardwood lignin by a high mole ratio of Cu, Fe, or Cu + Fe contained in the MOFs. The MOF’s were prepared in a microwave-assisted synthesis. One of the MOFs, a benzenetricar-boxylic acid complex of Cu (II and Fe (III, converted the phenylpropane (C9 units in in-situ poplar lignin to approximately 50% monomers. The ratio of syringyl (S to guiacyl (G monomers was similar to the S:G ratio obtained from nitrobenzene oxidation (NBO. The S:G ratio from NBO was then compared to that from MOF oxidation (MOFO for two other poplars. The S:G ratios for the three poplars by MOFO were 1.20, 1.51 and 1.67, respectively while the corresponding NBO values were 1.25, 1.45 and 1.68. These initial results indicate that MOFO could be developed into a credible replacement for NBO, because it affords a higher yield of monomers when a large MOF dose is used. Some preliminary results are also presented for MOF acting as a catalyst (100 ppm Cu (II plus 81 ppm Fe (III in NaOH for oxygenation of the hardwoods. The products from O2 + MOF are identical to MOF only, but the ratios amongst them are different.

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

    Science.gov (United States)

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

    2004-01-01

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

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

    DEFF Research Database (Denmark)

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

    2015-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-30

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

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

    NARCIS (Netherlands)

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

    2013-01-01

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

  6. Solubility study of Tc(IV) oxides

    International Nuclear Information System (INIS)

    Liu, D.J.; Fan, X.H.

    2005-01-01

    The deep geological disposal of the high level radioactive wastes is expected to be a safer disposal method in most countries. The long-lived fission product 99 Tc is present in large quantities in nuclear wastes and its chemical behavior in aqueous solution is of considerable interest. Under oxidizing conditions technetium exists as the anionic species TcO 4 - whereas under the reducing conditions, expected to exist in a deep geological repository, it is generally predicted that technetium will be present as TcO 2 ·nH 2 O. Hence, the mobility of Tc(IV) in reducing groundwater may be limited by the solubility of TcO 2 ·nH 2 O under these conditions. Due to this fact it is important to investigate the solubility of TcO 2 ·nH 2 O. The solubility determines the release of radionuclides from waste form and is used as a source term in radionuclide migration analysis in performance assessment of radioactive waste repository. Technetium oxide was prepared by reduction of a technetate solution with Sn 2 + . The solubility of Tc(IV) oxide has been determined in simulated groundwater and redistilled water under aerobic and anaerobic conditions. The effects of pH and CO 3 2- concentration of solution on solubility of Tc(IV) oxide were studied. The concentration of total technetium and Tc(IV) species in the solutions were periodically determined by separating the oxidized and reduced technetium species using a solvent extraction procedure and counting the beta activity of the 99 Tc with a liquid scintillation counter. The experimental results show that the rate of oxidation of Tc(IV) in simulated groundwater and redistilled water is about (1.49-1.86) x 10 -9 mol/(L·d) under aerobic conditions, but Tc(IV) in simulated groundwater and redistilled water is not oxidized under anaerobic conditions. Under aerobic or anaerobic conditions the solubility of Tc(IV) oxide in simulated groundwater and redistilled water is equal on the whole after centrifugation or ultrafiltration. The

  7. Water-Soluble Lignins from Different Bioenergy Crops Stimulate the Early Development of Maize (Zea mays, L.

    Directory of Open Access Journals (Sweden)

    Davide Savy

    2015-11-01

    Full Text Available The molecular composition of water-soluble lignins isolated from four non-food bioenergy crops (cardoon CAR, eucalyptus EUC, and two black poplars RIP and LIM was characterized in detail, and their potential bioactivity towards maize germination and early growth evaluated. Lignins were found to not affect seed germination rates, but stimulated the maize seedling development, though to a different extent. RIP promoted root elongation, while CAR only stimulated the length of lateral seminal roots and coleoptile, and LIM improved only the coleoptile development. The most significant bioactivity of CAR was related to its large content of aliphatic OH groups, C-O carbons and lowest hydrophobicity, as assessed by 31P-NMR and 13C-CPMAS-NMR spectroscopies. Less bioactive RIP and LIM lignins were similar in composition, but their stimulation of maize seedling was different. This was accounted to their diverse content of aliphatic OH groups and S- and G-type molecules. The poorest bioactivity of the EUC lignin was attributed to its smallest content of aliphatic OH groups and largest hydrophobicity. Both these features may be conducive of a EUC conformational structure tight enough to prevent its alteration by organic acids exuded from vegetal tissues. Conversely the more labile conformational arrangements of the other more hydrophilic lignin extracts promoted their bioactivity by releasing biologically active molecules upon the action of exuded organic acids. Our findings indicate that water-soluble lignins from non-food crops may be effectively used as plant biostimulants, thus contributing to increase the economic and ecological liability of bio-based industries.

  8. Selective cleavage of the C(α)-C(β) linkage in lignin model compounds via Baeyer-Villiger oxidation.

    Science.gov (United States)

    Patil, Nikhil D; Yao, Soledad G; Meier, Mark S; Mobley, Justin K; Crocker, Mark

    2015-03-21

    Lignin is an amorphous aromatic polymer derived from plants and is a potential source of fuels and bulk chemicals. Herein, we present a survey of reagents for selective stepwise oxidation of lignin model compounds. Specifically, we have targeted the oxidative cleavage of Cα-Cβ bonds as a means to depolymerize lignin and obtain useful aromatic compounds. In this work, we prepared several lignin model compounds that possess structures, characteristic reactivity, and linkages closely related to the parent lignin polymer. We observed that selective oxidation of benzylic hydroxyl groups, followed by Baeyer-Villiger oxidation of the resulting ketones, successfully cleaves the Cα-Cβ linkage in these model compounds.

  9. OXIDATION AND SULFOMETHYLATION OF ALKALI-EXTRACTED LIGNIN FROM CORN STALK

    Directory of Open Access Journals (Sweden)

    Huiran Wu,

    2012-05-01

    Full Text Available A lignosulfonate was prepared from alkali-extracted corn stalk lignin (AEL by oxidation under mild conditions and sulfomethylation. The oxidized AEL exhibited lower molecular weight, narrower molecular weight distribution, and higher phenolic hydroxyl content than AEL, demonstrating that oxidized AEL was more reactive than those before oxidation. The content of sulfonic groups was significantly increased with the increase in sodium sulphite to AEL ratio, while the content slightly decreased when the ratio was above 1:1. During the sulfomethylation, the content of sulfonic groups increased with time and then achieved a constant level with the increase in time. The content of sulfonic groups reached 1.29 mmol/g, the maximum value, at 5 h and a sodium sulphite to AEL ratio of 1:1. The solubility of AEL was obviously improved by sulfomethylation with the increase in the content of sulfonic groups. The surface activity of AEL was improved after sulfomethylation. The sulfomethylation products exhibited good dispersibility and showed potential for use as a dye dispersant.

  10. Solubility of Tc(IV) oxides

    International Nuclear Information System (INIS)

    Liu, D.J.; Fan, X.H.

    2005-01-01

    Full text of publication follows: The deep geological disposal of the high level radioactive wastes is expected to be a safer disposal method in most countries. The long-lived fission product 99 Tc is present in large quantities in nuclear wastes and its chemical behavior in aqueous solution is of considerable interest. Under the reducing conditions, expected to exist in a deep geological repository, it is generally predicted that technetium will be present as TcO 2 .nH 2 O. The solubility of Tc(IV) is used as a source term in performance assessment of radioactive waste repository. Technetium oxide was prepared by reduction of a technetate solution with Sn 2+ . The solubility of Tc(IV) oxide has been determined in simulated groundwater and re-distilled water under aerobic and anaerobic conditions. The effects of pH and CO 3 2- concentration of solution on solubility of Tc(IV) oxide were studied. The concentration of total technetium and Tc(IV) species in the solutions were periodically determined by separating the oxidized and reduced technetium species using a solvent extraction procedure and counting the beta activity of the 99 Tc with a liquid scintillation counter. The experimental results show that the rate of oxidation of Tc(IV) in simulated groundwater and re-distilled water is about (1.49∼1.86) x 10 -9 mol/(L.d) under aerobic conditions, but Tc(IV) in simulated groundwater and re-distilled water is not oxidized under anaerobic conditions. Under aerobic or anaerobic conditions the solubility of Tc(IV) oxide in simulated groundwater and re-distilled water is equal on the whole after centrifugation or ultrafiltration. The solubility of Tc(IV) oxide decreases with the increase of pH at pH 10 and is pH independent in the range 2 -8 to 10 -9 mol/L at 2 3 2- concentration. These data could be used to estimate the Tc(IV) solubility for cases where solubility limits transport of technetium in reducing environments of high-level waste repositories. (authors)

  11. Knocking on wood: base metal complexes as catalysts for selective oxidation of lignin models and extracts.

    Science.gov (United States)

    Hanson, Susan K; Baker, R Tom

    2015-07-21

    This work began as part of a biomass conversion catalysis project with UC Santa Barbara funded by the first NSF Chemical Bonding Center, CATSB. Recognizing that catalytic aerobic oxidation of diol C-C bonds could potentially be used to break down lignocellulose, we began to synthesize oxovanadium complexes and explore their fundamental reactivity. Of course there were theories regarding the oxidation mechanism, but our mechanistic studies soon revealed a number of surprises of the type that keep all chemists coming back to the bench! We realized that these reactions were also exciting in that they actually used the oxygen-on-every-carbon property of biomass-derived molecules to control the selectivity of the oxidation. When we found that these oxovanadium complexes tended to convert sugars predominantly to formic acid and carbon dioxide, we replaced one of the OH groups with an ether and entered the dark world of lignin chemistry. In this Account, we summarize results from our collaboration and from our individual labs. In particular, we show that oxidation selectivity (C-C vs C-O bond cleavage) of lignin models using air and vanadium complexes depends on the ancillary ligands, the reaction solvent, and the substrate structure (i.e., phenolic vs non-phenolic). Selected vanadium complexes in the presence of added base serve as effective alcohol oxidation catalysts via a novel base-assisted dehydrogenation pathway. In contrast, copper catalysts effect direct C-C bond cleavage of these lignin models, presumably through a radical pathway. The most active vanadium catalyst exhibits unique activity for the depolymerization of organosolv lignin. After Weckhuysen's excellent 2010 review on lignin valorization, the number of catalysis studies and approaches on both lignin models and extracts has expanded rapidly. Today we are seeing new start-ups and lignin production facilities sprouting up across the globe as we all work to prove wrong the old pulp and paper chemist

  12. A novel and efficient oxidative functionalization of lignin by layer-by-layer immobilised Horseradish peroxidase.

    Science.gov (United States)

    Perazzini, Raffaella; Saladino, Raffaele; Guazzaroni, Melissa; Crestini, Claudia

    2011-01-01

    Horseradish peroxidase (HRP) was chemically immobilised onto alumina particles and coated by polyelectrolytes layers, using the layer-by-layer technique. The reactivity of the immobilised enzyme was studied in the oxidative functionalisation of softwood milled wood and residual kraft lignins and found higher than the free enzyme. In order to investigate the chemical modifications in the lignin structure, quantitative (31)P NMR was used. The immobilised HRP showed a higher reactivity with respect to the native enzyme yielding extensive depolymerisation of lignin. Copyright © 2010 Elsevier Ltd. All rights reserved.

  13. Method to separate lignin-rich solid phase from acidic biomass suspension at an acidic pH

    Science.gov (United States)

    Yasarla, Kumar Lakshmi Rakesh; Ramarao, Bandaru V; Amidon, Thomas

    2017-09-05

    A method of separating a lignin-rich solid phase from a solution suspension, by pretreating a lignocellulosic biomass with a pretreatment fluid having remove soluble components, colloidal material and primarily lignin containing particles; separating the pretreated lignocellulosic biomass from the pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles; flocculating the separated pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles using polyethylene oxide (i.e., PEO) or cationic Poly acrylamide (i.e., CPAM) as a flocculating agent; and filtering the flocculated separated pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles to remove agglomerates.

  14. Role of Cu-Mg-Al mixed oxide catalysts in lignin depolymerization in supercritical ethanol

    NARCIS (Netherlands)

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

    2015-01-01

    We investigate the role of Cu-Mg-Al mixed oxides in depolymerization of soda lignin in supercritical ethanol. A series of mixed oxides with varying Cu content and (Cu+Mg)/Al ratio were prepared. The optimum catalyst containing 20 wt% Cu and having a (Cu+Mg)/Al ratio of 4 yielded 36 wt% monomers

  15. Oxidative degradation of lignin by photochemical and chemical radical generating systems

    International Nuclear Information System (INIS)

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

    1983-01-01

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

  16. Ultra-high performance supercritical fluid chromatography of lignin-derived phenols from alkaline cupric oxide oxidation.

    Science.gov (United States)

    Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta; Turner, Charlotta

    2016-08-01

    Traditional chromatographic methods for the analysis of lignin-derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra-high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin-derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5-2.5 μM, a limit of quantification of 2.5-5.0 μM, and a dynamic range of 5.0-2.0 mM (R(2) > 0.997). The new ultra-high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin-derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin-derived phenols in complex environmental samples. © 2016 The Authors, Journal of Separation Science Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2013-10-14

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

  18. Soluble and cell wall-bound phenolics and lignin in Ascocalyx abietina infected Norway spruces

    Czech Academy of Sciences Publication Activity Database

    Cvikrová, Milena; Malá, J.; Hrubcová, Marie; Eder, Josef

    2006-01-01

    Roč. 170, č. 3 (2006), s. 563-570 ISSN 0168-9452 R&D Projects: GA ČR GA206/04/0999 Institutional research plan: CEZ:AV0Z50380511 Keywords : Ascocalyx abietina (Lagerberg) * Lignin * Norway spruce Subject RIV: GK - Forestry Impact factor: 1.631, year: 2006

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

    Science.gov (United States)

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

    2016-10-01

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

  20. Calculated ionisation potentials to determine the oxidation of vanillin precursors by lignin peroxidase.

    NARCIS (Netherlands)

    Have, ten R.; Rietjens, I.M.C.M.; Hartmans, S.; Swarts, H.J.; Field, J.A.

    1998-01-01

    In view of the biocatalytic production of vanillin, this research focused on the lignin peroxidase (LiP) catalysed oxidation of naturally occurring phenolic derivatives: O-methyl ethers, O-acetyl esters, and O-glucosyl ethers. The ionisation potential (IP) of a series of model compounds was

  1. Catalytic Oxidation of Lignins into the Aromatic Aldehydes: General Process Trends and Development Prospects

    Directory of Open Access Journals (Sweden)

    Valery E. Tarabanko

    2017-11-01

    Full Text Available This review discusses principal patterns that govern the processes of lignins’ catalytic oxidation into vanillin (3-methoxy-4-hydroxybenzaldehyde and syringaldehyde (3,5-dimethoxy-4-hydroxybenzaldehyde. It examines the influence of lignin and oxidant nature, temperature, mass transfer, and of other factors on the yield of the aldehydes and the process selectivity. The review reveals that properly organized processes of catalytic oxidation of various lignins are only insignificantly (10–15% inferior to oxidation by nitrobenzene in terms of yield and selectivity in vanillin and syringaldehyde. Very high consumption of oxygen (and consequentially, of alkali in the process—over 10 mol per mol of obtained vanillin—is highlighted as an unresolved and unexplored problem: scientific literature reveals almost no studies devoted to the possibilities of decreasing the consumption of oxygen and alkali. Different hypotheses about the mechanism of lignin oxidation into the aromatic aldehydes are discussed, and the mechanism comprising the steps of single-electron oxidation of phenolate anions, and ending with retroaldol reaction of a substituted coniferyl aldehyde was pointed out as the most convincing one. The possibility and development prospects of single-stage oxidative processing of wood into the aromatic aldehydes and cellulose are analyzed.

  2. Catalytic Oxidation of Lignins into the Aromatic Aldehydes: General Process Trends and Development Prospects

    Science.gov (United States)

    Tarabanko, Valery E.; Tarabanko, Nikolay

    2017-01-01

    This review discusses principal patterns that govern the processes of lignins’ catalytic oxidation into vanillin (3-methoxy-4-hydroxybenzaldehyde) and syringaldehyde (3,5-dimethoxy-4-hydroxybenzaldehyde). It examines the influence of lignin and oxidant nature, temperature, mass transfer, and of other factors on the yield of the aldehydes and the process selectivity. The review reveals that properly organized processes of catalytic oxidation of various lignins are only insignificantly (10–15%) inferior to oxidation by nitrobenzene in terms of yield and selectivity in vanillin and syringaldehyde. Very high consumption of oxygen (and consequentially, of alkali) in the process—over 10 mol per mol of obtained vanillin—is highlighted as an unresolved and unexplored problem: scientific literature reveals almost no studies devoted to the possibilities of decreasing the consumption of oxygen and alkali. Different hypotheses about the mechanism of lignin oxidation into the aromatic aldehydes are discussed, and the mechanism comprising the steps of single-electron oxidation of phenolate anions, and ending with retroaldol reaction of a substituted coniferyl aldehyde was pointed out as the most convincing one. The possibility and development prospects of single-stage oxidative processing of wood into the aromatic aldehydes and cellulose are analyzed. PMID:29140301

  3. Oxidation of lignin-carbohydrate complex from bamboo with hydrogen peroxide catalyzed by Co(salen

    Directory of Open Access Journals (Sweden)

    Zhou Xue-Fei

    2014-01-01

    Full Text Available The reactivity of salen complexes toward hydrogen peroxide has been long recognized. Co(salen was tested as catalyst for the aqueous oxidation of a refractory lignin-carbohydrate complex (LCC isolated from sweet bamboo (Dendrocalamushamiltonii in the presence of hydrogen peroxide as oxidant. Co(salen catalyzed the reaction of hydrogen peroxide with LCC. From the spectra analyses, lignin units in LCC were undergoing ring-opening, side chain oxidation, demethoxylation, β-O-4 cleavage with Co(salen catalytic oxidation. The degradation was also observed in the carbohydrate of LCC. The investigation on the refractory LCC degradation catalyzed by Co(salen may be an important aspect for environmentally-oriented biomimetic bleaching in pulp and paper industry.

  4. In situ spectroscopic investigation of the cobalt-catalyzed oxidation of lignin model compounds in ionic liquids

    NARCIS (Netherlands)

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Bruijnincx, P.C.A.|info:eu-repo/dai/nl/33799529X; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2011-01-01

    The cobalt-catalyzed oxidation of lignin and lignin model compounds using molecular oxygen in ionic liquids proceeds readily under mild conditions, but mechanistic insight and evidence for the species involved in the catalytic cycle is lacking. In this study, a spectroscopic investigation of the

  5. Identification of Manganese Superoxide Dismutase from Sphingobacterium sp. T2 as a Novel Bacterial Enzyme for Lignin Oxidation.

    Science.gov (United States)

    Rashid, Goran M M; Taylor, Charles R; Liu, Yangqingxue; Zhang, Xiaoyang; Rea, Dean; Fülöp, Vilmos; Bugg, Timothy D H

    2015-10-16

    The valorization of aromatic heteropolymer lignin is an important unsolved problem in the development of a biomass-based biorefinery, for which novel high-activity biocatalysts are needed. Sequencing of the genomic DNA of lignin-degrading bacterial strain Sphingobacterium sp. T2 revealed no matches to known lignin-degrading genes. Proteomic matches for two manganese superoxide dismutase proteins were found in partially purified extracellular fractions. Recombinant MnSOD1 and MnSOD2 were both found to show high activity for oxidation of Organosolv and Kraft lignin, and lignin model compounds, generating multiple oxidation products. Structure determination revealed that the products result from aryl-Cα and Cα-Cβ bond oxidative cleavage and O-demethylation. The crystal structure of MnSOD1 was determined to 1.35 Å resolution, revealing a typical MnSOD homodimer harboring a five-coordinate trigonal bipyramidal Mn(II) center ligated by three His, one Asp, and a water/hydroxide in each active site. We propose that the lignin oxidation reactivity of these enzymes is due to the production of a hydroxyl radical, a highly reactive oxidant. This is the first demonstration that MnSOD is a microbial lignin-oxidizing enzyme.

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

    Science.gov (United States)

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

    2015-05-22

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

  7. Preoxidation and Activation of the Lignin Char: Carbonization and Oxidation Procedures

    Directory of Open Access Journals (Sweden)

    Saloua Sebbahi

    2014-01-01

    Full Text Available A comprehensive process of pretreatment and oxidation of lignin char was developed to optimize the production of activated carbon. The lignin char was obtained by carbonization of lignin under nitrogen at 600°C for 2 hours. The optimum time and temperature used to oxidize the char without destruction were, respectively, 6 hours and 245°C. The oxygen improves the reactivity of the sample in CO2 and evolved the sample of a thermoplastic behaviour to a thermosetting behaviour. The oxygenation in air of the lignin char does not change the mode of deformation acquired by the material during the carbonization. The preoxidized coal reacts more than the nonoxidized coal during the CO2 activation, whereas the reduction in volume in the first case is smaller than in the second. The preoxidized and then activated carbon shows the formation and the development of microporosity at the expense of macroporosity. This microstructure is one of the main characteristics of activated carbon, which can be used as adsorbent for different pollutants.

  8. On barium oxide solubility in barium-containing chloride melts

    International Nuclear Information System (INIS)

    Nikolaeva, Elena V.; Zakiryanova, Irina D.; Bovet, Andrey L.; Korzun, Iraida V.

    2016-01-01

    Oxide solubility in chloride melts depends on temperature and composition of molten solvent. The solubility of barium oxide in the solvents with barium chloride content is essentially higher than that in molten alkali chlorides. Spectral data demonstrate the existence of oxychloride ionic groupings in such melts. This work presents the results of the BaO solubility in two molten BaCl 2 -NaCl systems with different barium chloride content. The received data together with earlier published results revealed the main regularities of BaO solubility in molten BaO-BaCl 2 -MCl systems.

  9. Oxidative pyrolysis of kraft lignin in a bubbling fluidized bed reactor with air

    International Nuclear Information System (INIS)

    Li, Dongbing; Briens, Cedric; Berruti, Franco

    2015-01-01

    Fast pyrolysis of kraft lignin with partial (air) oxidation was studied in a bubbling fluidized bed reactor at reaction temperatures of 773 and 823 K. The bio-oil vapors were fractionated using a series of three condensers maintained at desired temperatures, providing a dry bio-oil with less than 1% water and over 96% of the total bio-oil energy. Oxygen feed was varied to study its effect on yield, composition, and energy recovery in the gas, char and oil products. The addition of oxygen to the pyrolysis process increased the production of gases such as CO and CO 2 . It also changed the dry bio-oil properties, reducing its heating value, increasing its oxygen content, reducing its average molecular weight and tar concentration, while increasing its phenolics concentration. The lower reaction temperature of 773 K was preferred for both dry bio-oil yield and quality. Autothermal operation of the pyrolysis process was achieved with an oxygen feed of 72 or 54 g per kg of biomass at the reaction temperatures of 773 and 823 K, respectively. Autothermal operation reduced both yield and total energy content of the dry bio-oil, with relative reductions of 24 and 20% for the yield, 28 and 23% for the energy content, at 773 and 823 K. - Highlights: • Autothermal pyrolysis of Kraft lignin is possible with introduction of air. • Under autothermal conditions, 24% of the dry bio-oil chemicals are lost at 773 K. • Partial oxidation helps produce more simple phenols and less pyrolytic lignin. • Bio-oil from lignin pyrolysis has a very high phenolics concentration

  10. Calculated ionisation potentials to determine the oxidation of vanillin precursors by lignin peroxidase.

    OpenAIRE

    Have, ten, R.; Rietjens, I.M.C.M.; Hartmans, S.; Swarts, H.J.; Field, J.A.

    1998-01-01

    In view of the biocatalytic production of vanillin, this research focused on the lignin peroxidase (LiP) catalysed oxidation of naturally occurring phenolic derivatives: O-methyl ethers, O-acetyl esters, and O-glucosyl ethers. The ionisation potential (IP) of a series of model compounds was calculated and compared to their experimental conversion by LiP, defining a relative IP threshold of approximately 9.0 eV. Based on this threshold value only the O-acetyl esters and glucosides of isoeugeno...

  11. H2O2 recycling during oxidation of the arylglycerol beta-aryl ether lignin structure by lignin peroxidase and glyoxal oxidase.

    Science.gov (United States)

    Hammel, K E; Mozuch, M D; Jensen, K A; Kersten, P J

    1994-11-15

    Oxidative C alpha-C beta cleavage of the arylglycerol beta-aryl ether lignin model 1-(3,4-dimethoxy-phenyl)-2-phenoxypropane-1,3-diol (I) by Phanerochaete chrysosporium lignin peroxidase in the presence of limiting H2O2 was enhanced 4-5-fold by glyoxal oxidase from the same fungus. Further investigation showed that each C alpha-C beta cleavage reaction released 0.8-0.9 equiv of glycolaldehyde, a glyoxal oxidase substrate. The identification of glycolaldehyde was based on 13C NMR spectrometry of reaction product obtained from beta-, gamma-, and beta,gamma-13C-substituted I, and quantitation was based on an enzymatic NADH-linked assay. The oxidation of glycolaldehyde by glyoxal oxidase yielded 0.9 oxalate and 2.8 H2O2 per reaction, as shown by quantitation of oxalate as 2,3-dihydroxyquinoxaline after derivatization with 1,2-diaminobenzene and by quantitation of H2O2 in coupled spectrophotometric assays with veratryl alcohol and lignin peroxidase. These results suggest that the C alpha-C beta cleavage of I by lignin peroxidase in the presence of glyoxal oxidase should regenerate as many as 3 H2O2. Calculations based on the observed enhancement of LiP-catalyzed C alpha-C beta cleavage by glyoxal oxidase showed that approximately 2 H2O2 were actually regenerated per cleavage of I when both enzymes were present. The cleavage of arylglycerol beta-aryl ether structures by ligninolytic enzymes thus recycles H2O2 to support subsequent cleavage reactions.

  12. Sensitivity analysis of uranium solubility under strongly oxidizing conditions

    International Nuclear Information System (INIS)

    Liu, L.; Neretnieks, I.

    1999-01-01

    To evaluate the effect of geochemical conditions in the repository on the solubility of uranium under strongly oxidizing conditions, a mathematical model has been developed to determine the solubility, by utilizing a set of nonlinear algebraic equations to describe the chemical equilibria in the groundwater environment. The model takes into account the predominant precipitation-dissolution reactions, hydrolysis reactions and complexation reactions that may occur under strongly oxidizing conditions. The model also includes the solubility-limiting solids induced by the presence of carbonate, phosphate, silicate, calcium, and sodium in the groundwater. The thermodynamic equilibrium constants used in the solubility calculations are essentially taken from the NEA Thermochemical Data Base of Uranium, with some modification and some uranium minerals added, such as soddyite, rutherfordite, uranophane, uranyl orthophosphate, and becquerelite. By applying this model, the sensitivities of uranium solubility to variations in the concentrations of various groundwater component species are systematically investigated. The results show that the total analytical concentrations of carbonate, phosphate, silicate, and calcium in deep groundwater play the most important role in determining the solubility of uranium under strongly oxidizing conditions

  13. Water-soluble highly fluorinated graphite oxide

    Czech Academy of Sciences Publication Activity Database

    Jankovský, O.; Šimek, P.; Sedmidubský, D.; Matějková, Stanislava; Janoušek, Zbyněk; Šembera, Filip; Pumera, M.; Sofer, Z.

    2014-01-01

    Roč. 4, č. 3 (2014), s. 1378-1387 ISSN 2046-2069 Institutional support: RVO:61388963 Keywords : graphene oxide * electronic- properties * monolayer graphene * raman-spectroscopy Subject RIV: CC - Organic Chemistry Impact factor: 3.840, year: 2014

  14. Exploring the Oxidation of Lignin-Derived Phenols by a Library of Laccase Mutants

    Directory of Open Access Journals (Sweden)

    Isabel Pardo

    2015-09-01

    Full Text Available Saturation mutagenesis was performed over six residues delimiting the substrate binding pocket of a fungal laccase previously engineered in the lab. Mutant libraries were screened using sinapic acid as a model substrate, and those mutants presenting increased activity were selected for exploring the oxidation of lignin-derived phenols. The latter comprised a battery of phenolic compounds of interest due to their use as redox mediators or precursors of added-value products and their biological activity. The new laccase variants were investigated in a multi-screening assay and the structural determinants, at both the substrate and the protein level, for the oxidation of the different phenols are discussed. Laccase activity greatly varied only by changing one or two residues of the enzyme pocket. Our results suggest that once the redox potential threshold is surpassed, the contribution of the residues of the enzymatic pocket for substrate recognition and binding strongly influence the overall rate of the catalytic reaction.

  15. Biomimetic Catalysts for Oxidation of Veratryl Alcohol, a Lignin Model Compound

    Directory of Open Access Journals (Sweden)

    Marcelino Maneiro

    2013-03-01

    Full Text Available Kraft pulp has to be bleached to eliminate the chromophoric structures, which cause a darkening of the pulp. In Nature, an equivalent role is assumed by ligninolytic enzymes such as lignin peroxidases, manganese peroxidases and laccases. The development of low molecular weight manganese peroxidase mimics may achieve environmentally-safe bleaching catalysts for the industry. Herein we report the synthesis and characterization of six manganese(III complexes 1–6, incorporating dianionic hexadentate Schiff base ligands (H2L1-H2L4 and different anions. Complex 4, Mn2L22(H2O2(DCA2 was crystallographically characterized. Complexes 1–4 behave as more efficient mimics of peroxidase in contrast to 5–6. We have studied the use of these complexes as catalysts for the degradation of the lignin model compound veratryl alcohol. The biomimetic catalysts were used in conjunction with chlorine-free inexpensive co-oxidants as dioxygen or hydrogen peroxide. Yields up to 30% of veratryl alcohol conversion to veratraldehyde have been achieved at room temperature in presence of air flow using 0.5% of catalyst.

  16. Calculated ionisation potentials determine the oxidation of vanillin precursors by lignin peroxidase.

    Science.gov (United States)

    ten Have, R; Rietjens, I M; Hartmans, S; Swarts, H J; Field, J A

    1998-07-03

    In view of the biocatalytic production of vanillin, this research focused on the lignin peroxidase (LiP) catalysed oxidation of naturally occurring phenolic derivatives: O-methyl ethers, O-acetyl esters, and O-glucosyl ethers. The ionisation potential (IP) of a series of model compounds was calculated and compared to their experimental conversion by LiP, defining a relative IP threshold of approximately 9.0 eV. Based on this threshold value only the O-acetyl esters and glucosides of isoeugenol and coniferyl alcohol would be potential LiP substrates. Both O-acetyl esters were tested and were shown to be converted to O-acetyl vanillin in molar yields of 51.8 and 2.3%, respectively.

  17. Synergy in lignin upgrading by a combination of Cu-based mixed oxide and Ni-phosphide catalysts in supercritical ethanol

    NARCIS (Netherlands)

    Koranyi, T.I.; Huang, X.; Coumans, A.E.; Hensen, E.J.M.

    2017-01-01

    The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu–Mg–Al oxide (CuMgAlOx) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e.

  18. Compound specific radiocarbon content of lignin oxidation products from the Altamaha river and Coastal Georgia

    Energy Technology Data Exchange (ETDEWEB)

    Culp, Randy, E-mail: rculp@uga.edu [Center for Applied Isotope Studies, University of Georgia, Athens, Georgia (United States)

    2013-01-15

    Compound-specific isotope analysis (CSIA) is a powerful tool in organic geochemistry by providing detailed information about an individual organic compound's history with regard to its source and process of formation. Most CSIA involves measurement of the stable isotope ratio of carbon ({sup 13}C/{sup 12}C) and hydrogen (D/H) following separation by gas or liquid chromatography. New applications are being developed using compound-specific radiocarbon ({sup 14}C) content for delineating age of materials, rates of decomposition and residence time in various environments. This paper details the isotopic work on specific lignin monomers derived from terrestrial plants transported and deposited within the Altamaha River, estuary and off-shore Georgia in the Atlantic Ocean. By using gas chromatographic separation and identification of selected lignin oxidation products (LOP), the harvesting of these compounds using preparative fraction collection, and measurement of their {sup 14}C content using accelerator mass spectrometry, details of the age and presence of specific biomarkers unique to a given terrestrial source are revealed. Radiocarbon ages determined from water-column particulate organic carbon and sediment LOPs indicate a range of ages from modern to well over 5,000 years for the former and latter respectively. Transport mechanisms and particle size associations on mineral grains may play a significant role in {sup 14}C distribution in estuary and near-shore coastal environments. This data indicates higher than modern {sup 14}C activities in large particle-size sediment fractions in contrast to older LOP {sup 14}C ages found associated with the same coarse grain sediments. Individual LOP ages substantiate older terrestrial materials persist in the off-shore environment even though in the presence of modern marine {sup 14}C sources.

  19. Compound specific radiocarbon content of lignin oxidation products from the Altamaha river and Coastal Georgia

    International Nuclear Information System (INIS)

    Culp, Randy

    2013-01-01

    Compound-specific isotope analysis (CSIA) is a powerful tool in organic geochemistry by providing detailed information about an individual organic compound’s history with regard to its source and process of formation. Most CSIA involves measurement of the stable isotope ratio of carbon ( 13 C/ 12 C) and hydrogen (D/H) following separation by gas or liquid chromatography. New applications are being developed using compound-specific radiocarbon ( 14 C) content for delineating age of materials, rates of decomposition and residence time in various environments. This paper details the isotopic work on specific lignin monomers derived from terrestrial plants transported and deposited within the Altamaha River, estuary and off-shore Georgia in the Atlantic Ocean. By using gas chromatographic separation and identification of selected lignin oxidation products (LOP), the harvesting of these compounds using preparative fraction collection, and measurement of their 14 C content using accelerator mass spectrometry, details of the age and presence of specific biomarkers unique to a given terrestrial source are revealed. Radiocarbon ages determined from water-column particulate organic carbon and sediment LOPs indicate a range of ages from modern to well over 5,000 years for the former and latter respectively. Transport mechanisms and particle size associations on mineral grains may play a significant role in 14 C distribution in estuary and near-shore coastal environments. This data indicates higher than modern 14 C activities in large particle-size sediment fractions in contrast to older LOP 14 C ages found associated with the same coarse grain sediments. Individual LOP ages substantiate older terrestrial materials persist in the off-shore environment even though in the presence of modern marine 14 C sources.

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...

  1. Catalytic wet-air oxidation of lignin in a three-phase reactor with aromatic aldehyde production

    Directory of Open Access Journals (Sweden)

    Sales F.G.

    2004-01-01

    Full Text Available In the present work a process of catalytic wet air oxidation of lignin obtained from sugar-cane bagasse is developed with the objective of producing vanillin, syringaldehyde and p-hydroxybenzaldehyde in a continuous regime. Palladium supported on g-alumina was used as the catalyst. The reactions in the lignin degradation and aldehyde production were described by a kinetic model as a system of complex parallel and series reactions, in which pseudo-first-order steps are found. For the purpose of producing aromatic aldehydes in continuous regime, a three-phase fluidized reactor was built, and it was operated using atmospheric air as the oxidizer. The best yield in aromatic aldehydes was of 12%. The experimental results were compatible with those values obtained by the pseudo-heterogeneous axial dispersion model (PHADM applied to the liquid phase.

  2. Graphene Oxide Filled Lignin/Starch Polymer Bionanocomposite: Structural, Physical, and Mechanical Studies.

    Science.gov (United States)

    Aqlil, Meryem; Moussemba Nzenguet, Annie; Essamlali, Younes; Snik, Asmae; Larzek, Mohamed; Zahouily, Mohamed

    2017-12-06

    In this study, graphene oxide (GO) was investigated as a potential nanoreinforcing agent in starch/lignin (ST/L) biopolymer matrix. Bionanocomposite films based on ST/L blend matrix and GO were prepared by solution-casting technique of the corresponding film-forming solution. The structures, morphologies, and properties of bionanocomposite films were characterized by Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), ultraviolet-visible (UV-vis), SEM, and tensile tests. The experimental results showed that content of GO have a significant influence on the mechanical properties of the produced films. The results revealed that the interfacial interaction formed in the bionanocomposite films improved the compatibility between GO fillers and ST/L matrix. The addition of GO also reduced moisture uptake (Mu) and water vapor permeability of ST/L blend film. In addition, TGA showed that the thermal stability of bionanocomposite films was better than that of neat starch film. These findings confirmed the effectiveness of the proposed approach to produce biodegradable films with enhanced properties, which may be used in packaging applications.

  3. Ionic liquid [OMIm][OAc] directly inducing oxidation cleavage of the β-O-4 bond of lignin model compounds.

    Science.gov (United States)

    Yang, Yingying; Fan, Honglei; Meng, Qinglei; Zhang, Zhaofu; Yang, Guanying; Han, Buxing

    2017-08-03

    We explored the oxidation reactions of lignin model compounds directly induced by ionic liquids under metal-free conditions. In this work, it was found that ionic liquid 1-octyl-3-methylimidazolium acetate as a solvent could promote the aerobic oxidation of lignin model compound 2-phenoxyacetophenone (1) and the yields of phenol and benzoic acid from 1 could be as high as 96% and 86%, respectively. A possible reaction pathway was proposed based on a series of control experiments. An acetate anion from the ionic liquid attacked the hydrogen from the β-carbon thereby inducing the cleavage of the C-O bond of the aromatic ether. Furthermore, it was found that 2-(2-methoxyphenoxy)-1-phenylethanone (4) with a methoxyl group could also be transformed into aromatic products in this simple reaction system and the yields of phenol and benzoic acid from 4 could be as high as 98% and 85%, respectively. This work provides a simple way for efficient transformation of lignin model compounds.

  4. Polymerization of different lignins by laccase

    NARCIS (Netherlands)

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

    2008-01-01

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

  5. Potentiometric chemical sensors from lignin-poly(propylene oxide) copolymers doped by carbon nanotubes.

    Science.gov (United States)

    Rudnitskaya, Alisa; Evtuguin, Dmitry V; Costa, Luis C; Graça, M Pedro F; Fernandes, António J S; Correia, M Rosario P; Gomes, M Teresa S R; Oliveira, J A B P

    2013-01-21

    Hardwood and softwood lignins obtained from industrial sulphite and kraft and laboratory oxygen-organosolv pulping processes were employed in co-polymerization with tolylene 2,4-diisocyanate terminated poly(propylene glycol). The obtained lignin-based polyurethanes were doped with 0.72 w/w% of multiwall carbon nanotubes (MWCNTs) with the aim of increasing their electrical conductivity to the levels suitable for sensor applications. Effects of the polymer doping with MWCNTs were assessed using electrical impedance (EIS) and UV-Resonance Raman (UV-RR) spectroscopy. Potentiometric sensors were prepared by drop casting of liquid polymer on the surface of carbon glass or platinum electrodes. Lignin-based sensors displayed a very low or no sensitivity to all alkali, alkali-earth and transition metal cations ions except Cr(VI) at pH 2. Response to Cr(VI) values of 39, 50 and 53 mV pX(-1) for the sensors based on kraft, organosolv and lignosulphonate lignins, respectively, were observed. Redox sensitivity values close to the theoretical values of 20 and 21 mV pX(-1) for organosolv and lignosulphonate based sensors respectively were detected in the Cr(III)/Cr(VI) solutions while a very low response was observed in the solutions containing Fe(CN)(6)(3-/4-). Conducting composite lignin-based polyurethanes doped with MWCNTs were suggested as being promising materials for Cr(VI)-sensitive potentiometric sensors.

  6. Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol.

    Science.gov (United States)

    Korányi, Tamás I; Huang, Xiaoming; Coumans, Alessandro E; Hensen, Emiel J M

    2017-04-03

    The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu-Mg-Al oxide (CuMgAlO x ) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO 2 , Ni 2 P/SiO 2 , and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlO x . A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlO x with Ni/SiO 2 and especially Ni 2 P/SiO 2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni 2 P/SiO 2 , the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products.

  7. Comparison studies on soda lignin and soda-anthraquinone lignin

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  8. Kinetic analysis of polyoxometalate (POM) oxidation of non-phenolic lignin model compound

    Science.gov (United States)

    Tomoya Yokoyama; Hou-min Chang; Ira A. Weinstock; Richard S. Reiner; John F. Kadla

    2003-01-01

    Kinetic and reaction mechanism of non-phenolic lignin model compounds under anaerobic polyoxometalate (POM), Na5(+1.9)[SiV1(-0.1)MoW10(+0.1) 40], bleaching conditions were examined. Analyses using a syringyl type model, 1-(3,4,5-trimethoxyphenyl)ethanol (1), a guaiacyl type, 1-(3,4- imethoxyphenyl)ethanol (2), and 1- (4-ethoxy-3,5-dimethoxyphenyl)ethanol (3) suggest...

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

    Science.gov (United States)

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

    2015-01-01

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

  10. Lignin Macromolecule

    Indian Academy of Sciences (India)

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

  11. Iron addition to soil specifically stabilized lignin

    Science.gov (United States)

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

    2016-01-01

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

  12. Solubilities of Actinide Oxides in the KURT Groundwater

    International Nuclear Information System (INIS)

    Kim, Seung Soo; Baik, Min Hoon; Choi, Jong Won

    2009-12-01

    For the estimation of solubilities of actinides in a deep underground condition, The solubilities of UO 2 , ThO 2 , NpO 2 and Am(OH) 3 in the KURT ground water have been measured under various redox conditions, and their solubilities and aqueous species in the same conditions as the experimental solutions were also calculated by using a geochemical code. Then these results were compared with each other as well as with literature results. For the calculation of solubility of a radionuclide, the thermodynamic data of the radionuclide complex from OECD/NEA, Nagra/PSI, KAERI, JAEA, SKB and recent literatures were collected and compared. Additionally, the methods for the correction of ionic strength and temperature of the solution were described in this report. The analysis techniques and recent research for measurement of species of actinides were also introduced. The concentrations of U, Th and Np dissolved were less than 10 -7 mol/L under Eh≤-0.2 of reducing condition from experiment and calculation, and the solubility of PuO 2 (cr) was estimated as lower than that of UO 2 (cr) by 1 ∼ 2 orders. However if amount of carbonate ion in the ground water increased, the concentration of tetra-valance actinides at pH 8 ∼ 11 would be greatly increased. The 1x10 -6 mol/L of americium might be a little conservative value in KURT groundwater. While carbonate or hydroxo-carbonatec complexes were presumed to be the dominant aqueous species in -0.2 ∼ -0.3 V of Eh and weakly alkaline solution, hydroxo complexes are dominant in strong reducing and high pH solution

  13. The solubilities and solubility products of zirconium hydroxide and oxide after aging at 278, 313, and 333 K

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Taishi; Uemura, Takuya; Sasaki, Takayuki; Takagi, Ikuji [Kyoto Univ. (Japan). Dept. of Nuclear Engineering; Moriyama, Hirotake [Kyoto Univ. (Japan). Research Reactor Inst.

    2016-07-01

    The solubilities of zirconium hydroxide and oxide after aging at 278, 313, and 333 K were measured at 278, 298, 313, and 333 K in the pH{sub c} range of 0.3-7 in a 0.5 M ionic strength solution of NaClO{sub 4} and HClO{sub 4}. Size distributions of the colloidal species were investigated by ultrafiltration using membranes with different pore sizes, and the solid phases were examined by X-ray diffraction. The apparent solubility of zirconium amorphous hydroxide (Zr(OH){sub 4}(am)), prepared by the oversaturation method, decreased with increasing aging temperature (T{sub a}), and the size distributions obtained after aging at elevated temperatures indicated the growth of the colloidal species. We, therefore, suggested that agglomeration of the colloidal species and dehydration and crystallization of Zr(OH){sub 4}(am) as the solubility-limiting solid phase occurred over the course of aging at elevated temperatures. For sample solutions of the crystalline oxide (ZrO{sub 2}(cr)), the aging temperature had no significant effect on the solubility, but the solubility data at lower temperatures were found to be slightly higher than those at higher temperatures, implying a small fraction of the amorphous components. In the analysis of different solid phases (Zr(OH){sub 4}(s,T{sub a}), T{sub a} = 278, 313, and 333 K) depending on the aging temperatures, the solubility products (K{sub sp}, T{sub a}) were determined at different measurement temperatures, and the enthalpy change (Δ{sub r}H {sup circle}) for Zr{sup 4+} 4OH{sup -} <=> Zr(OH){sub 4}(s,T{sub a}) was calculated using the van't Hoff equation. The solid-phase-transformation process at elevated temperatures was also analyzed based on the obtained K{sub sp}, T{sub a} and Δ{sub r}H {sup circle} values.

  14. A comparative genomic analysis of the oxidative enzymes potentially involved in lignin degradation by Agaricus bisporus

    Science.gov (United States)

    Harshavardhan Doddapaneni; Venkataramanan Subramanian; Bolei Fu; Dan Cullen

    2013-01-01

    The oxidative enzymatic machinery for degradation of organic substrates in Agaricus bisporus (Ab) is at the core of the carbon recycling mechanisms in this fungus. To date, 156 genes have been tentatively identified as part of this oxidative enzymatic machinery, which includes 26 peroxidase encoding genes, nine copper radical oxidase [including three...

  15. In vitro solubility of uranium tetrafluoride with oxidizing medium compared with in vivo solubility in rats

    International Nuclear Information System (INIS)

    Ansoborlo, E.; Chalabreysse, J.; Escallon, S.; Henge-Napoli, M.H.

    1990-01-01

    A simple in vitro solubility test for UF 4 was developed to investigate effects of addition of enzymes, proteins or gases (eg O 2 ) to synthetic biological fluid or Gamble solvent. Tests were made concomitantly with an in vivo inhalation study using male rats. With Gamble solvent alone, UF 4 showed class Y behaviour with dissolution half-time 300-500 days. When O 2 or carbonates were added to Gamble solvent, UF 4 showed class W behaviour (half-time 25-50 days). In the presence of oxygen and pyrogallol, the superoxide ion was formed and UF 4 behaved as class D (half-time 2-3 days). Results correlated with those of the inhalation experiment in which dissolution half-time was 2.5 and 5.2 days. Data also agree with urine monitoring data for workers exposed to UF 4 over 20 years. (author)

  16. Solubilities of iron and nickel oxides under high temperature and high pressure conditions

    International Nuclear Information System (INIS)

    Choi, Ke-Chon; Jung, Yong-Ju; Yeon, Jei-Won; Jee, Kwang-Yong

    2007-01-01

    The purposes of primary coolant chemistry are to assure fuel and material integrity and to minimize out of core radiation fields. During the PWR operation, crud deposits are expected on the cladding, leading to cladding failure and raising the radioactivity. Such deposits come from the corrosion products of system surface. To achieve optimal conditions for primary coolant, basic researches on mass transfer, deposition and solubility of corrosion products are needed. The initial stage of crud formation could be the studies on the solubility of a structural material. It has been known that the solubility of metal oxides in boric acid under high temperature and high pressure condition depends on the pH and dissolved hydrogen. Thus, the effect of various pH on the solubility of metal oxide in boric acid solution was investigated in this work

  17. Oxidative cleavage of a phenolic diarylpropane lignin model dimer by manganese peroxidase from Phanerochaete chrysosporium

    International Nuclear Information System (INIS)

    Wariishi, Hiroyuki; Valli, K.; Gold, M.H.

    1989-01-01

    In the presence of Mn II and H 2 O 2 , homogeneous manganese peroxidase oxidized 1-(3,5-dimethoxy-4-hydroxyphenyl)-2-(4-methoxyphenyl)-1,3-dihydroxypropane (I) to yield 1-(3,5-dimethoxy-4-hydroxyphenyl)-2-(4-methoxyphenyl)-1-oxo-3-hydroxypropane (II), 2,6-dimethoxy-1,4-benzoquinone (III), 2,6-dimethoxy-1,4-dihydroxybenzene (IV), 1-(4-methoxyphenyl)-1-oxo-2-hydroxyethane (V), 1-(4-methoxyphenyl)-1,2-dihydroxyethane (VI), syringaldehyde (VIII), and 2-(4-methoxyphenyl)-3-hydroxypropanal (IX). Chemically prepared manganese(III) malonate catalyzed the same reactions. Oxidation of I in H 2 18 O under argon resulted in >80% incorporation of 18 O into the phenylglycol VI, the hydroquinone IV, and the quinone III. Oxidation of I in H 2 18 O under aerobic conditions resulted in 40% incorporation of 18 O into VI but no 18 O incorporation into V. Finally, oxidation of I under 18 O 2 resulted in 89% and 28% incorporation of 18 O into V and VI, respectively. These results are explained by mechanisms involving the one-electron oxidation of the substrate I by enzyme-generated Mn III to produce a phenoxy radical intermediate I'. Subsequent C α -C β bond cleavage of the radical intermediate yields syringaldehyde (VIII) and a C 6 -C 2 benzylic radical. Syringaldehyde is oxidized by Mn III in several steps to a cyclohexadiene cation intermediate I double-prime, which is attacked by water to yield the benzoquinone III. The C 6 -C 2 radical is scavenged by O 2 to form a peroxy radical that decomposes to V and VI. In these reactions, Mn III generated by manganese peroxidase catalyzes both formation of the substrate phenoxy radical and oxidation of carbon-centered radical intermediates, to yield reactive cations

  18. Literature review for oxalate oxidation processes and plutonium oxalate solubility

    Energy Technology Data Exchange (ETDEWEB)

    Nash, C. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-10-01

    A literature review of oxalate oxidation processes finds that manganese(II)-catalyzed nitric acid oxidation of oxalate in precipitate filtrate is a viable and well-documented process. The process has been operated on the large scale at Savannah River in the past, including oxidation of 20 tons of oxalic acid in F-Canyon. Research data under a variety of conditions show the process to be robust. This process is recommended for oxalate destruction in H-Canyon in the upcoming program to produce feed for the MOX facility. Prevention of plutonium oxalate precipitation in filtrate can be achieved by concentrated nitric acid/ferric nitrate sequestration of oxalate. Organic complexants do not appear practical to sequester plutonium. Testing is proposed to confirm the literature and calculation findings of this review at projected operating conditions for the upcoming campaign.

  19. LITERATURE REVIEW FOR OXALATE OXIDATION PROCESSES AND PLUTONIUM OXALATE SOLUBILITY

    Energy Technology Data Exchange (ETDEWEB)

    Nash, C.

    2012-02-03

    A literature review of oxalate oxidation processes finds that manganese(II)-catalyzed nitric acid oxidation of oxalate in precipitate filtrate is a viable and well-documented process. The process has been operated on the large scale at Savannah River in the past, including oxidation of 20 tons of oxalic acid in F-Canyon. Research data under a variety of conditions show the process to be robust. This process is recommended for oxalate destruction in H-Canyon in the upcoming program to produce feed for the MOX facility. Prevention of plutonium oxalate precipitation in filtrate can be achieved by concentrated nitric acid/ferric nitrate sequestration of oxalate. Organic complexants do not appear practical to sequester plutonium. Testing is proposed to confirm the literature and calculation findings of this review at projected operating conditions for the upcoming campaign. H Canyon plans to commence conversion of plutonium metal to low-fired plutonium oxide in 2012 for eventual use in the Mixed Oxide Fuel (MOX) Facility. The flowsheet includes sequential operations of metal dissolution, ion exchange, elution, oxalate precipitation, filtration, and calcination. All processes beyond dissolution will occur in HB-Line. The filtration step produces an aqueous filtrate that may have as much as 4 M nitric acid and 0.15 M oxalate. The oxalate needs to be removed from the stream to prevent possible downstream precipitation of residual plutonium when the solution is processed in H Canyon. In addition, sending the oxalate to the waste tank farm is undesirable. This report addresses the processing options for destroying the oxalate in existing H Canyon equipment.

  20. Lignin based controlled release coatings

    NARCIS (Netherlands)

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

    2011-01-01

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

  1. Recovering hydrocarbons with surfactants from lignin

    Energy Technology Data Exchange (ETDEWEB)

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

    1988-11-29

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

  2. Effect of supplementation of water-soluble vitamins on oxidative stress and blood pressure in prehypertensives.

    Science.gov (United States)

    Talikoti, Prashanth; Bobby, Zachariah; Hamide, Abdoul

    2015-01-01

    The objective of the study was to evaluate the effect of water-soluble vitamins on oxidative stress and blood pressure in prehypertensives. Sixty prehypertensives were recruited and randomized into 2 groups of 30 each. One group received water-soluble vitamins and the other placebo for 4 months. Further increase in blood pressure was not observed in the vitamin group which increased significantly in the placebo group at the end of 4 months. Malonedialdehyde and protein carbonylation were reduced during the course of treatment with vitamins whereas in the placebo group there was an increase in the level of malondialdehyde. In conclusion, supplementation of water-soluble vitamins in prehypertension reduces oxidative stress and its progression to hypertension.

  3. Immobilized Lignin Peroxidase-Like Metalloporphyrins as Reusable Catalysts in Oxidative Bleaching of Industrial Dyes

    Directory of Open Access Journals (Sweden)

    Paolo Zucca

    2016-07-01

    Full Text Available Synthetic and bioinspired metalloporphyrins are a class of redox-active catalysts able to emulate several enzymes such as cytochromes P450, ligninolytic peroxidases, and peroxygenases. Their ability to perform oxidation and degradation of recalcitrant compounds, including aliphatic hydrocarbons, phenolic and non-phenolic aromatic compounds, sulfides, and nitroso-compounds, has been deeply investigated. Such a broad substrate specificity has suggested their use also in the bleaching of textile plant wastewaters. In fact, industrial dyes belong to very different chemical classes, being their effective and inexpensive oxidation an important challenge from both economic and environmental perspective. Accordingly, we review here the most widespread synthetic metalloporphyrins, and the most promising formulations for large-scale applications. In particular, we focus on the most convenient approaches for immobilization to conceive economical affordable processes. Then, the molecular routes of catalysis and the reported substrate specificity on the treatment of the most diffused textile dyes are encompassed, including the use of redox mediators and the comparison with the most common biological and enzymatic alternative, in order to depict an updated picture of a very promising field for large-scale applications.

  4. Molecular dynamics simulations of zinc oxide solubility: From bulk down to nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Escorihuela, Laura; Fernández, Alberto; Rallo, Robert; Martorell, Benjamí

    2018-02-01

    The solubility of metal oxides is one of the key descriptors for the evaluation of their potential toxic effects, both in the bulk form and in nanoparticulated aggregates. Current work presents a new methodology for the in silico assessment of the solubility of metal oxides, which is demonstrated using a well-studied system, ZnO. The calculation of the solubility is based on statistical thermodynamics tools combined with Density Functional Tight Binding theory for the evaluation of the free energy exchange during the dissolution process. Models of small ZnO clusters are used for describing the final dissolved material, since the complete ionic dissolution of ZnO is hindered by the formation of O2- anions in solution, which are highly unstable. Results show very good agreement between the computed solubility values and experimental data for ZnO bulk, up to 0.5 mg·L-1 and equivalents of 50 g·L-1 for the free Zn2+ cation in solution. However, the reference model for solid nanoparticles formed by free space nanoparticles can only give a limited quantitative solubility evaluation for ZnO nanoparticles.

  5. Lignin-degrading enzyme activities.

    Science.gov (United States)

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

    2012-01-01

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

  6. Solid state solubility of copper oxides in hydroxyapatite

    Science.gov (United States)

    Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

    2018-06-01

    Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

  7. On some regularities of metal oxide solubility in molten CsI at T = 973 K

    Energy Technology Data Exchange (ETDEWEB)

    Cherginets, V.L., E-mail: v_cherginets@ukr.net [Institute for Scintillation Materials, National Academy of Sciences of Ukraine, Lenin Avenue, 60, Kharkov 61001 (Ukraine); National Technical University ' Kharkiv Polytechnical Institute' , 21 Frunze St., 61002 Kharkov (Ukraine); Rebrova, T.P.; Datsko, Yu.N.; Shtitelman, V.A. [Institute for Scintillation Materials, National Academy of Sciences of Ukraine, Lenin Avenue, 60, Kharkov 61001 (Ukraine); Bryleva, E.Yu. [State Scientific Organization STC ' Institute for Single Crystals' , National Academy of Sciences of Ukraine, Lenin Avenue, 60, Kharkov 61001 (Ukraine)

    2011-08-15

    Highlights: > CdO, ZnO, NiO, and EuO are insoluble in CsI melt at 973 K. > The oxide solubilities are lower than those in chloride melts. > The oxide solubilities reduce with the cation radius. > ZnO, NiO, and EuO are suitable for scavenging CsO from oxide ion traces. - Abstract: Solubility products of CdO (pK{sub s,CdO} = 6.80 {+-} 0.2), ZnO (pK{sub s,ZnO} = 10.0 {+-} 0.5), NiO (pK{sub s,NiO} = 11.2 {+-} 0.2) and EuO (pK{sub s,EuO} = 13.1 {+-} 0.2) in molten CsI at T = 973 K are determined by potentiometric titration of (0.02 to 0.03) mol . kg{sup -1} solutions of the corresponding metal chlorides by strong base (KOH) using a membrane oxygen electrode Pt(O{sub 2})|ZrO{sub 2}(Y{sub 2}O{sub 3}) as an indicator. On the basis of pK{sub s,MeO} values, all the oxides studied are referred to practically insoluble in molten CsI. The values of the oxide solubility in CsI melt are lower than the corresponding values in molten alkali metal chlorides. This can be explained by 'softer' basic properties of I{sup -} as compared with Cl{sup -} in the frames of the Pearson 'hard' and 'soft' acid-base concept. In the oxide samples studied, the values of the solubility fall with the decreasing cation radius. The correlation between pK{sub s,MeO} and the polarizing action by Goldshmidt (Zr{sub Me{sup 2+}}{sup -2}) of the cation is practically linear and may be proposed for estimation of the solubility of s- and d- element oxides in molten CsI on the basis of their cation radii.

  8. Soluble Moringa oleifera leaf extract reduces intracellular cadmium accumulation and oxidative stress in Saccharomyces cerevisiae.

    Science.gov (United States)

    Kerdsomboon, Kittikhun; Tatip, Supinda; Kosasih, Sattawat; Auesukaree, Choowong

    2016-05-01

    Moringa oleifera leaves are a well-known source of antioxidants and traditionally used for medicinal applications. In the present study, the protective action of soluble M. oleifera leaf extract (MOLE) against cadmium toxicity was investigated in the model eukaryote Saccharomyces cerevisiae. The results showed that this extract exhibited a protective effect against oxidative stress induced by cadmium and H2O2 through the reduction of intracellular reactive oxygen species. Interestingly, not only the co-exposure of soluble MOLE with cadmium but also pretreatment of this extract prior to cadmium exposure significantly reduced the cadmium uptake through an inhibition of Fet4p, a low-affinity iron(II) transporter. In addition, the supplementation of soluble MOLE significantly reduced intracellular iron accumulation in a Fet4p-independent manner. Our findings suggest the potential use of soluble extract from M. oleifera leaves as a dietary supplement for protection against cadmium accumulation and oxidative stress. Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  9. Characterization of lignin during oxidative and hydrothermal pre-treatment processes of wheat straw and corn stover.

    Science.gov (United States)

    Kaparaju, Prasad; Felby, Claus

    2010-05-01

    The objective of the study was to characterize and map changes in lignin during hydrothermal and wet explosion pre-treatments of wheat straw and corn stover. Chemical composition, microscopic (atomic force microscopy and scanning electron microscopy) and spectroscopic (attenuated total reflectance Fourier transform infrared spectroscopy, ATR-FTIR) analyses were performed. Results showed that both pre-treatments improved the cellulose and lignin content with substantial removal of hemicellulose in the pre-treated biomasses. These values were slightly higher for hydrothermal compared to wet explosion pre-treatment. ATR-FTIR analyses also confirmed these results. Microscopic analysis showed that pre-treatments affected the biomass by partial difibration. Lignin deposition on the surface of the hydrothermally pre-treated fibre was very distinct while severe loss of fibril integrity was noticed with wet exploded fibre. The present study thus revealed that the lignin cannot be removed by the studied pre-treatments. However, both pre-treatments improved the accessibility of the biomass towards enzymatic hydrolysis. Copyright 2009 Elsevier Ltd. All rights reserved.

  10. Oxidative cleavage of non-phenolic β-O-4 lignin model dimers by an extracellular aromatic peroxygenase

    Science.gov (United States)

    Matthias Kinne; Marzena Poraj-Kobielska; Rene Ullrich; Paula Nousiainen; Jussi Sipilä; Katrin Scheibner; Kenneth E. Hammel; Martin Hofrichter

    2011-01-01

    The extracellular aromatic peroxygenase of the agaric fungus Agrocybe aegerita catalyzed the H2O2-dependent cleavage of non-phenolic arylgiycerol-ß-aryl ethers (ß-O-4 ethers). For instance 1-(3,4-dimethoxyphenyl)-2-(2-methoxy-phenoxy)propane-1,3-diol, a recalcitrant dimeric lignin model compound that represents the major...

  11. Treatment of model and galvanic waste solutions of copper(II) ions using a lignin/inorganic oxide hybrid as an effective sorbent.

    Science.gov (United States)

    Ciesielczyk, Filip; Bartczak, Przemysław; Klapiszewski, Łukasz; Jesionowski, Teofil

    2017-04-15

    A study was made concerning the removal of copper(II) ions from model and galvanic waste solutions using a new sorption material consisting of lignin in combination with an inorganic oxide system. Specific physicochemical properties of the material resulted from combining the activity of the functional groups present in the structure of lignin with the high surface area of the synthesized oxide system (585m 2 /g). Analysis of the porous structure parameters, particle size and morphology, elemental composition and characteristic functional groups confirmed the effective synthesis of the new type of sorbent. A key element of the study was a series of tests of adsorption of copper(II) ions from model solutions. It was determined how the efficiency of the adsorption process was affected by the process time, mass of sorbent, concentration of adsorbate, pH and temperature. Potential regeneration of adsorbent, which provides the possibility of its reusing and recovering the adsorbed copper, was also analyzed. The sorption capacity of the material was measured (83.98mg/g), and the entire process was described using appropriate kinetic models. The results were applied to the design of a further series of adsorption tests, carried out on solutions of real sewage from a galvanizing plant. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Lignin nanoparticle synthesis

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Soluble Iron in Alveolar Macrophages Modulates Iron Oxide Particle-Induced Inflammatory Response via Prostaglandin E2 Synthesis

    Science.gov (United States)

    Ambient particulate matter (PM)-associated metals have been shown to play an important role in cardiopulmonary health outcomes. To study the modulation of inflammation by PM-associated soluble metal, we investigated intracellular solubility of radiolabelled iron oxide (59

  14. Solubility of chromium (III) oxide and metal chromates: development of MULTEQ models

    International Nuclear Information System (INIS)

    Dickinson, Shirley; Henshaw, Jim; Bachet Martin; Hussey, Dennis; Marks, Chuck; Tremaine, Peter; Eaker, Richard

    2012-09-01

    High-temperature solubility predictions for metal oxide systems are important for the understanding of corrosion processes, corrosion product behaviour and activity transport in PWR coolant systems. In the current work, literature data on chromium oxide and iron chromium solubility measurement have been used to derive equilibrium constant expressions for dissolution and hydrolysis reactions which have been incorporated in the latest revision of the EPRI MULTEQ database. Predicting the stable chromium phases in a PWR is important as these constitute the compact inner oxide layer that forms on most ex-core alloys used in this system. Likewise understanding the chromium chemistry is necessary for rationalising high chromium content crud that has been observed on several plant fuel pins. Chromium (III) oxide solubility measurements have shown that the equilibrium solid phase under hydrothermal conditions is CrOOH rather than Cr 2 O 3 . Expressions for the solubility product of this solid and the equilibrium constant for the 4. Cr (III) hydrolysis reaction Cr (OH) 3 (aq) + H 2 O = Cr (OH) 4 - + H + have been derived by fitting to the experimental solubility data in neutral to alkaline solution. The equilibrium constant for the 3rd hydrolysis reaction Cr (OH) 2 + +H 2 O = Cr (OH) 3 (aq) + H + has been revised for consistency with literature estimates of the hydrolysis constants at 298 K. There are insufficient high-quality solubility data at low pH to derive the lower hydrolysis constants so the existing MULTEQ entries, based on thermodynamic estimations, have been retained. This revised model gave reasonable agreement with the available data in acidic solution. A revised expression for the Cr 2 O 3 solubility product was derived from measurements of Fe concentrations produced from FeCr 2 O 4 dissolution, and this was used to obtain a consistent solubility product expression for FeCr 2 O 4 . The resulting model predicts that FeCr 2 O 4 would be unstable at temperatures

  15. Solubility product of tetravalent neptunium hydrous oxide and its ionic strength dependence

    Energy Technology Data Exchange (ETDEWEB)

    Fujiwara, K.; Mori, T. [Japan Nuclear Cycle Development Institute (JNC), 4-33, Muramatsu, Tokai-mura, Naka-gun, Ibaraki-ken, 319-1194 (Japan); Kohara, Y. [Inspection and Development Company, 4-33, Muramatsu, Tokaimura, Naka-gun, Ibaraki-ken, 319-1112 (Japan)

    2005-07-01

    Full text of publication follows: Solubility products (K{sub sp}) are key parameters in the context of reliable assessment of actinides migration in the repository conditions of high level radioactive waste. Neptunium (Np(IV)) is one of the most important actinide elements in the assessment, because of its inventory and the long half-life. A few previous data for Np(IV) solubility are varied widely due to experimental difficulties related to the extremely low solubility. We carried out batch-type experiments under nitrogen atmosphere using a glovebox. Np(V) was reduced to Np(III) by bubbling 0.5 ppm H{sub 2} / N{sub 2} gas through the solution for 30 days in the presence of platinum black as catalyst. After reducing treatment, the Np(III) converted to Np(IV) by auto-oxidation within approximately three days. The solubilities of the Np(IV) were measured in the pHc ranging from 2 to 4, at room temperature (23 {+-} 2 deg. C), in ionic strength(I) = 0.1, 0.5, 1.0 and 2.0 M NaClO{sub 4}. The equilibrium condition was confirmed by over-saturation and under-saturation method. After the equilibrium, the pH{sub c} and the E{sub h} value of the suspension were measured. The suspension was then filtered using a filter with a NMWL of 3000 (less than 2 nm{phi}). The Np radio activity in the filtrate was determined by alpha spectrometry and absorption spectra of Np(IV). The solubility decreased with increasing pHc and the hydrolysis species are predominantly formed. From the obtained results, the solubility products (K{sub sp}) of Np hydroxide, for the reaction, NpO{sub 2} . xH{sub 2}O {r_reversible} Np{sup 4+} + 4OH{sup -} + (x-2)H{sub 2}O, at I = 0.1, 0.5, 1.0 and 2.0 were determined by using formation constants ({beta}{sub n}(I)), which were determined for the reaction, Np{sup 4+} + nOH{sup -} {r_reversible} Np(OH){sub n}{sup (4-n)+}. By using the specific interaction theory (SIT), the solubility product of tetravalent Np hydrous oxide is calculated to be log K{sub sp}{sup 0

  16. Copper(II) oxide solubility behavior in aqueous sodium phosphate solutions at elevated temperatures

    International Nuclear Information System (INIS)

    Ziemniak, S.E.; Jones, M.E.; Combs, K.E.S.

    1990-02-01

    A platinum-lined, flowing autoclave facility is used to investigate the solubility behavior of copper(II) oxide (CuO) in aqueous sodium phosphate solutions at temperatures between 292 and 535 K. Copper solubilities are observed to increase continuously with temperature and phosphate concentration. The measured solubility is examined via a Cu(II) ion hydrolysis/complexing model and thermodynamic functions for the hydrolysis/complexing reactions are obtained from a least- squares analysis of the data. Altogether, thermochemical properties are established for five anionic complexes: Cu(OH) 3 - , Cu(OH) 4 = , Cu(OH) 2 (HPO 4 ) = , Cu(OH) 3 (H 2 PO 4 ) = , and Cu(OH) 2 (PO 4 ) ≡ . Precise thermochemical parameters are also derived for the Cu(OH) + hydroxocomplex based on CuO solubility behavior previously observed in pure water (*) at elevated temperatures. The relative ease of Cu(II) ion hydrolysis is such that Cu(OH) 3 - species become the preferred hydroxocomplex for pH ≥ 9.4. 20 refs., 8 figs., 6 tabs

  17. The Solubility of metal oxides in molten carbonates - why the acid-basic chemistry fails?

    DEFF Research Database (Denmark)

    Bjerrum, Niels; Qingfeng, Li; Borup, Flemming

    1999-01-01

    Solubilities of various metal oxides in molten Li/K carbonates have been measured at 650°C under carbon dioxide atmosphere. It is found that the solubility of NiO and PbO decreases with increasing lithium mole fraction and decreasing CO2 partial pressure. On the other hand, the emf measurement...... shows opposite effects, i.e., decreasing CO2 pressure leads to more negative emf values but increasing lithium content gives more positive emf values. This contradiction is explained by means of a complex formation model. The possible species for lead are proposed to be [Pb(CO3)2]-2 and/or [Pb(CO3) 3...

  18. The flux of organic matter through a peatland ecosystem: The role of cellulose, lignin, and their control of the ecosystem oxidation state

    Science.gov (United States)

    Worrall, Fred; Moody, Catherine S.; Clay, Gareth D.; Burt, Tim P.; Rose, Rob

    2017-07-01

    This study used thermogravimetric analysis (TGA) to study the transit of organic C through a peatland ecosystem. The biomass, litter, peat soil profile, particulate organic matter (POM), and dissolved organic matter (DOM) fluxes were sampled from the Moor House National Nature Reserve, a peat-covered catchment in northern England where both the dry matter and carbon budget for the catchment were known. The study showed that although TGA traces showed distinct differences between organic matter reservoirs and fluxes, the traces could not readily be associated with particular functionalities or elemental properties. The TGA trace shows that polysaccharides are preferentially removed by humification and degradation with residual peat being dominated by lignin compositions. The DOM is derived from the degradation of lignin while the POM is derived from erosion of the peat profile. The carbon lost as gases (CO2 and CH4) was estimated to be composed of 92 to 95% polysaccharide carbon. The composition of the organic matter lost from the peat ecosystem means that the oxidative ratio (OR) of the ecosystem experienced by the atmosphere was between 0.96 and 0.99: currently, the Intergovernmental Panel on Climate Change uses an OR value of 1.1 for all ecosystems.

  19. Sorption processes affecting arsenic solubility in oxidized surface sediments from Tulare Lake Bed, California

    Science.gov (United States)

    Gao, S.; Goldberg, S.; Herbel, M.J.; Chalmers, A.T.; Fujii, R.; Tanji, K.K.

    2006-01-01

    Elevated concentrations of arsenic (As) in shallow groundwater in Tulare Basin pose an environmental risk because of the carcinogenic properties of As and the potential for its migration to deep aquifers that could serve as a future drinking water source. Adsorption and desorption are hypothesized to be the major processes controlling As solubility in oxidized surface sediments where arsenate [As(V)] is dominant. This study examined the relationship between sorption processes and arsenic solubility in shallow sediments from the dry Tulare Lake bed by determining sorption isotherms, pH effect on solubility, and desorption-readsorption behavior (hysteresis), and by using a surface complexation model to describe sorption. The sediments showed a high capacity to adsorb As(V). Estimates of the maximum adsorption capacity were 92 mg As kg- 1 at pH 7.5 and 70 mg As kg- 1 at pH 8.5 obtained using the Langmuir adsorption isotherm. Soluble arsenic [> 97% As(V)] did not increase dramatically until above pH 10. In the native pH range (7.5-8.5), soluble As concentrations were close to the lowest, indicating that As was strongly retained on the sediment. A surface complexation model, the constant capacitance model, was able to provide a simultaneous fit to both adsorption isotherms (pH 7.5 and 8.5) and the adsorption envelope (pH effect on soluble As), although the data ranges are one order of magnitude different. A hysteresis phenomenon between As adsorbed on the sediment and As in solution phase was observed in the desorption-readsorption processes and differs from conventional hysteresis observed in adsorption-desorption processes. The cause is most likely due to modification of adsorbent surfaces in sediment samples upon extensive extractions (or desorption). The significance of the hysteresis phenomenon in affecting As solubility and mobility may be better understood by further microscopic studies of As interaction mechanisms with sediments subjected to extensive leaching

  20. Lignin transformations and reactivity upon ozonation in aqueous media

    Science.gov (United States)

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

    2012-03-01

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

  1. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

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

    2015-01-01

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

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

    Science.gov (United States)

    Fukushima, Romualdo S; Hatfield, Ronald D

    2004-06-16

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

  3. Effects of fungal degradation on the CuO oxidation products of lignin: A controlled laboratory study

    Science.gov (United States)

    Hedges, John I.; Blanchette, Robert A.; Weliky, Karen; Devol, Allan H.

    1988-11-01

    Duplicate samples of birch wood were degraded for 0, 4, 8 and 12 weeks by the white-rot fungus, Phlebia tremellosus, and for 12 weeks by 6 other white-rot and brown-rot fungi. P. tremellosus caused progressive weight losses and increased the H/C and O/C of the remnant wood by preferentially degrading the lignin component of the middle lamellae. This fungus increased the absolute (weight loss-corrected) yield of the vanillic acid CuO reaction product above its initial level and exponentially decreased the absolute yields of all other lignin-derived phenols. Total yields of syringyl phenols were decreased 1.5 times as fast as total vanillyl phenol yields. Within both phenol families, aldehyde precursors were degraded faster than precursors of the corresponding ketones, which were obtained in constant proportion to the total phenol yield. Although two other white-rot fungi caused similar lignin compositional trends, a fourth white-rot species, Coriolus versicolor, simultaneously eroded all cell wall components and did not concentrate polysaccharides in the remnant wood. Wood degraded by the three brown-rot fungi exhibited porous cell walls with greatly reduced integrity. The brown-rot fungi also preferentially attacked syringyl structural units, but degraded all phenol precursors at a much slower rate than the white-rotters and did not produce excess vanillic acid. Degradation by P. tremellosus linearly increased the vanillic acid/vanillin ratio, (Ad/Al)v, of the remnant birch wood throughout the 12 week degradation study and exponentially decreased the absolute yields of total vanillyl phenols, total syringyl phenols and the syringyl/vanillyl phenol ratio, S/V. At the highest (Ad/Al)v of 0.50 (12 week samples), total yields of syringyl and vanillyl phenols were decreased by 65% and 80%, respectively, with a resulting reduction of 40% in the original S/V. Many of the diagenetically related compositional trends that have been previously reported for lignins in natural

  4. Preparation and characterization of nanostructured metal oxides for application to biomass upgrading Polar (111) metal oxide surfaces for pyrolysis oil upgrading and lignin depolymerization

    Science.gov (United States)

    Finch, Kenneth

    2013-01-01

    Pyrolysis oil, or bio-oil, is one of the most promising methods to upgrade a variety of biomass to transportation fuels. Moving toward a more "green" catalytic process requires heterogeneous catalysis over homogeneous catalysis to avoid extraction solvent waste. Nanoscale catalysts are showing great promise due to their high surface area and unusual surfaces. Base catalyzed condensation reactions occur much quicker than acid catalyzed condensation reactions. However, MgO is slightly soluble in water and is susceptible to degradation by acidic environments, similar to those found in fast-pyrolysis oil. Magnesium oxide (111) has a highly active Lewis base surface, which can catalyze Claisen-Schmidt condensation reactions in the organic phase. It has been shown previously that carbon coating a catalyst, such as a metal oxide, provides integrity while leaving the catalytic activity intact. Here, carbon-coated MgO(111) will be discussed with regards to synthesis, characterization and application to bio-oil upgrading through model compounds. Raman spectroscopy and HR-TEM are used to characterize the thickness and carbon-bonding environment of the carbon coating. Propanal self-condensation reactions have been conducted in the aqueous phase with varying amounts of acetic acid present. Quantitative analysis by gas chromatography was completed to determine the catalytic activity of CC-MgO(111). ICP-OES analysis has been conducted to measure the magnesium concentration in the product solution and give insight into the leaching of the catalyst into the reaction solution.

  5. Manufacturing of Dysprosium-Iron Alloys by Electrolysis in Fluoride-Based Electrolytes: Oxide Solubility Determinations

    Science.gov (United States)

    Martinez, Ana Maria; Støre, Anne; Osen, Karen Sende

    2018-04-01

    Electrolytic production of light rare earth elements and alloys takes place in a fluoride-based electrolyte using rare earth oxides as raw material. The optimization of this method, mainly in terms of the energy efficiency and environmental impact control, is rather challenging. Anode effects, evolution of fluorine-containing compounds, and side cathode reactions could largely be minimized by a good control of the amount of rare earth oxide species dissolved in the fluoride-based electrolyte and their dissolution rate. The oxide content of the fluoride melts REF3-LiF (RE = Nd, Dy) at different compositions and temperatures were experimentally determined by carbothermal analysis of melt samples. The highest solubility values of oxide species, added as Dy2O3 and Dy2(CO3)3, were obtained to be of ca. 3 wt pct (expressed as Dy2O3) in the case of the equimolar DyF3-LiF melt at 1323 K (1050 °C). The oxide saturation values increased with the amount of REF3 present in the molten bath and the working temperature.

  6. 3 and 4 oxidation state element solubilities in borosilicate glasses. Implement to actinides in nuclear glasses

    International Nuclear Information System (INIS)

    Cachia, J.N.

    2005-12-01

    In order to ensure optimal radionuclides containment, the knowledge of the actinide loading limits in nuclear waste glasses and also the comprehension of the solubilization mechanisms of these elements are essential. A first part of this manuscript deals with the study of the differences in solubility of the tri and tetravalent elements (actinides and surrogates) particularly in function of the melting temperature. The results obtained indicate that trivalent elements (La, Gd, Nd, Am, Cm) exhibit a higher solubility than tetravalent elements (Hf, Th, Pu). Consequently, it was planned to reduce plutonium at the oxidation state (III), the later being essentially tetravalent in borosilicate glasses. An innovating reduction process of multi-valent elements (cerium, plutonium) using silicon nitride has been developed in a second part of this work. Reduced plutonium-bearing glasses synthesized by Si 3 N 4 addition made it possible to double the plutonium solubility from 2 to 4 wt% at 1200 deg C. A structural approach to investigate the differences between tri and tetravalent elements was finally undertaken. These investigations were carried out by X-rays Absorption Spectroscopy (EXAFS) and NMR. Trivalent rare earth and actinide elements seem to behave as network modifiers while tetravalent elements rather present true intermediaries' behaviour. (author)

  7. Oxidation of lignin in hemp fibres by laccase: effects on mechanical properties of hemp fibres and unidirectional fibre/epoxy composites

    DEFF Research Database (Denmark)

    Liu, Ming; Baum, Andreas; Odermatt, Jürgen

    2017-01-01

    Laccase activity catalyzes oxidation and polymerization of phenols. The effect of laccase treatment on the mechanical properties of hemp fibres and hemp fibre/epoxy composites was examined. Laccase treatment on top of 0.5% EDTA + 0.2% endo-polygalacturonase (EPG) treatments increased the mechanical...... properties of hemp fibres and fibre/epoxy composites. Comparing all fibre treatments, composites with 0.5% EDTA + 0.2% EPG + 0.5% laccase treated fibres had highest stiffness of 42 GPa and highest ultimate tensile strength (UTS) of 326 MPa at a fibre volume content of 50%. The thermal resistance of hemp...... hemp fibres and their composites were due to laccase catalyzed polymerization of lignin moieties in hemp fibres....

  8. Centennial record of anthropogenic impacts in Galveston Bay: Evidence from trace metals (Hg, Pb, Ni, Zn) and lignin oxidation products.

    Science.gov (United States)

    Al Mukaimi, Mohammad E; Kaiser, Karl; Williams, Joshua R; Dellapenna, Timothy M; Louchouarn, Patrick; Santschi, Peter H

    2018-06-01

    During the 20th century the impacts of industrialization and urbanization in Galveston Bay resulted in significant shifts in trace metals (Hg, Pb, Ni, Zn) and vascular plant biomarkers (lignin phenols) recorded within the surface sediments and sediment cores profile. A total of 22 sediment cores were collected in Galveston Bay in order to reconstruct the historical input of Hg, Pb, Ni, Zn and terrestrial organic matter. Total Hg (T-Hg) concentration ranged between 6 and 162 ng g -1 in surface sediments, and showed decreasing concentrations southward from the Houston Ship Channel (HSC) toward the open estuary. Core profiles of T-Hg and trace metals (Ni, Zn) showed substantial inputs starting in 1905, with peak concentrations between 1960 and 1970's, and decreasing thereafter with exception to Pb, which peaked around 1930-1940s. Stable carbon isotopes and lignin phenols showed an increasing input of terrestrial organic matter driven by urban development within the watershed in the early 1940s. Both the enrichment factor and the geoaccumulation index (I geo ) for T-Hg as a measure of the effectiveness of environmental management practices showed substantial improvements since the 1970s. The natural recovery rate in Galveston Bay since the peak input of T-Hg was non-linear and displayed a slow recovery during the twenty-first century. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1984-01-01

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

  10. Paraquat induces oxidative stress and neuronal cell death; neuroprotection by water-soluble Coenzyme Q10

    International Nuclear Information System (INIS)

    McCarthy, S.; Somayajulu, M.; Sikorska, M.; Borowy-Borowski, H.; Pandey, S.

    2004-01-01

    Neuronal cell death induced by oxidative stress is correlated with numerous neurodegenerative diseases, including Alzheimer's disease (AD), Parkinson's disease (PD), and stroke. The causes of sporadic forms of age-related neurodegenerative diseases are still unknown. Recently, a correlation between paraquat exposure and neurodegenerative diseases has been observed. Paraquat, a nonselective herbicide, was once widely used in North America and is still routinely used in Taiwan. We have used differentiated Human Neuroblastoma (SHSY-5Y) cells as an in vitro model to study the mechanism of cell death induced by paraquat. We observed that paraquat-induced oxidative stress in differentiated SHSY-5Y cells as indicated by an increase in the production of cellular reactive oxygen species (ROS). Furthermore, apoptosis was evident as indicated by cellular and nuclear morphology and DNA fragmentation. Interestingly, pretreatment of SHSY-5Y cells with water-soluble Coenzyme Q 10 (CoQ 10 ) before paraquat exposure inhibited ROS generation. Pretreatment with CoQ 10 also significantly reduced the number of apoptotic cells and DNA fragmentation. We also analyzed the effect of paraquat and CoQ 10 on isolated mitochondria. Our results indicated that treatment with paraquat induced the generation of ROS from isolated mitochondria and depolarization of the inner mitochondrial membrane. Pretreatment with CoQ 10 was able to inhibit ROS generation from isolated mitochondria as well as the collapse of mitochondrial membrane potential. Our results indicate that water-soluble CoQ 10 can prevent oxidative stress and neuronal damage induced by paraquat and therefore, can be used for the prevention and therapy of neurodegenerative diseases caused by environmental toxins

  11. Cadmium solubility in paddy soils: Effects of soil oxidation, metal sulfides and competitive ions

    Energy Technology Data Exchange (ETDEWEB)

    Livera, Jennifer de, E-mail: Jennifer.deLivera@adelaide.edu.au [Soil Science, School of Agriculture Food and Wine, Waite Research Institute, University of Adelaide, Adelaide, SA (Australia); McLaughlin, Mike J. [Soil Science, School of Agriculture Food and Wine, Waite Research Institute, University of Adelaide, Adelaide, SA (Australia); CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); Hettiarachchi, Ganga M. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); Department of Agronomy, Kansas state University, Manhattan, KS (United States); Kirby, Jason K. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); CSIRO Land and Water, Environmental Biogeochemistry Program, Water for a Healthy Country Flagship, Adelaide, SA (Australia); Beak, Douglas G. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia)

    2011-03-15

    Cadmium (Cd) is a non-essential element for human nutrition and is an agricultural soil contaminant. Cadmium solubility in paddy soils affects Cd accumulation in the grain of rice. This is a human health risk, exacerbated by the fact that rice grains are deficient in iron (Fe) and zinc (Zn) for human nutrition. To find ways of limiting this potential risk, we investigated factors influencing Cd solubility relative to Fe and Zn during pre-harvest drainage of paddy soils, in which soil oxidation is accompanied by the grain-filling stage of rice growth. This was simulated in temperature-controlled 'reaction cell' experiments by first excluding oxygen to incubate soil suspensions anaerobically, then inducing aerobic conditions. In treatments without sulfur addition, the ratios of Cd:Fe and Cd:Zn in solution increased during the aerobic phase while Cd concentrations were unaffected and the Fe and Zn concentrations decreased. However, in treatments with added sulfur (as sulfate), up to 34 % of sulfur (S) was precipitated as sulfide minerals during the anaerobic phase and the Cd:Fe and Cd:Zn ratios in solution during the aerobic phase were lower than for treatments without S addition. When S was added, Cd solubility decreased whereas Fe and Zn were unaffected. When soil was spiked with Zn the Cd:Zn ratio was lower in solution during the aerobic phase, due to higher Zn concentrations. Decreased Cd:Fe and Cd:Zn ratios during the grain filling stage could potentially limit Cd enrichment in paddy rice grain due to competitive ion effects for root uptake. - Research Highlights: {yields} Cd:Fe and Cd:Zn ratios increase in paddy soil solution during oxidation. {yields} Cd:Fe and Cd:Zn ratios increase because Fe and Zn concentrations decrease. {yields} Cd concentrations do not change during oxidation. {yields} Cd:Fe and Cd:Zn ratios in solution decrease when Zn is added to soil. {yields} Metal sulfide precipitation lowers Cd:Fe and Cd:Zn ratios in soil solution.

  12. Soluble (Prorenin Receptor and Obstructive Sleep Apnea Syndrome: Oxidative Stress in Brain?

    Directory of Open Access Journals (Sweden)

    Kazuhiro Takahashi

    2017-06-01

    Full Text Available (Prorenin receptor ((PRR is a multi-functional molecule that is related to both the renin-angiotensin system (RAS and vacuolar H+-ATPase (v-ATPase, an ATP-dependent multi-subunit proton pump. Soluble (PRR (s(PRR, which consists of the extracellular domain of (PRR, is present in blood and urine. Elevated plasma s(PRR concentrations are reported in patients with chronic kidney disease and pregnant women with hypertension or diabetes mellitus. In addition, we have shown that plasma s(PRR concentrations are elevated in patients with obstructive sleep apnea syndrome (OSAS. Interestingly, the levels are elevated in parallel with the severity of OSAS, but are not related to the presence of hypertension or the status of the circulating RAS in OSAS. It is known that v-ATPase activity protects cells from endogenous oxidative stress, and loss of v-ATPase activity results in chronic oxidative stress. We hypothesize that hypoxia and subsequent oxidative stress, perhaps in the brain, may be one of the factors that elevate plasma s(PRR levels in OSAS.

  13. Microbial oxidation of soluble sulfide in produced water from the Bakkeen Sands

    Energy Technology Data Exchange (ETDEWEB)

    Gevertz, D.; Zimmerman, S. [Agouron Institute, La Jolla, CA (United States); Jenneman, G.E. [Phillips Petroleum Company, Bartlesville, OK (United States)] [and others

    1995-12-31

    The presence of soluble sulfide in produced water results in problems for the petroleum industry due to its toxicity, odor, corrosive nature, and potential for wellbore plugging. Sulfide oxidation by indigenous nitrate-reducing bacteria (NRB) present in brine collected from wells at the Coleville Unit (CVU) in Saskatchewan, Canada, was investigated. Sulfide oxidation took place readily when nitrate and phosphate were added to brine enrichment cultures, resulting in a decrease in sulfide levels of 99-165 ppm to nondetectable levels (< 3.3 ppm). Produced water collected from a number of producing wells was screened to determine the time required for complete sulfide oxidation, in order to select candidate wells for treatment. Three wells were chosen, based on sulfide removal in 48 hours or less. These wells were treated down the backside of the annulus with a solution containing 10 mM KNO{sub 3} and 100 {mu}M NaH{sub 2}PO{sub 4}. Following a 24- to 72-hour shut-in, reductions in pretreatment sulfide levels of greater than 90% were observed for two of the wells, as well as sustained sulfide reductions of 50% for at least two days following startup. NRB populations in the produced brine were observed to increase significantly following treatment, but no significant increases in sulfate-reducing bacteria were observed. These results demonstrate the technical feasibility of stimulating indigenous populations of NRB to remediate and control sulfide in produced brine.

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

    Science.gov (United States)

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

    2015-09-18

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

  15. Enzymatic Synthesis of Lignin-Based Concrete Dispersing Agents.

    Science.gov (United States)

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

    2018-03-15

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

  16. Solubility of indium-tin oxide in simulated lung and gastric fluids: Pathways for human intake.

    Science.gov (United States)

    Andersen, Jens Christian Østergård; Cropp, Alastair; Paradise, Diane Caroline

    2017-02-01

    From being a metal with very limited natural distribution, indium (In) has recently become disseminated throughout the human society. Little is known of how In compounds behave in the natural environment, but recent medical studies link exposure to In compounds to elevated risk of respiratory disorders. Animal tests suggest that exposure may lead to more widespread damage in the body, notably the liver, kidneys and spleen. In this paper, we investigate the solubility of the most widely used In compound, indium-tin oxide (ITO) in simulated lung and gastric fluids in order to better understand the potential pathways for metals to be introduced into the bloodstream. Our results show significant potential for release of In and tin (Sn) in the deep parts of the lungs (artificial lysosomal fluid) and digestive tract, while the solubility in the upper parts of the lungs (the respiratory tract or tracheobronchial tree) is very low. Our study confirms that ITO is likely to remain as solid particles in the upper parts of the lungs, but that particles are likely to slowly dissolve in the deep lungs. Considering the prolonged residence time of inhaled particles in the deep lung, this environment is likely to provide the major route for uptake of In and Sn from inhaled ITO nano- and microparticles. Although dissolution through digestion may also lead to some uptake, the much shorter residence time is likely to lead to much lower risk of uptake. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  17. Water-soluble thin film transistors and circuits based on amorphous indium-gallium-zinc oxide.

    Science.gov (United States)

    Jin, Sung Hun; Kang, Seung-Kyun; Cho, In-Tak; Han, Sang Youn; Chung, Ha Uk; Lee, Dong Joon; Shin, Jongmin; Baek, Geun Woo; Kim, Tae-il; Lee, Jong-Ho; Rogers, John A

    2015-04-22

    This paper presents device designs, circuit demonstrations, and dissolution kinetics for amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistors (TFTs) comprised completely of water-soluble materials, including SiNx, SiOx, molybdenum, and poly(vinyl alcohol) (PVA). Collections of these types of physically transient a-IGZO TFTs and 5-stage ring oscillators (ROs), constructed with them, show field effect mobilities (∼10 cm2/Vs), on/off ratios (∼2×10(6)), subthreshold slopes (∼220 mV/dec), Ohmic contact properties, and oscillation frequency of 5.67 kHz at supply voltages of 19 V, all comparable to otherwise similar devices constructed in conventional ways with standard, nontransient materials. Studies of dissolution kinetics for a-IGZO films in deionized water, bovine serum, and phosphate buffer saline solution provide data of relevance for the potential use of these materials and this technology in temporary biomedical implants.

  18. Solubility of metal oxides in molten equimolar KBr-NaBr mixture at 973 K

    Science.gov (United States)

    Cherginets, V. L.; Rebrova, T. P.; Naumenko, V. A.

    2014-09-01

    Solubility products (p K s,MO, molality) are measured by potentiometric titration with a Pt(O2)|ZrO2(Y2O3) oxygen electrode in the molten KBr-NaBr equimolar mixture at 973 K for the following oxides: CaO (5.00 ± 0.3), MnO (7.85 ± 0.3), NiO (9.72 ± 0.04), PbO (5.20 ± 0.3), and SrO (3.81 ± 0.3). The correlation between p K s,MeO and the polarization of the corresponding cations by Goldschmidt is obtained.

  19. Modulating lignin in plants

    Science.gov (United States)

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

    2013-01-29

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

  20. Noncatalytic Direct Liquefaction of Biorefinery Lignin by Ethanol

    DEFF Research Database (Denmark)

    Nielsen, Joachim Bachmann; Jensen, Anders; Madsen, Line Riis

    2017-01-01

    There is a growing interest in lignin valorization to biofuels and chemicals. Here, we propose a novel and simple noncatalytic process to directly liquefy lignin rich solid residual from second generation bioethanol production by solvolysis with ethanol. Through an extensive parameter study...... in batch autoclaves assessing the effects of varying reaction temperature, reaction time, and solvent:lignin ratio, it is shown that hydrothermally pretreated enzymatic hydrolysis lignin solvolysis in supercritical ethanol can produce a heptane soluble bio-oil without the need for exhaustive deoxygenation....... The process does not require addition of catalyst or a reducing agent such as hydrogen. The process is advantageously carried out with a low reaction period ((ethanol:lignin (w/w) ratio of 2:1) which is a previously unexplored domain for lignin...

  1. Water soluble nano-scale transient material germanium oxide for zero toxic waste based environmentally benign nano-manufacturing

    KAUST Repository

    Almuslem, A. S.

    2017-02-14

    In the recent past, with the advent of transient electronics for mostly implantable and secured electronic applications, the whole field effect transistor structure has been dissolved in a variety of chemicals. Here, we show simple water soluble nano-scale (sub-10 nm) germanium oxide (GeO) as the dissolvable component to remove the functional structures of metal oxide semiconductor devices and then reuse the expensive germanium substrate again for functional device fabrication. This way, in addition to transiency, we also show an environmentally friendly manufacturing process for a complementary metal oxide semiconductor (CMOS) technology. Every year, trillions of complementary metal oxide semiconductor (CMOS) electronics are manufactured and billions are disposed, which extend the harmful impact to our environment. Therefore, this is a key study to show a pragmatic approach for water soluble high performance electronics for environmentally friendly manufacturing and bioresorbable electronic applications.

  2. Lignin Valorization: Emerging Approaches

    Energy Technology Data Exchange (ETDEWEB)

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

    2018-04-03

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

  3. Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses.

    Science.gov (United States)

    Brehault, Antoine; Patil, Deepak; Kamat, Hrishikesh; Youngman, Randall E; Thirion, Lynn M; Mauro, John C; Corkhill, Claire L; McCloy, John S; Goel, Ashutosh

    2018-02-08

    Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO 4 2- ) exhibit very low solubility (∼1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO 3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO 3 with incorporation of rare-earth oxides (for example, Nd 2 O 3 ) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO 3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO 3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO 3 in rare-earth containing aluminoborosilicate

  4. Lignin depolymerization by fungal secretomes and a microbial sink

    Energy Technology Data Exchange (ETDEWEB)

    Salvachúa, Davinia; Katahira, Rui; Cleveland, Nicholas S.; Khanna, Payal; Resch, Michael G.; Black, Brenna A.; Purvine, Samuel O.; Zink, Erika M.; Prieto, Alicia; Martínez, María J.; Martínez, Angel T.; Simmons, Blake A.; Gladden, John M.; Beckham, Gregg T.

    2016-08-25

    In Nature, powerful oxidative enzymes secreted by white rot fungi and some bacteria catalyze lignin depolymerization and some microbes are able to catabolize the resulting aromatic compounds as carbon and energy sources. Taken together, these two processes offer a potential route for microbial valorization of lignin. However, many challenges remain in realizing this concept, including that oxidative enzymes responsible for lignin depolymerization also catalyze polymerization of low molecular weight (LMW) lignin. Here, multiple basidiomycete secretomes were screened for ligninolytic enzyme activities in the presence of a residual lignin solid stream from a corn stover biorefinery, dubbed DMR-EH (Deacetylation, Mechanical Refining, and Enzymatic Hydrolysis) lignin. Two selected fungal secretomes, with high levels of laccases and peroxidases, were utilized for DMR-EH lignin depolymerization assays. The secretome from Pleurotus eryngii, which exhibited the highest laccase activity, reduced the lignin average molecular weight by 63% and 75% at pH 7 compared to the Mw of the control treated at the same conditions and the initial DMR-EH lignin, respectively, and was applied in further depolymerization assays as a function of time. As repolymerization was observed after 3 days of incubation, an aromatic-catabolic microbe (Pseudomonas putida KT2440) was incubated with the fungal secretome and DMR-EH lignin. These experiments demonstrated that the presence of the bacterium enhances lignin depolymerization, likely due to bacterial catabolism of LMW lignin, which may partially prevent repolymerization. In addition, proteomics was also applied to the P. eryngii secretome to identify the enzymes present in the fungal cocktail utilized for the depolymerization assays, which highlighted a significant number of glucose/ methanol/choline (GMC) oxidoreductases and laccases. Overall, this study demonstrates that ligninolytic enzymes can be used to partially depolymerize a solid, high

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1981-01-01

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

  6. Plutonium solubilities

    International Nuclear Information System (INIS)

    Puigdomnech, I.; Bruno, J.

    1991-02-01

    Thermochemical data has been selected for plutonium oxide, hydroxide, carbonate and phosphate equilibria. Equilibrium constants have been evaluated in the temperature range 0 to 300 degrees C at a pressure of 1 bar to T≤100 degrees C and at the steam saturated pressure at higher temperatures. Measured solubilities of plutonium that are reported in the literature for laboratory experiments have been collected. Solubility data on oxides, hydroxides, carbonates and phosphates have been selected. No solubility data were found at temperatures higher than 60 degrees C. The literature solubility data have been compared with plutonium solubilities calculated with the EQ3/6 geochemical modelling programs, using the selected thermodynamic data for plutonium. (authors)

  7. Chemical factors that control lignin polymerization.

    Science.gov (United States)

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

    2014-01-09

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

  8. Lignin biomass conversion into chemicals and fuels

    DEFF Research Database (Denmark)

    Melián Rodríguez, Mayra

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

  9. Analytical methodology for sulfonated lignins

    NARCIS (Netherlands)

    Brudin, S.; Schoenmakers, P.

    2010-01-01

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

  10. Noncovalently-functionalized reduced graphene oxide sheets by water-soluble methyl green for supercapacitor application

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Xiaoying; Hu, Zhongai, E-mail: zhongai@nwnu.edu.cn; Hu, Haixiong; Qiang, Ruibin; Li, Li; Li, Zhimin; Yang, Yuying; Zhang, Ziyu; Wu, Hongying

    2015-10-15

    Graphical abstract: Electroactive methyl green (MG) is selected to functionalize reduced graphene oxide (RGO) through non-covalent modification and the composite achieves high specific capacitance, good rate capability and excellent long life cycle. - Highlights: • MG–RGO composites were firstly prepared through non-covalent modification. • The mass ratio in composites is a key for achieving high specific capacitance. • MG–RGO 5:4 exhibits the highest specific capacitance of 341 F g{sup −1}. • MG–RGO 5:4 shows excellent rate capability and long life cycle. - Abstract: In the present work, water-soluble electroactive methyl green (MG) has been used to non-covalently functionalize reduced graphene oxide (RGO) for enhancing supercapacitive performance. The microstructure, composition and morphology of MG–RGO composites are systematically characterized by UV–vis absorption, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The electrochemical performances are investigated by cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). The fast redox reactions from MG could generate additional pseudocapacitance, which endows RGO higher capacitances. As a result, the MG–RGO composite (with the 5:4 mass ratio of MG:RGO) achieve a maximum value of 341 F g{sup −1} at 1 A g{sup −1} within the potential range from −0.25 to 0.75 V and provide a 180% enhancement in specific capacitance in comparison with pure RGO. Furthermore, excellent rate capability (72% capacitance retention from 1 A g{sup −1} to 20 A g{sup −1}) and long life cycle (12% capacitance decay after 5000 cycles) are achieved for the MG–RGO composite electrode.

  11. Bacteria and lignin degradation

    Institute of Scientific and Technical Information of China (English)

    Jing LI; Hongli YUAN; Jinshui YANG

    2009-01-01

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

  12. In vitro oxidation of indoleacetic acid by soluble auxin-oxidases and peroxidases from maize roots

    International Nuclear Information System (INIS)

    Beffa, R.; Martin, H.V.; Pilet, P.E.

    1990-01-01

    Soluble auxin-oxidases were extracted from Zea mays L. cv LG11 apical root segments and partially separated from peroxidases (EC 1.11.1.7) by size-exclusion chromatography. Auxin-oxidases were resolved into one main peak corresponding to a molecular mass of 32.5 kilodaltons and a minor peak at 54.5 kilodaltons. Peroxidases were separated into at least four peaks, with molecular masses from 32.5 to 78 kilodaltons. In vitro activity of indoleacetic acid-oxidases was dependent on the presence of MnCl 2 and p-coumaric acid. Compound(s) present in the crude extract and several synthetic auxin transport inhibitors (including 2,3,5-triiodobenzoic acid and N-1-naphthylphthalamic acid) inhibited auxin-oxidase activity, but had no effect on peroxidases. The products resulting from the in vitro enzymatic oxidation of [ 3 H]indoleacetic acid were separated by HPLC and the major metabolite was found to cochromatograph with indol-3yl-methanol

  13. Zinc oxide nanoparticles and monocytes: Impact of size, charge and solubility on activation status

    International Nuclear Information System (INIS)

    Prach, Morag; Stone, Vicki; Proudfoot, Lorna

    2013-01-01

    Zinc oxide (ZnO) particle induced cytotoxicity was dependent on size, charge and solubility, factors which at sublethal concentrations may influence the activation of the human monocytic cell line THP1. ZnO nanoparticles (NP; average diameter 70 nm) were more toxic than the bulk form ( 2+ ion with protein. This association with protein may influence interaction of the ZnO particles and NP with THP1 cells. After 24 h exposure to the ZnO particles and NP at sublethal concentrations there was little effect on immunological markers of inflammation such as HLA DR and CD14, although they may induce a modest increase in the adhesion molecule CD11b. The cytokine TNFα is normally associated with proinflammatory immune responses but was not induced by the ZnO particles and NP. There was also no effect on LPS stimulated TNFα production. These results suggest that ZnO particles and NP do not have a classical proinflammatory effect on THP1 cells. -- Highlights: ► ZnO is cytotoxic to THP-1 monocytes. ► ZnO nanoparticles are more toxic than the bulk form. ► Positive charge enhances ZnO nanoparticle cytotoxicity. ► Sublethal doses of ZnO particles do not induce classical proinflammatory markers.

  14. Lignin-based cement fluid loss control additive

    Energy Technology Data Exchange (ETDEWEB)

    Schilling, P.

    1990-05-22

    This patent describes a hydraulic cement slurry composition. It comprises: a hydraulic cement, and the following expressed as parts by weight per 100 parts of the hydraulic cement, water from about 25 to 105 parts, and from abut 0.5 to 2.5 parts of a compound selected from the group consisting of a sulfonated lignin and a sulfomethylated lignin, wherein the lignin has been sequentially crosslinked by reacting the lignin with a member of the group consisting of formaldehyde and epichlorohydrin and alkoxylated with between about 2 to about 6 moles of a compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and a combination thereof per 1000 g of the lignin.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

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

    Science.gov (United States)

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

    2013-02-01

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

  17. Production of Flocculants, Adsorbents, and Dispersants from Lignin.

    Science.gov (United States)

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

    2018-04-10

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

  18. Production of Flocculants, Adsorbents, and Dispersants from Lignin

    Directory of Open Access Journals (Sweden)

    Jiachuan Chen

    2018-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-05

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

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

    Science.gov (United States)

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

    2012-02-01

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

  1. The participation of soluble factors in the omega-oxidation of fatty acids in the liver of the sheep

    International Nuclear Information System (INIS)

    Hare, W.R.; Wahle, K.W.

    1991-01-01

    The removal of soluble components from an ovine hepatic microsomal preparation decreased the omega-hydroxylation of dodecanoic and hexadecanoic acids. The results suggest that one or more soluble components play a role in the microsomal omega-hydroxylation of fatty acids. The possible roles in the reaction of catalase (known to stimulate the microsomal desaturations of fatty acids and alkylglycerols) and superoxide dismutase were investigated. The addition of these enzymes to the complete (but not the washed) microsomal preparation stimulated both the initial omega-hydroxylation reaction and the subsequent dehydrogenation reactions of the omega-oxidation pathway. The similarity of the effects of catalase and superoxide dismutase and stimulation of two different steps of the omega-oxidation pathway suggest that these agents are acting indirectly by removing active oxygen species rather than directly on the enzymes of microsomal fatty acid omega-hydroxylation

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

    Science.gov (United States)

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

    2013-01-01

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

  3. Zinc oxide nanoparticles and monocytes: Impact of size, charge and solubility on activation status

    Energy Technology Data Exchange (ETDEWEB)

    Prach, Morag [Edinburgh Napier University, School of Life, Sport and Social Science, Edinburgh (United Kingdom); Stone, Vicki [Heriot-Watt University, School of Life Sciences, Edinburgh (United Kingdom); Proudfoot, Lorna, E-mail: l.proudfoot@napier.ac.uk [Edinburgh Napier University, School of Life, Sport and Social Science, Edinburgh (United Kingdom)

    2013-01-01

    Zinc oxide (ZnO) particle induced cytotoxicity was dependent on size, charge and solubility, factors which at sublethal concentrations may influence the activation of the human monocytic cell line THP1. ZnO nanoparticles (NP; average diameter 70 nm) were more toxic than the bulk form (< 44 μm mesh) and a positive charge enhanced cytotoxicity of the NP despite their relatively high dissolution. A positive charge of the particles has been shown in other studies to have an influence on cell viability. Centrifugal filtration using a cut off of 5 kDa and Zn element analysis by atomic absorption spectroscopy confirmed that exposure of the ZnO particles and NP to 10% foetal bovine serum resulted in a strong association of the Zn{sup 2+} ion with protein. This association with protein may influence interaction of the ZnO particles and NP with THP1 cells. After 24 h exposure to the ZnO particles and NP at sublethal concentrations there was little effect on immunological markers of inflammation such as HLA DR and CD14, although they may induce a modest increase in the adhesion molecule CD11b. The cytokine TNFα is normally associated with proinflammatory immune responses but was not induced by the ZnO particles and NP. There was also no effect on LPS stimulated TNFα production. These results suggest that ZnO particles and NP do not have a classical proinflammatory effect on THP1 cells. -- Highlights: ► ZnO is cytotoxic to THP-1 monocytes. ► ZnO nanoparticles are more toxic than the bulk form. ► Positive charge enhances ZnO nanoparticle cytotoxicity. ► Sublethal doses of ZnO particles do not induce classical proinflammatory markers.

  4. Exploring bacterial lignin degradation.

    Science.gov (United States)

    Brown, Margaret E; Chang, Michelle C Y

    2014-04-01

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

  5. Biotechnological modification of lignin

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

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

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

    Science.gov (United States)

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

    2013-01-01

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

  7. A FUNDAMENTAL STUDY ON SOLUBILITY OF HEAVY METAL OXIDES IN AMMONIUM AND PHOSPHONIUM BASED DEEP EUTECTIC SOLVENTS

    Directory of Open Access Journals (Sweden)

    SHANGGARY RAJENDRAN

    2016-02-01

    Full Text Available Water pollution has become increasingly prevalent in our daily lives and has caused a serious threat at a global level. Among the various pollutants that exist,heavy metal pollution has become an issue of great concern due to their high toxicity, greater bioaccumulation in human body and food chain, nonbiodegradability nature, and carcinogenic effects to humans. This study aims to address the heavy metal ion contamination in wastewater by providing a low cost and efficient removal technique using DESs. In this investigation, the solubility of CuO and ZnO heavy metal oxide ions with concentration of 20g/L was studied in ammonium and phosphonium based DESs. The samples were left to stir at 250 rpm at 28, 45 and 65°C respectively for four hours in an incubator orbital shaker and the solubility of the heavy metal ions were analysed using Atomic Absorption Spectrometer (AAS using serial dilution technique. Phosphonium based DES which contain Methyl Triphenyl Phosphonium Bromide (MTPB showed higher solubility of CuO and ZnO ions. Based on the results obtained, DES 6 (MTPB: Glycerol has the highest solubility of CuO, 0.197 mg/L at 65°C and the solubility of ZnO was found to be the highest in DES 7 (MTPB: Glycerol, 1.225 mg/L at 65°C. Higher solubility was observed in samples containing ZnO as they are more ionic compared to CuO.

  8. Radiotracer experiments on lignin reactions, 2

    International Nuclear Information System (INIS)

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

    1977-01-01

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

  9. Reductive Catalytic Fractionation of Corn Stover Lignin

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-05

    that soluble oligomers are formed via solvolysis, followed by further fragmentation on the catalyst surface via hydrogenolysis. Overall, the results show that clear trade-offs exist between the levels of lignin extraction, monomer yields, and carbohydrate retention in the residual solids for different RCF conditions of corn stover.

  10. Amelioration of radiation induced oxidative stress using water soluble chitosan produced by Aspergillus niger

    International Nuclear Information System (INIS)

    EL-Sonbaty, S.M.; Swailam, H.M.; Noaman, E.

    2012-01-01

    Chitosan is a natural polysaccharide synthesized by a great number of living organisms and considered as a source of potential bioactive material and has many biological applications which are greatly affected by its solubility in neutral ph. In this study low molecular weight water soluble chitosan was prepared by chemical degradation of chitosan produced by Aspergillus niger using H 2 O 2 . Chitosan chemical structure was detected before and after treatment using FTIR spectrum, and its molecular weight was determined by its viscosity using viscometer. Its antioxidant activity against gamma radiation was evaluated in vivo using rats. Rats were divided into 4 groups; group 1: control, group 2: exposed to acute dose of gamma radiation (6 Gy), group 3: received water soluble chitosan, group 4: received water soluble chitosan then exposed to gamma radiation as group 2. Gamma radiation significantly increased malonaldehyde, decreased glutathione concentration, activity of superoxide dismutase, catalase, and glutatione peroxidase, while significantly increase the activity of alanine transferase, aspartate transferase, urea and creatinine concentration. Administration of water soluble chitosan has ameliorated induced changes caused by gamma radiation. It could be concluded that water soluble chitosan by scavenging free radicals directly or indirectly may act as a potent radioprotector against ionizing irradiation.

  11. Redox Fluctuations Increase the Contribution of Lignin to Soil Respiration

    Science.gov (United States)

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

    2014-12-01

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

  12. Acidity of cations and the solubility of oxides in the eutectic KCl-LiCl melt at 700 Deg C

    International Nuclear Information System (INIS)

    Cherginets, V.L.; Rebrova, T.P.

    1999-01-01

    Products of MgO, NiO and CoO solubility in KCl-LiCl melt at 700 Deg C were determined by the method of potentiometric titration using Pt(O 2 )IZrO 2 (Y 2 O 3 ) membrane oxygen electrode. It was ascertained that acid properties of Cd 2+ and Pb'2 + cations are levelled to Li + properties, a break in E-pO graduation dependence in KCl-LiCl melt was observed at pO ∼ 2. Increase in oxides solubility in the melt studied compared with KCl-NaCl and CsCl-KCl-NaCl melts stems from the presence of Li + cations in the melt studied, which possess stronger acid properties than those of Na + or K + [ru

  13. Emission Properties, Solubility, Thermodynamic Analysis and NMR Studies of Rare-Earth Complexes with Two Different Phosphine Oxides

    Directory of Open Access Journals (Sweden)

    Hiroki Iwanaga

    2010-07-01

    Full Text Available The paper proposes novel molecular designs for rare-earth complexes involving the introduction of two different phosphine oxide structures into one rare-earth ion. These designs are effective for improving solubility and emission intensity. Additionally, the complexes are indispensable for realizing high performances in LEDs and security media. The thermodynamic properties of Eu(III complexes are correlated with the solubility. Correlations between coordination structures and emission intensity were explained by NMR analysis. The luminous flux of red LED devices with Eu(III complexes is very high (20 mA, 870 m lumen. A new white LED has its largest spectra intensity in the red region and a human look much more vividly under this light.

  14. Characterization of electrospun lignin based carbon fibers

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-22

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

  15. Characterization of electrospun lignin based carbon fibers

    International Nuclear Information System (INIS)

    Poursorkhabi, Vida; Mohanty, Amar; Misra, Manjusri

    2015-01-01

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

  16. Crystalline Ethylene Oxide and Propylene Oxide Triblock Copolymer Solid Dispersion Enhance Solubility, Stability and Promoting Time- Controllable Release of Curcumin.

    Science.gov (United States)

    Alves, Thais F R; das Neves Lopes, Franciely C C; Rebelo, Marcia A; Souza, Juliana F; da Silva Pontes, Katiusca; Santos, Carolina; Severino, Patricia; Junior, Jose M O; Komatsu, Daniel; Chaud, Marco V

    2018-01-01

    The design and development of an effective medicine are, however, often faced with a number of challenges. One of them is the close relationship of drug's bioavailability with solubility, dissolution rate and permeability. The use of curcumin's (CUR) therapeutic potential is limited by its poor water solubility and low chemical stability. The purpose was to evaluate the effect of polymer and solid dispersion (SD) preparation techniques to enhance the aqueous solubility, dissolution rate and stability of the CUR. The recent patents on curcumin SD were reported as (i) curcumin with polyvinylpyrrolidone (CN20071 32500 20071214, WO2006022012 and CN20151414227 20150715), (ii) curcumin-zinc/polyvinylpyrrolidone (CN20151414227 20150715), (iii) curcumin-poloxamer 188 (CN2008171177 20080605), (iv) curcumin SD prepared by melting method (CN20161626746-20160801). SD obtained by co-preciptation or microwave fusion and the physical mixture of CUR with Poloxamer-407 (P-407), Hydroxypropylmetylcellulose-K4M (HPMC K4M) and Polyvinylpyrrolidone-K30 (PVP-K30) were prepared at the ratios of 1:2; 1:1 and 2:1. The samples were evaluated by solubility, stability, dissolution rate and characterized by SEM, PXRD, DSC and FTIR. The solubility, stability (pH 7.0) and dissolution rate were significantly greater for SD (CUR:P-407 1:2). The PXRD,SEM and DSC indicated a change in the crystalline state of CUR. The enhancement of solubility was dependent on a combination of factors including the weight ratio, preparation techniques and carrier properties. The drug release data fitted well with the Weibull equation, indicating that the drug release was controlled by diffusion, polymer relaxation and erosion occurring simultaneously. Thus, these SDs, specifically CUR:P-407 1:2 w/w, can overcome the barriers of poor bioavailability to reap many beneficial properties. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

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

    Science.gov (United States)

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

    2017-10-01

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

  18. Atomistic simulation of CO 2 solubility in poly(ethylene oxide) oligomers

    KAUST Repository

    Hong, Bingbing; Panagiotopoulos, Athanassios Z.

    2013-01-01

    We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide

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

    Science.gov (United States)

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

    2012-06-20

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

  20. CADMIUM SOLUBILITY IN PADDY SOILS: EFFECTS OF SOIL OXIDATION, METAL SULFIDES AND COMPETITIVE IONS.

    Science.gov (United States)

    Cadmium (Cd) is a non-essential element for human nutrition and is an agricultural soil contaminant. Cadmium solubility in paddy soils affects Cd accumulation in the grain of rice. This is a human health risk, exacerbated by the fact that rice grains are deficient in iron (Fe) an...

  1. Soluble CD40 Ligand and Oxidative Response Are Reciprocally Stimulated during Shiga Toxin-Associated Hemolytic Uremic Syndrome

    Directory of Open Access Journals (Sweden)

    Maria J. Abrey Recalde

    2017-10-01

    Full Text Available Shiga toxin (Stx, produced by Escherichia coli, is the main pathogenic factor of diarrhea-associated hemolytic uremic syndrome (HUS, which is characterized by the obstruction of renal microvasculature by platelet-fibrin thrombi. It is well known that the oxidative imbalance generated by Stx induces platelet activation, contributing to thrombus formation. Moreover, activated platelets release soluble CD40 ligand (sCD40L, which in turn contributes to oxidative imbalance, triggering the release of reactive oxidative species (ROS on various cellular types. The aim of this work was to determine if the interaction between the oxidative response and platelet-derived sCD40L, as consequence of Stx-induced endothelium damage, participates in the pathogenic mechanism during HUS. Activated human glomerular endothelial cells (HGEC by Stx2 induced platelets to adhere to them. Although platelet adhesion did not contribute to endothelial damage, high levels of sCD40L were released to the medium. The release of sCD40L by activated platelets was inhibited by antioxidant treatment. Furthermore, we found increased levels of sCD40L in plasma from HUS patients, which were also able to trigger the respiratory burst in monocytes in a sCD40L-dependent manner. Thus, we concluded that platelet-derived sCD40L and the oxidative response are reciprocally stimulated during Stx2-associated HUS. This process may contribute to the evolution of glomerular occlusion and the microangiopathic lesions.

  2. Soluble CD40 Ligand and Oxidative Response Are Reciprocally Stimulated during Shiga Toxin-Associated Hemolytic Uremic Syndrome

    Science.gov (United States)

    Abrey Recalde, Maria J.; Alvarez, Romina S.; Alberto, Fabiana; Mejias, Maria P.; Ramos, Maria V.; Fernandez Brando, Romina J.; Bruballa, Andrea C.; Exeni, Ramon A.; Alconcher, Laura; Ibarra, Cristina A.; Amaral, María M.; Palermo, Marina S.

    2017-01-01

    Shiga toxin (Stx), produced by Escherichia coli, is the main pathogenic factor of diarrhea-associated hemolytic uremic syndrome (HUS), which is characterized by the obstruction of renal microvasculature by platelet-fibrin thrombi. It is well known that the oxidative imbalance generated by Stx induces platelet activation, contributing to thrombus formation. Moreover, activated platelets release soluble CD40 ligand (sCD40L), which in turn contributes to oxidative imbalance, triggering the release of reactive oxidative species (ROS) on various cellular types. The aim of this work was to determine if the interaction between the oxidative response and platelet-derived sCD40L, as consequence of Stx-induced endothelium damage, participates in the pathogenic mechanism during HUS. Activated human glomerular endothelial cells (HGEC) by Stx2 induced platelets to adhere to them. Although platelet adhesion did not contribute to endothelial damage, high levels of sCD40L were released to the medium. The release of sCD40L by activated platelets was inhibited by antioxidant treatment. Furthermore, we found increased levels of sCD40L in plasma from HUS patients, which were also able to trigger the respiratory burst in monocytes in a sCD40L-dependent manner. Thus, we concluded that platelet-derived sCD40L and the oxidative response are reciprocally stimulated during Stx2-associated HUS. This process may contribute to the evolution of glomerular occlusion and the microangiopathic lesions. PMID:29068360

  3. The optical and electrical properties of graphene oxide with water-soluble conjugated polymer composites by radiation.

    Science.gov (United States)

    Jungo, Seung Tae; Oh, Seung-Hwan; Kim, Hyun Bin; Jeun, Joon-Pyo; Lee, Bum-Jae; Kang, Phil-Hyun

    2013-11-01

    In order to overcome the difficulty of dispersion and low conductivity in composite containing graphene, graphene oxide (GO) has been used instead of neat graphene. And the GO treated by radiation, could give improved conductivity of the GO-containing polymer composite. In this study, fluorene based water-soluble conjugated polymer (WPF-6-oxy-F) was introduced in GO solution to investigate the change of optical and electrical properties through radiation process. UV-Vis absorption of irradiated WPF-6-oxy-F-GO composite was red shifted and I(D)/I(G) ratio of Raman spectra decreased. XPS analysis showed that C-N bonds was formed after the irradiation and confirmed the increased bonds between the GO and the water-soluble conjugated polymer matrix. From the AFM and XPS analysis, it was found that the water-soluble conjugated polymer matrix was stacked between the modified GO in the morphology of irradiated WPF-6-oxy-F-GO composite was increased after gamma ray irradiation up to 10(-2) S/cm.

  4. Effect of radio-oxidative ageing and pH on the release of soluble organic matter from bitumen

    International Nuclear Information System (INIS)

    Libert, M.F.; Walczak, I.

    2000-01-01

    Bitumen is employed as an embedding matrix for low and medium level radioactive wastes. An high impermeability and a great resistance against most of chemicals are two of main bitumen properties. These characteristics of bitumen confinement properties may be modified under environmental parameters during intermediate storage or deep repository such as radiations or the presence of water. The radio-oxidation induces an increase of the quantity of leached organic matter. The evolution of the soluble organic species release seems to be linear with the irradiation dose, as soon as the dose is higher than 20 kGy, and seems to be no dependant of the dose rate. The generation of water-soluble organic complexing agents can affect the integrity of the wasteform due to an increase of the radionuclides solubility. An increase of the quantity of leached organic matter is also observed in presence of alkaline solutions. Identified molecules, by GC/MS analysis, are aromatics like naphthalene, oxidised compounds like alcohols, linear carbonyls, aromatics, glycols and nitrogen compounds. (authors)

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

    Science.gov (United States)

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

    2014-06-18

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

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

    Science.gov (United States)

    Ross, Kelly; Mazza, Giuseppe

    2010-01-01

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

  7. Speciation and Oxidative Stability of Alkaline Soluble, Non-Pertechnetate Technetium

    Energy Technology Data Exchange (ETDEWEB)

    Levitskaia, Tatiana G. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Rapko, Brian M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Anderson, Amity [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Peterson, James M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Chatterjee, Sayandev [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walter, Eric D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cho, Herman M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washton, Nancy M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2014-09-30

    The long half-life, complex chemical behavior in tank waste, limited incorporation in mid- to high-temperature immobilization processes, and high mobility in subsurface environments make technetium (Tc) one of the most difficult contaminants to dispose of and/or remediate. Technetium exists predominantly in the liquid tank waste phase as the relatively mobile form of pertechnetate, TcO4-. However, based on experimentation to date a significant fraction of the soluble Tc cannot be effectively separated from the wastes and may be present as a non- pertechnetate species. The presence of a non-pertechnetate species significantly complicates disposition of low-activity waste (LAW), and the development of methods to either convert them to pertechnetate or to separate directly is needed. The challenge is the uncertainty regarding the chemical form of the alkaline-soluble low-valent non-pertechnetate species in the liquid tank waste. This report summarizes work done in fiscal year (FY) 2014 exploring the chemistry of a low-valence technetium(I) species, [(CO)3Tc(H2O)3]+, a compound of interest due to its implication in the speciation of alkaline-soluble technetium in several Hanford tank waste supernatants.

  8. New techniques for the characterization of lignins

    International Nuclear Information System (INIS)

    Javor, T.

    2001-09-01

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

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

    International Nuclear Information System (INIS)

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

    1986-01-01

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

  10. Hydroxide catalysts for lignin depolymerization

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-04-25

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

  11. Hydroxide catalysts for lignin depolymerization

    Science.gov (United States)

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

    2017-10-17

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

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

    Science.gov (United States)

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

    2015-01-01

    Lignin was isolated from the residue of bioethanol production with oak wood via alkaline and catalyzed organosolv treatments at ambient temperature to improve the purity of lignin for the materials application. The isolated lignins were analyzed for their chemical composition by nitrobenzene oxidation method and their functionality was characterized via wet chemistry method, element analysis, (1)H NMR, GPC and FTIR-ATR. The isolated lignin by acid catalyzed organosolv treatment (Acid-OSL) contained a higher lignin content, aromatic proton, phenolic hydroxyl group and a lower nitrogen content that is more reactive towards chemical modification. The lignin-based adhesives were prepared and the bond strength was measured to evaluate the enhanced reactivity of lignin by the isolation. Two steps of phenolation and methylolation were applied for the modification of the isolated lignins and their tensile strengths were evaluated for the use as an adhesive. The acid catalyzed organosolv lignin-based adhesives had comparable bond strength to phenol-formaldehyde adhesives. The analysis of lignin-based adhesives by FTIR-ATR and TGA showed structural similarity to phenol adhesive. The results demonstrate that the reactivity of lignin was enhanced by isolation from hardwood bioethanol production residues at ambient temperature and it could be used in a value-added application to produce lignin-based adhesives. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Differential expression in Phanerochaete chrysosporium of membrane- associated proteins relevant to lignin degradation

    Science.gov (United States)

    Semarjit Shary; Alexander N. Kapich; Ellen A. Panisko; Jon K. Magnuson; Daniel Cullen; Kenneth E. Hammel

    2008-01-01

    Fungal lignin-degrading systems likely include membrane-associated proteins that participate in diverse processes such as uptake and oxidation of lignin fragments, production of ligninolytic secondary metabolites, and defense of the mycelium against ligninolytic oxidants. Little is known about the nature or regulation of these membrane-associated components. We grew...

  14. Chapter 16: Lignin Visualization: Advanced Microscopy Techniques for Lignin Characterization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Yining [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Donohoe, Bryon S [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2018-04-03

    Visualization of lignin in plant cell walls, with both spatial and chemical resolution, is emerging as an important tool to understand lignin's role in the plant cell wall's nanoscale architecture and to understand and design processes intended to modify the lignin. As such, this chapter reviews recent advances in advanced imaging methods with respect to lignin in plant cell walls. This review focuses on the importance of lignin detection and localization for studies in both plant biology and biotechnology. Challenges going forward to identify and delineate lignin from other plant cell wall components and to quantitatively analyze lignin in whole cell walls from native plant tissue and treated biomass are also discussed.

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

    DEFF Research Database (Denmark)

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

    2017-01-01

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

  16. NMR of lignins

    Science.gov (United States)

    John Ralph; Larry L. Landucci

    2010-01-01

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

  17. Sulphate solubility and sulphate diffusion in oxide glasses: implications for the containment of sulphate-bearing nuclear wastes

    International Nuclear Information System (INIS)

    Lenoir, M.

    2009-09-01

    The thesis deals with sulphate solubility and sulphate diffusion in oxide glasses, in order to control sulphate incorporation and sulphate volatilization in nuclear waste glasses. It was conducted on simplified compositions, in the SiO 2 -B 2 O 3 -R 2 O (R = Li, Na, K, Cs), SiO 2 -B 2 O 3 -BaO and V 2 O 5 -B 2 O 3 -BaO systems. These compositions allowed us to study the influence of the nature of network-modifying ions (Li + , Na + , K + , Cs + or Ba 2+ ) and also of former elements (Si, B, V), on structure and properties of glasses. Sulphate volatility is studied in sodium borosilicate melts using an innovative technique of sulphate quantitation with Raman spectroscopy. This technique is useful to obtain kinetic curves of sulphate volatilization. The establishment of a model to fit these curves leads to the determination of diffusion coefficients of sulphate. These diffusion coefficients can thus be compared to diffusion coefficients of other species, determined by other techniques and presented in the literature. They are also linked to diffusion coefficients in relation with the viscosity of the melts. Concerning sulphate solubility in glasses, it depends on glass composition and on the nature of sulphate incorporated. Sulphate incorporation in alkali borosilicate glasses leads to the formation of a sulphate layer floating on top of the melt. Sulphate incorporation in barium borosilicate and boro-vanadate glasses leads to the crystallization of sulphate species inside the vitreous matrix. Moreover, sulphate solubility is higher in these glasses than in alkali borosilicates. Finally, exchanges between cations present in glasses and cations present in the sulphate phase are also studied. (author)

  18. Lignin blockers and uses thereof

    Science.gov (United States)

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

    2011-01-25

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

  19. Water-Soluble Dinitrosyl Iron Complex (DNIC): a Nitric Oxide Vehicle Triggering Cancer Cell Death via Apoptosis.

    Science.gov (United States)

    Wu, Shou-Cheng; Lu, Chung-Yen; Chen, Yi-Lin; Lo, Feng-Chun; Wang, Ting-Yin; Chen, Yu-Jen; Yuan, Shyng-Shiou; Liaw, Wen-Feng; Wang, Yun-Ming

    2016-09-19

    Nitric oxide (NO) is an important cellular signaling molecule that modulates various physiological activities. Angiogenesis-promoting activities of NO-donor drugs have been explored in both experimental and clinical studies. In this study, a structurally well characterized and water-soluble neutral {Fe(NO)2}(9) DNIC [(S(CH2)2OH)(S(CH2)2NH3)Fe(NO)2] (DNIC 2) was synthesized to serve as a NO-donor species. The antitumor activity of DNIC 2 was determined by MTT assay, confocal imaging, and Annexin-V/PI staining. The IC50 values of DNIC 2 were 18.8, 42.9, and 38.6 μM for PC-3, SKBR-3, and CRL5866 tumor cells, respectively. Moreover, DNIC 2 promoted apoptotic cell death via activation of apoptosis-associated proteins and inhibition of survival associated proteins. In particular, DNIC 2 treatment suppressed PC-3 tumor growth by 2.34- and 19.3-fold at 7 and 21 days, in comparison with the control group. These results indicate that water-soluble DNIC 2 may serve as a promising drug for cancer therapy.

  20. Compilation of PZC and IEP of sparingly soluble metal oxides and hydroxides from literature.

    Science.gov (United States)

    Kosmulski, Marek

    2009-11-30

    The values of PZC and IEP of metal oxides reported in the literature are affected by the choice of the specimens to be studied. The specimens, which have PZC and IEP similar to the "recommended" value, are preferred by the scientists. The biased choice leads to accumulation of results for a few specimens, and the other specimens are seldom studied or they are subjected to washing procedures aimed at shift of the original IEP toward the "recommended" value. Taking the average or median of all published PZC and IEP for certain oxide as the "recommended" value leads to substantiation of previously published results due to overrepresentation of certain specimens in the sample.

  1. Influence of iron solubility and charged surface-active compounds on lipid oxidation in fatty acid ethyl esters containing association colloids.

    Science.gov (United States)

    Homma, Rika; Johnson, David R; McClements, D Julian; Decker, Eric A

    2016-05-15

    The impact of iron compounds with different solubilities on lipid oxidation was studied in the presence and absence of association colloids. Iron (III) sulfate only accelerated lipid oxidation in the presence of association colloids while iron (III) oleate accelerated oxidation in the presence and absence of association colloids. Further, iron (III) oxide retarded lipid oxidation both with and without association colloids. The impact of charged association colloids on lipid oxidation in ethyl oleate was also investigated. Association colloids consisting of the anionic surface-active compound dodecyl sulphosuccinate sodium salt (AOT), cationic surface-active compound hexadecyltrimethylammonium bromide (CTAB), and nonionic surface-active compound 4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol (Triton X-100) retarded, promoted, and had no effect on lipid oxidation rates, respectively. These results indicate that the polarity of metal compounds and the charge of association colloids play a big role in lipid oxidation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Water-soluble Manganese and Iron Mesotetrakis(carboxyl)porphyrin: DNA Binding, Oxidative Cleavage, and Cytotoxic Activities.

    Science.gov (United States)

    Shi, Lei; Jiang, Yi-Yu; Jiang, Tao; Yin, Wei; Yang, Jian-Ping; Cao, Man-Li; Fang, Yu-Qi; Liu, Hai-Yang

    2017-06-29

    Two new water-soluble metal carboxyl porphyrins, manganese (III) meso -tetrakis (carboxyl) porphyrin and iron (III) meso -tetrakis (carboxyl) porphyrin, were synthesized and characterized. Their interactions with ct-DNA were investigated by UV-Vis titration, fluorescence spectra, viscosity measurement and CD spectra. The results showed they can strongly bind to ct-DNA via outside binding mode. Electrophoresis experiments revealed that both complexes can cleave pBR322 DNA efficiently in the presence of hydrogen peroxide, albeit 2-Mn exhibited a little higher efficiency. The inhibitor tests suggest the oxidative DNA cleavage by these two complexes may involve hydroxyl radical active intermediates. Notably, 2-Mn exhibited considerable photocytotoxicity against Hep G2 cell via triggering a significant generation of ROS and causing disruption of MMP after irradiation.

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

    Energy Technology Data Exchange (ETDEWEB)

    Rahikainen, J.

    2013-11-01

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

  4. A radioimmunoassay for lignin in plant cell walls

    International Nuclear Information System (INIS)

    Dawley, R.M.

    1989-01-01

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

  5. Plutonium chemistry: a synthesis of experimental data and a quantitative model for plutonium oxide solubility

    International Nuclear Information System (INIS)

    Haschke, J.M.; Oversby, V.M.

    2002-01-01

    The chemistry of plutonium is important for assessing potential behavior of radioactive waste under conditions of geologic disposal. This paper reviews experimental data on dissolution of plutonium oxide solids, describes a hybrid kinetic-equilibrium model for predicting steady-state Pu concentrations, and compares laboratory results with predicted Pu concentrations and oxidation-state distributions. The model is based on oxidation of PuO 2 by water to produce PuO 2+x , an oxide that can release Pu(V) to solution. Kinetic relationships between formation of PuO 2+x , dissolution of Pu(V), disproportionation of Pu(V) to Pu(IV) and Pu(VI), and reduction of Pu(VI) are given and used in model calculations. Data from tests of pyrochemical salt wastes in brines are discussed and interpreted using the conceptual model. Essential data for quantitative modeling at conditions relevant to nuclear waste repositories are identified and laboratory experiments to determine rate constants for use in the model are discussed

  6. Formation, stability, and solubility of metal oxide nanoparticles: surface entropy, and free energy of ferrihydrite

    NARCIS (Netherlands)

    Hiemstra, T.

    2015-01-01

    Ferrihydrite (Fh) is an excellent model for understanding nanoparticle behavior in general. Moreover, Fh is one of the most important Fe (hydr) oxides in nature. Fh particles can be extremely small leading to a very high reactive surface area that changes its chemical potential, strongly affecting

  7. Surface modification of iron oxide nanoparticles and their conjuntion with water soluble polymers for biomedical application

    International Nuclear Information System (INIS)

    Nguyen Thanh Huong; Lam Thi Kieu Giang; Nguyen Thanh Binh; Le Quoc Minh

    2009-01-01

    Superparamagnetic iron oxide nanoparticles (SPION) coated with suitable bio-compatible substances have been used in biomedicine, particularly in magnetic resonance imaging (MRI), tissue engineering, and hyperthermia and drug delivery. In this study, we describe the synthesis of SPION and its surface modification for in-vitro experiments. The particle diameter and structure were estimated by FESEM, TEM, XRD analyses. The saturation magnetization was characterized. SPION with a mean size of 12 nm have been prepared under N 2 atmosphere, with support of natural polymeric starch, by controlling chemical coprecipitation of magnetite phase from aqueous solutions containing suitable salts ratios of Fe 2+ and Fe 3+ . The surface of SPION-nanoparticles was treated with a coordinatable agent for higher dispersion ability in water and remaining the superparamagnetic behavior. The prepared iron oxide nanoparticles were coated with starch, dextran, PEG or MPEG to extend the application potential in the quite different engineering field of nano biomedicine.

  8. Dissolved Vanillin as Tracer for Estuarine Lignin Conversion

    Science.gov (United States)

    Edelkraut, F.

    1996-12-01

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

  9. Water-soluble building blocks for terpyridine-containing supramolecular polymers : synthesis, complexation, and pH stability studies of poly(ethylene oxide) moieties

    NARCIS (Netherlands)

    Lohmeijer, B.G.G.; Schubert, U.S.

    2003-01-01

    Poly(ethylene oxide) of various molecular weights ([bar M ]n = 3 000, 5 200, 10 000, 16 500 g · mol-1) has been modified with terpyridine end groups as building blocks for water-soluble metallo-supramolecular polymers. Metallo-supramolecular A-A homopolymers have been prepared and characterized by

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

    CSIR Research Space (South Africa)

    Spark, A

    2006-12-01

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

  11. Atomistic simulation of CO 2 solubility in poly(ethylene oxide) oligomers

    KAUST Repository

    Hong, Bingbing

    2013-10-02

    We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide) dimethyl ether, CH3O(CH 2CH2O)nCH3 (PEO for short) is a widely applied physical solvent that forms the major organic constituent of a class of novel nanoparticle-based absorbents. Good predictions were obtained for pressure-composition-density relations for CO2 + PEO oligomers (2 ≤ n ≤ 12), using the Potoff force field for PEO [J. Chem. Phys. 136, 044514 (2012)] together with the TraPPE model for CO2 [AIChE J. 47, 1676 (2001)]. Water effects on Henrys constant of CO2 in PEO have also been investigated. Addition of modest amounts of water in PEO produces a relatively small increase in Henrys constant. Dependence of the calculated Henrys constant on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length. © 2013 Taylor & Francis.

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-06-01

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

  13. Oxidative stress contributes to soluble fms-like tyrosine kinase-1 induced vascular dysfunction in pregnant rats.

    Science.gov (United States)

    Bridges, Jason P; Gilbert, Jeffrey S; Colson, Drew; Gilbert, Sara A; Dukes, Matthew P; Ryan, Michael J; Granger, Joey P

    2009-05-01

    Recent evidence indicates that both increased oxidative stress and an altered balance between pro- and anti-angiogenic factors such as vascular-endothelial growth factor (VEGF) and the soluble VEGF receptor (sFlt-1) contribute to endothelial dysfunction in preeclampsia. We hypothesized that chronic infusion of sFlt-1 to mimic the increase observed in preeclamptic patients would reduce plasma VEGF concentrations, increase blood pressure (BP) and vascular superoxide levels, and cause endothelial dysfunction in the pregnant rat. Recombinant sFlt-1 was infused (500 ng/h) during days 13-18 of pregnancy. BP, fetal and placental weight, oxidative stress and vessel vasorelaxation were determined on day 18 of pregnancy. Plasma sFlt-1 concentrations (299 +/- 33 vs. 100 +/- 16 pg/ml; P 570 +/- 77 vs. 780 +/- 48 pg/ml; P < 0.01) were decreased when compared to vehicle infused dams. sFlt-1 rats had smaller fetuses (1.3 +/- 0.03 vs. 1.5 +/- 0.04 g, P < 0.01) and placentas (0.41 +/- 0.01 vs. 0.47 +/- 0.02 g; P < 0.05). Placental (180 +/- 66 vs. 24 +/- 2.3 RLU/min/mg; P < 0.05) and vascular (34 +/- 8 vs. 12 +/- 5 RLU/min/mg; P < 0.05) superoxide production was increased in the sFlt-1 compared to vehicle infused rats. Vasorelaxation to acetylecholine (ACh) and sodium nitroprusside (SNP) were both decreased (P < 0.05) in the sFlt-1 infusion group compared to the vehicle and this decrease was attenuated (P < 0.05) by the superoxide scavenger Tiron. These data indicate elevated maternal sFlt-1 and decreased VEGF concentrations results in increased oxidative stress that contributes to vascular dysfunction during pregnancy.

  14. Lignin biodegradation and industrial implications

    Directory of Open Access Journals (Sweden)

    Adam B Fisher

    2014-12-01

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

  15. Synthesis of reduced carbon nitride at the reduction by hydroquinone of water-soluble carbon nitride oxide (g-C{sub 3}N{sub 4})O

    Energy Technology Data Exchange (ETDEWEB)

    Kharlamov, Alexey [Frantsevich Institute for Problems of Materials Science of NASU, Krzhyzhanovsky St. 3, 03680 Kiev (Ukraine); Bondarenko, Marina, E-mail: mebondarenko@ukr.net [Frantsevich Institute for Problems of Materials Science of NASU, Krzhyzhanovsky St. 3, 03680 Kiev (Ukraine); Kharlamova, Ganna [Taras Shevchenko National University of Kiev, Volodymyrs' ka St. 64, 01601 Kiev (Ukraine); Fomenko, Veniamin [Frantsevich Institute for Problems of Materials Science of NASU, Krzhyzhanovsky St. 3, 03680 Kiev (Ukraine)

    2016-09-15

    For the first time at the reduction by hydroquinone of water-soluble carbon nitride oxide (g-C{sub 3}N{sub 4})O reduced carbon nitride (or reduced multi-layer azagraphene) is obtained. It is differed from usually synthesized carbon nitride by a significantly large (on 0.09 nm) interplanar distance is. At the same time, the chemical bonds between atoms in a heteroatomic plane of reduced carbon nitride correspond to the bonds in a synthesized g-C{sub 3}N{sub 4}. The samples of water-soluble carbon nitride oxide were synthesized under the special reactionary conditions of a pyrolysis of melamine and urea. We believe that reduced carbon nitride consists of weakly connected carbon-nitrogen monosheets (azagraphene sheets) as well as reduced (from graphene oxide) graphene contains weakly connected graphene sheets. - Graphical abstract: XRD pattern and schematic atomic model of one layer of reduced carbon nitride, carbon nitride oxide and synthesized carbon nitride. For the first time at the reduction by hydroquinone of the water-soluble carbon nitride oxide (g-C{sub 3}N{sub 4})O is obtained the reduced carbon nitride (or reduced multi-layer azagraphene). Display Omitted - Highlights: • First the reduced carbon nitride (RCN) at the reduction of the carbon nitride oxide was obtained. • Water-soluble carbon nitride oxide was reduced by hydroquinone. • The chemical bonds in a heteroatomic plane of RCN correspond to the bonds in a synthesized g-C{sub 3}N{sub 4}. • Reduced carbon nitride consists of poorly connected heteroatomic azagraphene layers.

  16. Facile synthesis of soluble functional graphene by reduction of graphene oxide via acetylacetone and its adsorption of heavy metal ions

    International Nuclear Information System (INIS)

    Xu, Minghan; Chai, Jing; Hu, Nantao; Huang, Da; Wang, Yuxi; Huang, Xiaolu; Wei, Hao; Yang, Zhi; Zhang, Yafei

    2014-01-01

    The synthesis of graphene (GR) from graphene oxide (GO) typically involves harmful chemical reducing agents that are undesirable for most practical applications. Here we report a green and facile synthesis method for the synthesis of GR that is soluble in water and organic solvents and that includes the additional benefit of adsorption of heavy metal ions. Acetylacetone, as both a reducing agent and a stabilizer, was used to prepare soluble GR from GO. Transmission electron microscopy and atomic force microscopy provide clear evidence for the formation of few-layer GR. The results from Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy show that reduction of GO to GR has occurred. Raman spectroscopy and X-ray photoelectron spectroscopy also indicate the removal of oxygen-containing functional groups from GO, resulting in the formation of GR. The results of dispersion experiments show that GR can be highly dispersed in water and N,N-Dimethylformamide. The reaction mechanism for acetylacetone reduction of exfoliated GO was also proposed. This method is a facile and environmentally friendly approach to the synthesis of GR and opens up new possibilities for preparing GR and GR-based nanomaterials for large-scale applications. Of even greater interest is that inductively coupled plasma atomic emission spectroscopy suggests that synthesized GR may be applied in the absorption of Cd 2+ and Co 2+ due to the strong coordination capacity of acetylacetone on the surfaces and edges of GR and the large surface area of GR in aqueous solutions. The maximum adsorptions are 49.28 mg g −1 for Cd 2+ , which is 4.5 times higher than that of carbon nanotubes, and 27.78 mg g −1 for Co 2+ , which is 3.6 times higher than that of titania beans. (paper)

  17. Comparison of soluble guanylate cyclase stimulators and activators in models of cardiovascular disease associated with oxidative stress

    Directory of Open Access Journals (Sweden)

    Melissa H Costell

    2012-07-01

    Full Text Available Soluble guanylate cyclase (sGC, the primary mediator of nitric oxide (NO bioactivity, exists as reduced (NO-sensitive and oxidized (NO-insensitive forms. We tested the hypothesis that the cardiovascular protective effects of NO-insensitive sGC activation would be potentiated under conditions of oxidative stress compared to NO-sensitive sGC stimulation. The cardiovascular effects of the NO-insensitive sGC activator GSK2181236A (a non-depressor dose and a higher dose which lowered mean arterial pressure [MAP] by 5-10mmHg and equi-efficacious doses of the NO-sensitive sGC stimulator BAY 60-4552 were assessed in Sprague Dawley rats during coronary artery ischemia/reperfusion (I/R and spontaneously hypertensive stroke prone rats (SHR-SP on a high salt/fat diet (HSFD. In I/R, neither compound reduced infarct size. In SHR-SP, HSFD increased MAP, urine output, microalbuminuria and mortality, caused left ventricular hypertrophy and impaired endothelium-dependent vasorelaxation. The low dose of BAY 60-4552 but not GSK2181236A decreased urine output and mortality. Conversely, the low dose of GSK2181236A attenuated cardiac hypertrophy. The high doses of both compounds similarly attenuated cardiac hypertrophy and mortality. In addition, the high dose of BAY 60-4552 reduced urine output, microalbuminuria and MAP. Neither compound improved endothelium-dependent vasorelaxation. In SHR-SP aorta, the vasodilatory responses to the NO-dependent compounds carbachol and sodium nitroprusside were attenuated by HSFD. In contrast, the vasodilatory responses to GSK2181236A and BAY 60-4552 were unaltered by HSFD, indicating that reduced NO-bioavailability and not changes in the sGC oxidative state is responsible for the vascular dysfunction. In summary, GSK2181236A and BAY 60-4552 provide partial benefit against hypertension-induced end organ damage. The differential beneficial effects observed between these compounds could reflect tissue-specific changes in the s

  18. Lignin-Furfural Based Adhesives

    OpenAIRE

    Dongre, Prajakta; Driscoll, Mark; Amidon, Thomas; Bujanovic, Biljana

    2015-01-01

    Lignin recovered from the hot-water extract of sugar maple ( Acer saccharum ) is used in this study to synthesize adhesive blends to replace phenol-formaldehyde (PF) resin. Untreated lignin is characterized by lignin content and nuclear magnetic resonance (NMR) analysis. The molecular weight distribution of the lignin and the blends are characterized by size exclusion chromatography (SEC). The effect of pH (0.3, 0.65 and 1), ex situ furfural, and curing conditions on the tensile properties of...

  19. Comparison between micro- and nanosized copper oxide and water soluble copper chloride: interrelationship between intracellular copper concentrations, oxidative stress and DNA damage response in human lung cells.

    Science.gov (United States)

    Strauch, Bettina Maria; Niemand, Rebecca Katharina; Winkelbeiner, Nicola Lisa; Hartwig, Andrea

    2017-08-01

    Nano- and microscale copper oxide particles (CuO NP, CuO MP) are applied for manifold purposes, enhancing exposure and thus the potential risk of adverse health effects. Based on the pronounced in vitro cytotoxicity of CuO NP, systematic investigations on the mode of action are required. Therefore, the impact of CuO NP, CuO MP and CuCl 2 on the DNA damage response on transcriptional level was investigated by quantitative gene expression profiling via high-throughput RT-qPCR. Cytotoxicity, copper uptake and the impact on the oxidative stress response, cell cycle regulation and apoptosis were further analysed on the functional level. Cytotoxicity of CuO NP was more pronounced when compared to CuO MP and CuCl 2 in human bronchial epithelial BEAS-2B cells. Uptake studies revealed an intracellular copper overload in the soluble fractions of both cytoplasm and nucleus, reaching up to millimolar concentrations in case of CuO NP and considerably lower levels in case of CuO MP and CuCl 2 . Moreover, CuCl 2 caused copper accumulation in the nucleus only at cytotoxic concentrations. Gene expression analysis in BEAS-2B and A549 cells revealed a strong induction of uptake-related metallothionein genes, oxidative stress-sensitive and pro-inflammatory genes, anti-oxidative defense-associated genes as well as those coding for the cell cycle inhibitor p21 and the pro-apoptotic Noxa and DR5. While DNA damage inducible genes were activated, genes coding for distinct DNA repair factors were down-regulated. Modulation of gene expression was most pronounced in case of CuO NP as compared to CuO MP and CuCl 2 and more distinct in BEAS-2B cells. GSH depletion and activation of Nrf2 in HeLa S3 cells confirmed oxidative stress induction, mainly restricted to CuO NP. Also, cell cycle arrest and apoptosis induction were most distinct for CuO NP. The high cytotoxicity and marked impact on gene expression by CuO NP can be ascribed to the strong intracellular copper ion release, with subsequent

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

    NARCIS (Netherlands)

    Munk, L.; Punt, A.M.; Kabel, M.A.; Meyer, A.S.

    2017-01-01

    Lignin is an underexploited resource in biomass refining. Laccases (EC 1.10.3.2) catalyze oxidation of phenolic hydroxyls using O2 as electron acceptor and may facilitate lignin modification in the presence of mediators. This study assessed the reactivity of four different synthetic mediators by

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

    NARCIS (Netherlands)

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

    2018-01-01

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

  2. Studies of lignin transformation in polyoxometalate (POM) bleaching of kraft pulp

    Science.gov (United States)

    Biljana Bujanovic; Richard S. Reiner; Kolby C. Hirth; Sally A. Ralph; Rajai H. Atalla

    2005-01-01

    In order to elucidate changes occurring in lignin during polyoxometalate delignification of kraft pulp, residual lignins of a series of POM- delignified kraft pulps of decreasing kappa number were isolated and characterized. Oxidative treatment of commercial unbleached kraft pulp was performed using complex POM solutions containing the active [SiVW11O40]anion. For...

  3. Laccase/Mediator Systems: Their Reactivity toward Phenolic Lignin Structures.

    Science.gov (United States)

    Hilgers, Roelant; Vincken, Jean-Paul; Gruppen, Harry; Kabel, Mirjam A

    2018-02-05

    Laccase-mediator systems (LMS) have been widely studied for their capacity to oxidize the nonphenolic subunits of lignin (70-90% of the polymer). The phenolic subunits (10-30% of the polymer), which can also be oxidized without mediators, have received considerably less attention. Consequently, it remains unclear to what extent the presence of a mediator influences the reactions of the phenolic subunits of lignin. To get more insight in this, UHPLC-MS was used to study the reactions of a phenolic lignin dimer (GBG), initiated by a laccase from Trametes versicolor , alone or in combination with the mediators HBT and ABTS. The role of HBT was negligible, as its oxidation by laccase occurred slowly in comparison to that of GBG. Laccase and laccase/HBT oxidized GBG at a comparable rate, resulting in extensive polymerization of GBG. In contrast, laccase/ABTS converted GBG at a higher rate, as GBG was oxidized both directly by laccase but also by ABTS radical cations, which were rapidly formed by laccase. The laccase/ABTS system resulted in Cα oxidation of GBG and coupling of ABTS to GBG, rather than polymerization of GBG. Based on these results, we propose reaction pathways of phenolic lignin model compounds with laccase/HBT and laccase/ABTS.

  4. Effect of an electron beam on the subsequent pyrogenic distillation of lignin and cellulose

    International Nuclear Information System (INIS)

    Metreveli, P.K.; Metreveli, A.K.; Kholodkova, E.M.; Ponomarev, A.V.

    2014-01-01

    The irradiation notably influences responsiveness of cellulose and lignin to the subsequent pyrogenic distillation though both weight and the form of samples do not change almost at doses up to 3 MGy. Decreases in overpoint of lignin and cellulose irradiated at 2.2 MGy are ∼80°and ∼100°, respectively. Third of condensate from cellulose and almost half from lignin are distilled-off at lower temperatures. The thermally instable compounds convertible mainly to furans via subsequent heating are forming in cellulose. Distillation of the irradiated lignin gives less tar which, however, is richer by methoxy-phenols. In distilled-off water–organic fraction the content of soluble organic compounds is increased. - Highlights: • Irradiation facilitates subsequent dry distillation of cellulose and lignin. • Overpoints of irradiated samples are decreasing. • Furans and methoxy-phenols formation improves

  5. Lignin derivatives from desilicated rice straw soda black liquor

    Energy Technology Data Exchange (ETDEWEB)

    El-Taraboulsi, M A; Nasser, M M

    1979-01-01

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

  6. Effect of water soluble vitamins on Zn transport of Caco-2 cells and their implications under oxidative stress conditions.

    Science.gov (United States)

    Tupe, Rashmi Santosh; Agte, Vaishali Vilas

    2010-02-01

    The role of different water soluble vitamins in Zn metabolism beyond intestinal Zn absorption is poorly explored. Using Caco-2 cells, effects of different vitamins on intestinal Zn transport and their implications under oxidative stress (OS) were investigated. Cells were apically treated with Zn (25 muM) and vitamins (Folic acid (FA), Nicotinic acid (NA), Ascorbic acid (AA), riboflavin, thiamine, pyridoxine) for 60 min. The effect of most promising vitamins on zinc transport, antioxidant enzymes (Catalase, Glutathione peroxidase, and superoxide dismutase), and intracellular OS status (ROS generation and mitochondrial transmembrane potential) were investigated. OS was generated by tert-butyl hydro peroxide and results for each vitamin were compared with respective Zn containing controls with and without OS. Without OS, Zn transport was slightly enhanced in presence of NA, while it was significantly reduced by thiamine, riboflavin, and pyridoxine. Under OS, NA significantly (P vitamins. With Zn + FA + OS, enzyme activities decreased maximally, with twofold increase in 2',7'-dichlorofluorescin diacetate (DCF-DA) (P < 0.01) and lowering of rhodamine fluorescence (P < 0.05). In Zn + AA + OS, DCF-DA fluorescence increased (P < 0.05) but with NA, cellular enzymes, and antioxidant profile were improved. Results for the first time demonstrate advantageous effects of NA and deleterious consequences of FA with no effect by AA on Zn transport, especially under OS. These observed changes in the transport of Zn seem to have an impact on OS markers.

  7. Theoretical Approaches to Lignin Chemistry

    OpenAIRE

    Shevchenko, Sergey M.

    1994-01-01

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

  8. Low-solubility particles and a Trojan-horse type mechanism of toxicity: the case of cobalt oxide on human lung cells

    International Nuclear Information System (INIS)

    Ortega, Richard; Roudeau, Stephane; Perrin, Laura; Carmona, Asuncion; Bresson, Carole; Darolles, Carine; Aloin, Valerie; Malard, Veronique; Gautier, Celine; Janin, Myriam; Floriani, Magali

    2014-01-01

    The mechanisms of toxicity of metal oxide particles towards lung cells are far from being understood. In particular, the relative contribution of intracellular particulate versus solubilized fractions is rarely considered as it is very challenging to assess, especially for low-solubility particles such as cobalt oxide (Co_3O_4). This study was possible owing to two highly sensitive, independent, analytical techniques, based on single-cell analysis, using ion beam microanalysis, and on bulk analysis of cell lysates, using mass spectrometry. Our study shows that cobalt oxide particles, of very low solubility in the culture medium, are readily incorporated by BEAS-2B human lung cells through endocytosis via the clathrin-dependent pathway. They are partially solubilized at low pH within lysosomes, leading to cobalt ions release. Solubilized cobalt was detected within the cytoplasm and the nucleus. As expected from these low-solubility particles, the intracellular solubilized cobalt content is small compared with the intracellular particulate cobalt content, in the parts-per-thousand range or below. However, we were able to demonstrate that this minute fraction of intracellular solubilized cobalt is responsible for the overall toxicity. Cobalt oxide particles are readily internalized by pulmonary cells via the endo-lysosomal pathway and can lead, through a Trojan-horse mechanism, to intracellular release of toxic metal ions over long periods of time, involving specific toxicity. (authors)

  9. Catalytic Depolymerization and Upgrading of Lignin for Vanillin Production: Cooperative Research and Development Final Report, CRADA Number CRD-14-545

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2017-03-31

    Examine catalytic conversion of lignin using multifunctional catalysts that are able to depolymerize and oxidize lignin to a vanillin-rich stream. Examine separation processes for isolation of vanillin from product mixtures. Conduct preliminary experiments to determine if deconstructed lignin streams can be metabolized by Pseudomonas putida.

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

    OpenAIRE

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

    2017-01-01

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

  11. Enzymes that cleave non-glycosidic ether bonds between lignins or derivatives thereof and saccharides

    Science.gov (United States)

    Kravit, Nancy G.; Schmidt, Katherine A.

    2017-10-24

    The patent application relates to isolated polypeptides that specifically cleave non-glycosidic ether bonds between lignins or derivatives thereof and saccharides, and to cDNAs encoding the polypeptides. The patent application also relates to nucleic acid constructs, expression vectors and host cells comprising the cDNAs, as well as methods of producing and using the isolated polypeptides for treating pulp and biomass to increase soluble saccharide yield and enrich lignin fractions.

  12. Stage specific effects of soluble copper and copper oxide nanoparticles during sea urchin embryo development and their relation to intracellular copper uptake.

    Science.gov (United States)

    Torres-Duarte, Cristina; Ramos-Torres, Karla M; Rahimoff, René; Cherr, Gary N

    2017-08-01

    The effects of exposure to either soluble copper (copper sulfate) or copper oxide nanoparticles (nano-CuO) during specific early developmental stages of sea urchin embryos were analyzed. Soluble copper caused significant malformations in embryos (skeletal malformations, delayed development or gut malformations) when present at any given stage, while cleavage stage was the most sensitive to nano-CuO exposure causing skeletal malformations and decreased total antioxidant capacity. The stage specificity was linked to higher endocytic activity during the first hours of development that leads to higher accumulation of copper in specific cells critical for development. Results indicate that nano-CuO results in higher accumulation of copper inside of embryos and this intracellular copper is more persistent as compared to soluble copper. The possible implications later in development are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Interactions of Kraft lignin and wheat gluten during biomaterial processing: evidence for the role of phenolic groups.

    Science.gov (United States)

    Kaewtatip, Kaewta; Menut, Paul; Auvergne, Remi; Tanrattanakul, Varaporn; Morel, Marie-Helene; Guilbert, Stephane

    2010-04-14

    The chemical interactions between Kraft lignin and wheat gluten under processing conditions were investigated by determining the extent of the protein network formation. To clarify the role of different chemical functions found in lignin, the effect of Kraft lignin was compared with that of an esterified lignin, in which hydroxyl groups had been suppressed by esterification, and with a series of simple aromatics and phenolic structures with different functionalities (conjugated double bonds, hydroxyl, carboxylic acid, and aldehyde). The protein solubility was determined by using the Kjeldahl method. The role of the hydroxyl function was assessed by the significantly lower effect of esterified lignin. The importance of the phenolic radical scavenging structure is evidenced by the effect of guaiacol, which results in a behavior similar to that of the Kraft lignin. In addition, the significant effect of conjugated double bonds on gluten reactivity, through nucleophilic addition, was demonstrated.

  14. Role of Nitric Oxide, Nitric Oxide Synthase, Soluble Guanylyl Cyclase, and cGMP-Dependent Protein Kinase I in Mouse Stem Cell Cardiac Development

    Directory of Open Access Journals (Sweden)

    Valentina Spinelli

    2016-01-01

    Full Text Available Introduction and Aim. Nitric oxide (NO can trigger cardiac differentiation of embryonic stem cells (ESCs, indicating a cardiogenic function of the NO synthetizing enzyme(s (NOS. However, the involvement of the NO/NOS downstream effectors soluble guanylyl cyclase (sGC and cGMP activated protein kinase I (PKG-I is less defined. Therefore, we assess the involvement of the entire NO/NOS/sGC/PKG-I pathway during cardiac differentiation process. Methods. Mouse ESCs were differentiated toward cardiac lineages by hanging drop methodology for 21 days. NOS/sGC/PKG-I pathway was studied quantifying genes, proteins, enzymatic activities, and effects of inhibition during differentiation. Percentages of beating embryoid bodies (mEBs were evaluated as an index of cardiogenesis. Results and Discussion. Genes and protein expression of enzymes were increased during differentiation with distinctive kinetics and proteins possessed their enzymatic functions. Exogenous administered NO accelerated whereas the blockade of PKG-I strongly slowed cardiogenesis. sGC inhibition was effective only at early stages and NOS blockade ineffective. Of NOS/sGC/PKG-I pathway, PKG-I seems to play the prominent role in cardiac maturation. Conclusion. We concluded that exogenous administered NO and other pharmacological strategies able to increase the activity of PKG-I provide new tools to investigate and promote differentiation of cardiogenic precursors.

  15. Raman spectra of lignin model compounds

    Science.gov (United States)

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

    2005-01-01

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

  16. Laccase-mediator catalyzed conversion of model lignin compounds

    Science.gov (United States)

    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...

  17. Pharmacological hypothesis: Nitric oxide-induced inhibition of ADAM-17 activity as well as vesicle release can in turn prevent the production of soluble endothelin-converting enzyme.

    Science.gov (United States)

    Kuruppu, Sanjaya; Rajapakse, Niwanthi W; Parkington, Helena C; Smith, Ian

    2017-10-01

    Endothelin-1 (ET-1) and nitric oxide (NO) are two highly potent vasoactive molecules with opposing effects on the vasculature. Endothelin-converting enzyme (ECE) and nitric oxide synthase (NOS) catalyse the production of ET-1 and NO, respectively. It is well established that these molecules play a crucial role in the initiation and progression of cardiovascular diseases and have therefore become targets of therapy. Many studies have examined the mechanism(s) by which NO regulates ET-1 production. Expression and localization of ECE-1 is a key factor that determines the rate of ET-1 production. ECE-1 can either be membrane bound or be released from the cell surface to produce a soluble form. NO has been shown to reduce the expression of both membrane-bound and soluble ECE-1. Several studies have examined the mechanism(s) behind NO-mediated inhibition of ECE expression on the cell membrane. However, the precise mechanism(s) behind NO-mediated inhibition of soluble ECE production are unknown. We hypothesize that both exogenous and endogenous NO, inhibits the production of soluble ECE-1 by preventing its release via extracellular vesicles (e.g., exosomes), and/or by inhibiting the activity of A Disintegrin and Metalloprotease-17 (ADAM17). If this hypothesis is proven correct in future studies, these pathways represent targets for the therapeutic manipulation of soluble ECE-1 production. © 2017 The Authors. Pharmacology Research & Perspectives published by John Wiley & Sons Ltd, British Pharmacological Society and American Society for Pharmacology and Experimental Therapeutics.

  18. Inhibition of lignin-derived phenolic compounds to cellulase.

    Science.gov (United States)

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

    2016-01-01

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

  19. Functional Group and Structural Characterization of Unmodified and Functionalized Lignin by Titration, Elemental Analysis, 1H NMR and FTIR Techniques

    Directory of Open Access Journals (Sweden)

    Ramin Bairami Habashi

    2017-11-01

    Full Text Available Lignin is the second most abundant polymer in the world after cellulose. Therefore, characterization of the structure and functional groups of lignin in order to assess its potential applications in various technical fields has become a necessity. One of the major problems related to the characterization of lignin is the lack of well-defined protocols and standards. In this paper, systematic studies have been done to characterize the structure and functional groups of lignin quantitatively using different techniques such as elemental analysis, titration and 1H NMR and FTIR techniques. Lignin as a black liquor was obtained from Choka Paper Factory and it was purified before any test. The lignin was reacted with α-bromoisobutyryl bromide to calculate the number of hydroxyl and methoxyl moles. Using 1H NMR spectroscopic method on α-bromoisobutyrylated lignin (BiBL in the presence of a given amount of N,N-dimethylformamide (DMF as an internal standard, the number of moles of hydroxyl and methoxyl groups per gram of lignin was found to be 6.44 mmol/g and 6.64 mmol/g, respectively. Using aqueous titration, the number of moles of phenolic hydroxyl groups and carboxyl groups of the lignin were calculated as 3.13 mmol/g and 2.84 mmol/g, respectively. The findings obtained by 1H NMR and elemental analysis indicated to phenyl propane unit of the lignin with C9 structural formula as C9 HAl 3.84HAr2.19S0.2O0.8(OH1.38(OCH31.42. Due to poor solubility of the lignin in tetrahydrofuran (THF, acetylated lignin was used in the GPC analysis, by which number-average molecular weight  of the lignin was calculated as 992 g/mol.

  20. Rationalization and in vitro modeling of the chemical mechanisms of the enzymatic oxidation of phenolic compounds in planta: from flavonols and stilbenoids to lignins.

    Science.gov (United States)

    Cottyn, Betty; Kollmann, Albert; Waffo-Teguo, Pierre; Ducrot, Paul-Henri

    2011-06-20

    Enzymatic oxidation of phenolic compounds is a widespread phenomenon in plants. It is responsible for the formation of many oligomers and polymers, which are generally described as the result of a combinatorial coupling of the different radicals formed through oxidation of the phenol group and delocalization of the radical. We focused our interest on several phenolic compounds that are present in plants and known to form, under enzymatic oxidation, oligomers with different type of linkages between monomers. To explain this diversity of inter-monomer linkages and their variation according to the experimental procedure used for the enzymatic oxidation, we report an alternative mechanistic pathway involving dismutation of the radicals, leading to the formation of carbocations which, thereafter, react with nucleophilic species present in the medium. This alternative pathway allows the understanding of peculiar linkages between monomeric units in the oligomer and offers new insights for understanding the formation of phenolic biopolymers in plants. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Lignin-Furfural Based Adhesives

    Directory of Open Access Journals (Sweden)

    Prajakta Dongre

    2015-07-01

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

  2. Mechanistic studies of the oxidation of soluble species of ruthenium in nitric acid solutions. Application to the removal of ruthenium from nuclear fuel dissolution solutions

    International Nuclear Information System (INIS)

    Carron, V.

    2001-01-01

    Ruthenium is one of the most troublesome fission products during nuclear fuel reprocessing. His removal from nitric acid fuel dissolution solutions, above the PUREX process, is under consideration. Electro-volatilization could be a possible way to eliminate this element. It consists in the oxidation of soluble ruthenium species coupled with the volatilization of formed RuO 4 . Soluble species are nitrate and nitro complexes of nitrosyl ruthenium RuNO 3+ . The first part of this work deals with the direct oxidation of RuNO 3+ at a golden or a platinum anode. It has been investigated by cyclic voltammetry and infrared and UV-visible reflectance spectroscopy. The oxidation of RuNO 3+ begins with an adsorption step, which precedes the formation of RuO 4 . Then a reaction between RuO 4 and RuNO 3+ occurs to produce a Ru IV compound, which is also electro-oxidized to RuO 4 . The second part concerns potentiostatic electro-volatilization experiences. The rate of electro-volatilization decreases with increasing HNO 3 concentration. At low concentrations, kinetic is controlled by the volatilization of RuO 4 . The rate-determining step is the oxidation of RuNO 3+ at concentrations higher than 1 M. In HNO 3 4 M, the addition of AgNO 3 is required to accelerate the oxidation of RuNO 3+ . The last part is devoted to the study of the indirect oxidation of RuNO 3+ . The electrocatalytic power of electro-generated Ag II is illustrated by voltammetric techniques and potentiostatic electrolysis. The existence of a limit concentration of AgNO 3 is shown (which value depends on experimental conditions) beyond which kinetic is controlled by the RuO 4 volatilization step. These results indicate that the electro-volatilization kinetic could be increased by optimizing the volatilization conditions. (author)

  3. The thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores. XI. Solubility of synthetic chalcomenite analog and zinc selenite at 25°C

    Science.gov (United States)

    Charykova, M. V.; Krivovichev, V. G.; Ivanova, N. M.; Semenova, V. V.

    2015-12-01

    The aim of this study is the synthesis of CuSeO3·2H2O (chalcomenite analog), ZnSeO3·2H2O, and ZnSeO3·H2O and the investigation of their solubility in water. CuSeO3·2H2O has been synthesized from solutions of Cu nitrate and Na selenite, while Zn selenites were synthesized from solutions of Zn nitrate and Na selenite. The samples obtained have been examined with X-ray diffraction and infrared and Raman spectroscopy. The solubility has been determined using the isothermal saturation method in ampoules at 25°C. The solubility has been calculated using the Geochemist's Workbench (GMB 9.0) software package. Solubility products have been calculated for CuSeO3·2H2O (10-10.63), ZnSeO3·2H2O (10-8.35), and ZnSeO3·H2O (10-7.96). The database used comprises thermodynamic characteristics of 46 elements, 47 base particles, 48 redox pairs, 551 particles in solution, and 624 solid phases. The Eh-pH diagrams of the Zn-Se-H2O and Cu-Se-H2O systems were plotted for the average contents of these elements in underground water in oxidation zones of sulfide deposits.

  4. Solubility of uranium oxide in molten salt electrolysis bath of LiF–BaF{sub 2} with LaF{sub 3} additive

    Energy Technology Data Exchange (ETDEWEB)

    Alangi, Nagaraj, E-mail: nagaraj@barc.gov.in [Laser & Plasma Technology Division, Bhabha Atomic Research Centre, Mumbai (India); Homi Bhabha National Institute, Mumbai (India); Mukherjee, Jaya [Laser & Plasma Technology Division, Bhabha Atomic Research Centre, Mumbai (India); Gantayet, L.M. [Homi Bhabha National Institute, Mumbai (India)

    2016-03-15

    The solubility of UO{sub 2} in the molten mixtures of equimolar LiF–BaF{sub 2}(1:1) with LaF{sub 3} as additive was studied in the range of 1423 K–1523 K. The molten fluoride salt mixture LiF–BaF{sub 2} LaF{sub 3} was equilibrated with a sintered uranium oxide pellet at 1423 K, 1473 K, 1523 K and the salt samples were collected after equilibration. Studies were conducted in the range of 10%–50% by weight additions of LaF{sub 3} in the equimolar LiF–BaF{sub 2}(1:1) base fluoride salt bath. Solubility of UO{sub 2} increased with rise in LaF{sub 3} concentration in the molten fluoride in the temperature range of 1423 K–1523 K. At a given concentration of LaF{sub 3}, the UO{sub 2} solubility increased monotonously with temperature. With mixed solvent, when UF{sub 4} was added as a replacement of part of LaF{sub 3} in LiF–BaF{sub 2}(1:1)-10 wt% LaF{sub 3} and LiF–BaF{sub 2}(1:1)-30 wt% LaF{sub 3}, there was an enhancement of solubility of UO{sub 2}.

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

    Science.gov (United States)

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

    1996-12-01

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

  6. Modification of lignin for the production of new compounded materials.

    Science.gov (United States)

    Hüttermann, A; Mai, C; Kharazipour, A

    2001-05-01

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

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

    Directory of Open Access Journals (Sweden)

    Catherine I Lacayo

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

  8. Sevelamer does not decrease lipopolysaccharide or soluble CD14 levels but decreases soluble tissue factor, low-density lipoprotein (LDL) cholesterol, and oxidized LDL cholesterol levels in individuals with untreated HIV infection.

    Science.gov (United States)

    Sandler, Netanya G; Zhang, Xinyan; Bosch, Ronald J; Funderburg, Nicholas T; Choi, Andrew I; Robinson, Janet K; Fine, Derek M; Coombs, Robert W; Jacobson, Jeffrey M; Landay, Alan L; Douek, Daniel C; Tressler, Randall; Read, Sarah W; Wilson, Cara C; Deeks, Steven G; Lederman, Michael M; Gandhi, Rajesh T

    2014-11-15

    Abnormal levels of inflammation are associated with cardiovascular disease and mortality in human immunodeficiency virus (HIV)-infected patients. Microbial translocation, which may cause inflammation, is decreased by sevelamer in patients undergoing hemodialysis. In this single-arm study, we evaluated the effects of 8 weeks of sevelamer therapy on 36 HIV-infected subjects who were not receiving antiretroviral therapy. Sevelamer did not significantly change markers of microbial translocation, inflammation, or T-cell activation. During sevelamer treatment, however, levels of soluble tissue factor, low-density lipoprotein (LDL) cholesterol, and oxidized LDL cholesterol decreased significantly, whereas D-dimer levels increased. Thus, in this study population, sevelamer did not reduce microbial translocation but may have yielded cardiovascular benefits. NCT 01543958. © The Author 2014. Published by Oxford University Press on behalf of the Infectious Diseases Society of America. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  9. Mechanochemical production of lignin-containing powder fuels from biotechnical industry waste: A review

    Directory of Open Access Journals (Sweden)

    Lomovsky Oleg

    2015-01-01

    Full Text Available In biotechnological processing of plant raw materials, carbohydrates that are soluble and accessible for microorganisms are the only usable components. The lignin-rich part of the plant raw materials usually ends up in the waste. Lignin transferred into water suspensions cannot be used efficiently as a fuel. In this review, a new processing scheme of plant raw materials is presented, which includes mechanochemical treatment of the plant raw materials and separation of the powder product into particles of lignified and non-lignified tissues rich in lignin and cellulose, respectively. The cellulose-rich powders can then be used in biotechnological processes. Lignin-rich powder aerodynamically separated using cyclone-type apparatus can be used as a powder fuel to satisfy the needs of the main biotechnological plant in heat and steam.

  10. Free radical scavenging and anti-oxidative activities of an ethanol-soluble pigment extract prepared from fermented Zijuan Pu-erh tea.

    Science.gov (United States)

    Fan, Jiang Ping; Fan, Chong; Dong, Wen Min; Gao, Bin; Yuan, Wei; Gong, Jia Shun

    2013-09-01

    An ethanol-soluble pigment extract was separated from fermented Zijuan Pu-erh tea. The compositions of the ethanol soluble pigment extract were analyzed by high-performance liquid chromatography-tandem mass spectroscopy (HPLC-MS/MS). The extract was prepared into a series of ethanol solutions and analyzed for free radical-scavenging activities (against two free radicals: 1,1-diphenyl-2-picrylhydrazyl (DPPH) and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)) and in vitro anti-oxidative properties. Electron spin resonance spectroscopy showed that the peaks of DPPH and TEMPO decreased with increasing extract concentration, suggesting that the extract had excellent free radical-scavenging activities. In vitro cell culture suggested that, at 50-200 mg/L, the extract had no measurable effect on the viability of vascular endothelial cells (ECV340) but produced significant protective effects for cells that underwent oxidative injuries due to hydrogen peroxide (H₂O₂) treatment. Compared with the H₂O₂ treatment alone cells group, 200 mg/L of the extract increased the activity of superoxide dismutase (SOD) in cells by 397.3%, and decreased the concentration of malondialdehyde (MDA) and the activity of lactate acid dehydrogenase (LDH) by 47.8% and 69.6%, respectively. These results suggest that the extract has excellent free radical scavenging and anti-oxidative properties. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Water soluble nano-scale transient material germanium oxide for zero toxic waste based environmentally benign nano-manufacturing

    KAUST Repository

    Almuslem, A. S.; Hanna, Amir; Yapici, Tahir; Wehbe, N.; Diallo, Elhadj; Kutbee, Arwa T.; Bahabry, Rabab R.; Hussain, Muhammad Mustafa

    2017-01-01

    , in addition to transiency, we also show an environmentally friendly manufacturing process for a complementary metal oxide semiconductor (CMOS) technology. Every year, trillions of complementary metal oxide semiconductor (CMOS) electronics are manufactured

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

    Science.gov (United States)

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

    1990-01-01

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

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

    International Nuclear Information System (INIS)

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

    1990-01-01

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

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

    Science.gov (United States)

    Waggoner, Derek Charles

    largely on oxygen content. Additionally, results indicate that partially oxidized lignin could react further with ROS to generate compounds resembling condensed aromatic-like compounds, previously believed to be primarily pyrogenic in origin, as well as alicyclic compounds commonly observed in marine DOM.

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

    Science.gov (United States)

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

    2014-03-01

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

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

    Science.gov (United States)

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

    2018-05-17

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

  17. Pyrolysis - gas chromatography - mass spectrometry of lignins

    Energy Technology Data Exchange (ETDEWEB)

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

    1979-01-01

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

  18. Lignin poly(lactic acid) copolymers

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-14

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

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

    Science.gov (United States)

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

    2018-01-01

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

  20. Lignin recovery. A resource to value

    International Nuclear Information System (INIS)

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

    1999-01-01

    In the present paper, the effects of the steam explosion (ES) pretreatment conditions on recovery and chemical structure of wheat straw lignin are reported. The experimental data of lignin recovery by caustic extraction, followed by acid precipitation, have been interpolated to obtain the dependence on the time and temperature of SE. The lignin has been characterised by using several methods. Preliminary results on the synthesis of copolymers lignin-styrene are also reported [it

  1. Lignin biopolymer based triboelectric nanogenerators

    Science.gov (United States)

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

    2017-07-01

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

  2. Structure variations of carbonizing lignin

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  3. Lignin pyrolysis for profitable lignocellulosic biorefineries

    NARCIS (Netherlands)

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

    2014-01-01

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

  4. Cationic electrodepositable coating composition comprising lignin

    Science.gov (United States)

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

    2013-07-30

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

  5. Liquid Fuels from Lignins: Annual Report

    Energy Technology Data Exchange (ETDEWEB)

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

    1986-01-01

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

  6. Converting lignin to aromatics: step by step

    NARCIS (Netherlands)

    Strassberger, Z.I.

    2014-01-01

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

  7. Biobleaching chemistry of laccase-mediator systems on high-lignin-content kraft pulps

    International Nuclear Information System (INIS)

    Chakar, F.S.; Ragauskas, A.J.

    2004-01-01

    A high-lignin-content softwood kraft pulp was reacted with laccase in the presence of 1-hydroxybenzotriazole (HBT), N-acetyl-N-phenylhydroxylamine (NHA), and violuric acid (VA). The biodelignification response with violuric acid was superior to both 1-hydroxybenzotriazole and N-acetyl-N-phenylhydroxylamine. NMR analysis of residual lignins isolated before and after the biobleaching treatments revealed that the latter material was highly oxidized and that the magnitude of structural changes was most pronounced with the laccase - violuric acid biobleaching system. An increase in the content of carboxylic acid groups and a decrease in methoxyl groups were noted with all three laccase-mediator systems. The oxidation biobleaching pathway is directed primarily towards noncondensed C5 phenolic lignin functional structures for all three laccase-mediated systems. The laccase - violuric acid system was also reactive towards C5-condensed phenolic lignin structures. (author)

  8. Improvement of the photovoltaic parameters of perovskite solar cells using a reduced-graphene-oxide-modified titania layer and soluble copper phthalocyanine as a hole transporter.

    Science.gov (United States)

    Nouri, Esmaiel; Mohammadi, Mohammad Reza; Xu, Zong-Xiang; Dracopoulos, Vassilios; Lianos, Panagiotis

    2018-01-24

    Functional perovskite solar cells can be made by using a simple, inexpensive and stable soluble tetra-n-butyl-substituted copper phthalocyanine (CuBuPc) as a hole transporter. In the present study, TiO 2 /reduced graphene oxide (T/RGO) hybrids were synthesized via an in situ solvothermal process and used as electron acceptor/transport mediators in mesoscopic perovskite solar cells based on soluble CuBuPc as a hole transporter and on graphene oxide (GO) as a buffer layer. The impact of the RGO content on the optoelectronic properties of T/RGO hybrids and on the solar cell performance was studied, suggesting improved electron transport characteristics and photovoltaic parameters. An enhanced electron lifetime and recombination resistance led to an increase in the short circuit current density, open circuit voltage and fill factor. The device based on a T/RGO mesoporous layer with an optimal RGO content of 0.2 wt% showed 22% higher photoconversion efficiency and higher stability compared with pristine TiO 2 -based devices.

  9. The effect of zinc injection into PWR primary coolant on the reduction of radiation buildup and corrosion control. The solubilities of zinc, nickel and cobalt spinel oxides

    International Nuclear Information System (INIS)

    Miyajima, Kaori; Hirano, Hideo

    1999-01-01

    The use of zinc injection into PWR primary coolant to reduce radiation buildup has been widely studied, and te reduction effect has been experimentally confirmed. However, some items, such as the optimal concentration of zinc required to reduce radiation buildup, the corrosion control effect of zinc injection, and the influence of zinc injection on the integrity of fuel cladding, have not been clarified yet. In particular, the corrosion suppression effect of zinc remains unconfirmed. Therefore, it is necessary to measure and calculate the solubilities of zinc and nickel spinel oxides, which are formed on the surface of Ni-based alloys in PWR primary systems. In this study, in order to assess the effectiveness of zinc injection in the reduction of radiation buildup and the corrosion control of Ni-based alloy, the potential-pH diagrams for Zn-Cr-H 2 O, Ni-Cr-H 2 O, and Co-Cr-H 2 O systems at 300degC were constructed and the solubilities of Zn-Cr, Ni-Cr, and Co-Cr spinel oxides were calculated. It is concluded that under pH conditions for which NiCr 2 O 4 is stable, zinc injection is effective in corrosion control as well as in reducing radiation buildup. (author)

  10. Variation of solubility, biokinetics and dose coefficient of industrial uranium oxides according to the specific surface area

    International Nuclear Information System (INIS)

    Chazel, V.; Houpert, P.; Ansorbolo, E.; Henge-Napoli, M.H.; Paquet, F.

    2000-01-01

    The in vitro solubility, absorption to blood, lung retention and dose coefficient of industrial UO 2 samples were studied as a function of the specific surface area (SSA) of the particles. An in vitro study has been carried out on two samples of industrial UO 4 to compare the results with those obtained with UO 2 . Ten UO 2 samples supplied by different fuel factories or research laboratories, presented specific surface areas from 1.00 to 4.45 m 2 .g -1 . The wide range of values of SSA was due to the different conditions of fabrication. Dissolution tests in cell culture medium made on these ten samples have shown that the solubility increased 2.5-fold when the SSA increased 1.7-fold. The same tendency has been found for UO 4 , a soluble compound, and for U 3 O 8 , a moderately soluble compound. Four in vivo experiments carried out on rats by intratracheal instillation of dust suspensions of UO 2 , have highlighted the decrease in lung retention and the increase of absorption to blood with the SSA. The experimental absorption parameters calculated from the in vivo data allowed specific dose coefficients to be obtained which decreased from 6.6 to 4.3 μSv.Bq -1 when the SSA increased from 1.60 to 3.08 m 2 .g -1 . Thus, the medical monitoring of workers at the workplace has to take into account any change in the fabrication process of the uranium compound which can affect the physiochemical properties and consequently the dose coefficient. (author)

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

    Directory of Open Access Journals (Sweden)

    Andrzej Staniszewski

    2001-12-01

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

  12. Lignin Sulfonation - A different Approach

    DEFF Research Database (Denmark)

    Bjørkmann, Anders

    2001-01-01

    The research on sulfite pulping has been characterized by the attempts to explain its chemistry. The. different approach presented is incited by perceptions about the (still) unsolved problem of the ultrastructural features of lignin in wood. A simple kinetic model has been chosen to describe the...

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

    Science.gov (United States)

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

    2017-12-01

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

  14. One-step oxidation preparation of unfolded and good soluble graphene nanoribbons by longitudinal unzipping of carbon nanotubes

    Science.gov (United States)

    Hu, Xiaolin; Hu, Yizhen; Huang, Jindan; Zhou, Ning; Liu, Yuhan; Wei, Lin; Chen, Xin; Zhuang, Naifeng

    2018-04-01

    A simple one-step method to prepare graphene nanoribbon (GNR) is reported in this paper. Compared with water steam etching, the oxidation and co-etching of dilute sulfuric acid can result in the more complete longitudinal unzipping of carbon nanotube, although there is no other strong oxidant. As-prepared GNRs are more flat and have more oxygenated functional groups along the edge. Moreover, they can steadily disperse in a water system. These make them suitable as a carrier for supporting palladium (Pd) nanoparticles. The Pd/GNR composite exhibits a superior electrocatalytic activity for ethanol oxidation.

  15. A study of lignin degradation in leaf and needle litter using 13C-labelled tetramethylammonium hydroxide (TMAH) thermochemolysis: comparison with CuO oxidation and van Soest methods.

    NARCIS (Netherlands)

    Klotzbücher, T.; Filley, T.R.; Kaiser, K.; Kalbitz, K.

    2011-01-01

    We studied the degradation of lignin in leaf and needle litter of ash, beech, maple, pine and spruce using 13C-labelled tetramethylammonium hydroxide (13C TMAH) thermochemolysis. Samples were allowed to decompose for 27 months in litter bags at a German spruce forest site, resulting in a range of

  16. On dithiothreitol (DTT as a measure of oxidative potential for ambient particles: evidence for the importance of soluble ewline transition metals

    Directory of Open Access Journals (Sweden)

    J. G. Charrier

    2012-10-01

    Full Text Available The rate of consumption of dithiothreitol (DTT is increasingly used to measure the oxidative potential of particulate matter (PM, which has been linked to the adverse health effects of PM. While several quinones are known to be very reactive in the DTT assay, it is unclear what other chemical species might contribute to the loss of DTT in PM extracts. To address this question, we quantify the rate of DTT loss from individual redox-active species that are common in ambient particulate matter. While most past research has indicated that the DTT assay is not sensitive to metals, our results show that seven out of the ten transition metals tested do oxidize DTT, as do three out of the five quinones tested. While metals are less efficient at oxidizing DTT compared to the most reactive quinones, concentrations of soluble transition metals in fine particulate matter are generally much higher than those of quinones. The net result is that metals appear to dominate the DTT response for typical ambient PM2.5 samples. Based on particulate concentrations of quinones and soluble metals from the literature, and our measured DTT responses for these species, we estimate that for typical PM2.5 samples approximately 80% of DTT loss is from transition metals (especially copper and manganese, while quinones account for approximately 20%. We find a similar result for DTT loss measured in a small set of PM2.5 samples from the San Joaquin Valley of California. Because of the important contribution from metals, we also tested how the DTT assay is affected by EDTA, a chelator that is sometimes used in the assay. EDTA significantly suppresses the response from both metals and quinones; we therefore recommend that EDTA should not be included in the DTT assay.

  17. Lignin from Micro- to Nanosize: Applications

    Directory of Open Access Journals (Sweden)

    Stefan Beisl

    2017-11-01

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

  18. Lignin biodegradation by the ascomycete Chrysonilia sitophila.

    Science.gov (United States)

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

    1997-01-01

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

  19. All Biomass and UV Protective Composite Composed of Compatibilized Lignin and Poly (Lactic-acid)

    Science.gov (United States)

    Kim, Youngjun; Suhr, Jonghwan; Seo, Hee-Won; Sun, Hanna; Kim, Sanghoon; Park, In-Kyung; Kim, Soo-Hyun; Lee, Youngkwan; Kim, Kwang-Jin; Nam, Jae-Do

    2017-03-01

    Utilization of carbon-neutral biomass became increasingly important due to a desperate need for carbon reduction in the issue of global warming in light of replacing petroleum-based materials. We used lignin, which was an abundant, low cost, and non-food based biomass, for the development of all biomass-based films and composites through reactive compatibilization with poly (lactic-acid) (PLA). Using a facile and practical route, the hydrophilic hydroxyl groups of lignin were acetylated to impose the compatibility with PLA. The solubility parameter of the pristine lignin at 26.3 (J/cm3)0.5 was altered to 20.9 (J/cm3)0.5 by acetylation allowing the good compatibility with PLA at 20.2 (J/cm3)0.5. The improved compatibility of lignin and PLA provided substantially decreased lignin domain size in composites (12.7 μm), which subsequently gave transparent and UV-protection films (visual transmittance at 76% and UV protection factor over 40). The tensile strength and elongation of the developed composite films were increased by 22% and 76%, respectively, and the biobased carbon content was confirmed as 96 ± 3%. The developed PLA/lignin composites provided 100% all-biomass contents and balanced optical and mechanical properties that could broaden its eco-friendly applications in various industries.

  20. 14C-labeled lignins as substrates for the study of lignin biodegradation and transformation

    International Nuclear Information System (INIS)

    Crawford, R.L.; Robinson, L.E.; Chen, A.M.

    1980-01-01

    Methods, both classical and isotopic, for quantifying lignin degradation are reviewed. Preparation and chemical characterization of 14 C-labeled lignins (both synthetic and plant-synthesized) are reviewed, with emphasis on the utilization of these 14 C-labeled substrates in biodegradation and biotransformation experiments. The scientific literature is reviewed concerning the use of 14 C-lignins to examine the following: microbial groups that are able to degrade lignins; lignin degradation in natural environments; biochemistry and microbial physiology of lignin degradation; biodegradability of industrial lignins and their by-products; and screening for industrially valuable, lignin-modifying microorganisms. Recent results obtained in our laboratory concerning lignin degradation by eubacteria are presented. Future directions for 14 C-methodology are examined

  1. Cytocompatible cellulose hydrogels containing trace lignin

    International Nuclear Information System (INIS)

    Nakasone, Kazuki; Kobayashi, Takaomi

    2016-01-01

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

  2. Cytocompatible cellulose hydrogels containing trace lignin

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-01

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

  3. N-3 Polyunsaturated Fatty Acids Decrease the Protein Expression of Soluble Epoxide Hydrolase via Oxidative Stress-Induced P38 Kinase in Rat Endothelial Cells.

    Science.gov (United States)

    Okada, Takashi; Morino, Katsutaro; Nakagawa, Fumiyuki; Tawa, Masashi; Kondo, Keiko; Sekine, Osamu; Imamura, Takeshi; Okamura, Tomio; Ugi, Satoshi; Maegawa, Hiroshi

    2017-06-24

    N -3 polyunsaturated fatty acids (PUFAs) improve endothelial function. The arachidonic acid-derived metabolites (epoxyeicosatrienoic acids (EETs)) are part of the endothelial hyperpolarization factor and are vasodilators independent of nitric oxide. However, little is known regarding the regulation of EET concentration by docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA) in blood vessels. Sprague-Dawley rats were fed either a control or fish oil diet for 3 weeks. Compared with the control, the fish oil diet improved acetylcholine-induced vasodilation and reduced the protein expression of soluble epoxide hydrolase (sEH), a key EET metabolic enzyme, in aortic strips. Both DHA and EPA suppressed sEH protein expression in rat aorta endothelial cells (RAECs). Furthermore, the concentration of 4-hydroxy hexenal (4-HHE), a lipid peroxidation product of n -3 PUFAs, increased in n -3 PUFA-treated RAECs. In addition, 4-HHE treatment suppressed sEH expression in RAECs, suggesting that 4-HHE (derived from n -3 PUFAs) is involved in this phenomenon. The suppression of sEH was attenuated by the p38 kinase inhibitor (SB203580) and by treatment with the antioxidant N-acetyl-L-cysteine. In conclusion, sEH expression decreased after n -3 PUFAs treatment, potentially through oxidative stress and p38 kinase. Mild oxidative stress induced by n -3 PUFAs may contribute to their cardio-protective effect.

  4. Quantification of nitrous oxide (N2O) emissions and soluble microbial product (SMP) production by a modified AOB-NOB-N2O-SMP model.

    Science.gov (United States)

    Kim, MinJeong; Wu, Guangxue; Yoo, ChangKyoo

    2017-03-01

    A modified AOB-NOB-N 2 O-SMP model able to quantify nitrous oxide (N 2 O) emissions and soluble microbial product (SMP) production during wastewater treatment is proposed. The modified AOB-NOB-N 2 O-SMP model takes into account: (1) two-step nitrification by ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), (2) N 2 O production by AOB denitrification under oxygen-limited conditions and (3) SMP production by microbial growth and endogenous respiration. Validity of the modified model is demonstrated by comparing the simulation results with experimental data from lab-scale sequencing batch reactors (SBRs). To reliably implement the modified model, a model calibration that adjusts model parameters to fit the model outputs to the experimental data is conducted. The results of this study showed that the modeling accuracy of the modified AOB-NOB-N 2 O-SMP model increases by 19.7% (NH 4 ), 51.0% (NO 2 ), 57.8% (N 2 O) and 16.7% (SMP) compared to the conventional model which does not consider the two-step nitrification and SMP production by microbial endogenous respiration. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Susanne Bylin

    2014-08-01

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

  6. Immunization with PIII, a fraction of Schistosoma mansoni soluble adult worm antigenic preparation, affects nitric oxide production by murine spleen cells

    Directory of Open Access Journals (Sweden)

    Diana Magalhães de Oliveira

    1998-01-01

    Full Text Available Nitric oxide (NO is an important effector molecule involved in immune regulation and defense. NO produced by cytokine-activated macrophages was reported to be cytotoxic against the helminth Schistosoma mansoni. Identification and characterization of S. mansoni antigens that can provide protective immunity is crucial for understanding the complex immunoregulatory events that modulate the immune response in schistosomiasis. It is, then, essential to have available defined, purified parasite antigens. Previous work by our laboratory identified a fraction of S. mansoni soluble adult worm antigenic preparation (SWAP, named PIII, able to elicit significant in vitro cell proliferation and at the same time lower in vitro and in vivo granuloma formation when compared either to SEA (soluble egg antigen or to SWAP. In the present work we report the effect of different in vivo trials with mice on their spleen cells ability to produce NO. We demonstrate that PIII-immunization is able to significantly increase NO production by spleen cells after in vitro stimulation with LPS. These data suggest a possible role for NO on the protective immunity induced by PIII.

  7. Fabrication of environmentally biodegradable lignin nanoparticles.

    Science.gov (United States)

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

    2012-12-21

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

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

    Science.gov (United States)

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

    2017-11-06

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

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

    Science.gov (United States)

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

    2018-04-27

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

  10. Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zheming; Shi, Zhi; Shi, Liang; White, Gaye F.; Richardson, David J.; Clarke, Thomas A.; Fredrickson, Jim K.; Zachara, John M.

    2015-08-25

    Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, some evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin that are proposed to mediate electron transfer (Marsili et al., 2008). In this work, we used methyl viologen (MV•+)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of secreted flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 µM) by MELs ([MV•+] ~ 42 µM and MtrABC ≤ 1 nM) were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MV•+ and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 seconds. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (≤ 1 µM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. However, at higher FMN concentrations (> 1 µM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer

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

    Directory of Open Access Journals (Sweden)

    Chia-Jung eLu

    2016-06-01

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

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

    Science.gov (United States)

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

    2008-05-01

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

  13. Conformational analysis of lignin models

    International Nuclear Information System (INIS)

    Santos, Helio F. dos

    2001-01-01

    The conformational equilibrium for two 5,5' biphenyl lignin models have been analyzed using a quantum mechanical semiempirical method. The gas phase and solution structures are discussed based on the NMR and X-ray experimental data. The results obtained showed that the observed conformations are solvent-dependent, being the geometries and the thermodynamic properties correlated with the experimental information. This study shows how a systematic theoretical conformational analysis can help to understand chemical processes at a molecular level. (author)

  14. Lignin-Retaining Transparent Wood.

    Science.gov (United States)

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

    2017-09-11

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

  15. Environmental economics of lignin derived transport fuels

    OpenAIRE

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

    2017-01-01

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

  16. Radical nature of C- lignin

    Science.gov (United States)

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

    2016-01-01

    The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous...

  17. The effect of temperature on the catalytic conversion of Kraft lignin using near-critical water

    DEFF Research Database (Denmark)

    Nguyen, Thi Dieu Huyen; Maschietti, Marco; Åmand, Lars-Erik

    2014-01-01

    The catalytic conversion of suspended LignoBoost Kraft lignin was performed in near-critical water using ZrO2/K2CO3 as the catalytic system and phenol as the co-solvent and char suppressing agent. The reaction temperature was varied from 290 to 370 C and its effect on the process was investigated...... in a continuous flow (1 kg/h). The yields of water-soluble organics (WSO), bio-oil and char (dry lignin basis) were in the ranges of 5–11%, 69–87% and 16–22%, respectively. The bio-oil, being partially deoxygenated, exhibited higher carbon content and heat value, but lower sulphur content than lignin. The main 1...

  18. Modifying sulfomethylated alkali lignin by horseradish peroxidase to improve the dispersibility and conductivity of polyaniline

    Science.gov (United States)

    Yang, Dongjie; Huang, Wenjing; Qiu, Xueqing; Lou, Hongming; Qian, Yong

    2017-12-01

    Pine and wheat straw alkali lignin (PAL and WAL) were sulfomethylated to improve water solubility, polymerized with horseradish peroxidase (HRP) to improve the molecular weight (Mw) and applied to dope and disperse polyaniline (PANI). The structural effect of lignin from different origins on the reactivities of sulfomethylation and HRP polymerization was investigated. The results show that WAL with less methoxyl groups and lower Mw have higher reactivity in sulfomethylation (SWAL). More phenolic hydroxyl groups and lower Mw benefit the HRP polymerization of sulfomethylated PAL (SPAL). Due to the natural three-dimensional aromatic structure and introduced sulfonic groups, SPAL and SWAL could effectively dope and disperse PANI in water by π-π stacking and electrostatic interaction. HRP modified SPAL (HRP-SPAL) with much higher sulfonation degree and larger Mw significantly increased the conductivity and dispersibility of lignin/PANI composites.

  19. Biological and Catalytic Conversion of Sugars and Lignin Publications |

    Science.gov (United States)

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

  20. Studies on Lignin-Based Adhesives for Particleboard Panels

    OpenAIRE

    ÇETİN, Nihat Sami; ÖZMEN, Nilgül

    2003-01-01

    The ultimate aim of this work was to develop a phenolic resin for partially replacing phenol with modified organosolv lignin in phenol-formaldehyde (PF) resin production. The lignin-formaldehyde relationship was determined in a reactivity test. Organosolv lignin-phenol-formaldehyde (LPF) resins were produced in a two-step preparation with different additions of lignin. The method selected for the manufacture of lignin resins dealt with modification of the lignin by the methylolation route. Th...

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

    Science.gov (United States)

    Hill Bembenic, Meredith A.

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

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

    Science.gov (United States)

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

    2015-01-01

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

  3. Fluorescent fusion proteins of soluble guanylyl cyclase indicate proximity of the heme nitric oxide domain and catalytic domain.

    Directory of Open Access Journals (Sweden)

    Tobias Haase

    Full Text Available BACKGROUND: To examine the structural organisation of heterodimeric soluble guanylyl cyclase (sGC Förster resonance energy transfer (FRET was measured between fluorescent proteins fused to the amino- and carboxy-terminal ends of the sGC beta1 and alpha subunits. METHODOLOGY/PRINCIPAL FINDINGS: Cyan fluorescent protein (CFP was used as FRET donor and yellow fluorescent protein (YFP as FRET acceptor. After generation of recombinant baculovirus, fluorescent-tagged sGC subunits were co-expressed in Sf9 cells. Fluorescent variants of sGC were analyzed in vitro in cytosolic fractions by sensitized emission FRET. Co-expression of the amino-terminally tagged alpha subunits with the carboxy-terminally tagged beta1 subunit resulted in an enzyme complex that showed a FRET efficiency of 10% similar to fluorescent proteins separated by a helix of only 48 amino acids. Because these findings indicated that the amino-terminus of the alpha subunits is close to the carboxy-terminus of the beta1 subunit we constructed fusion proteins where both subunits are connected by a fluorescent protein. The resulting constructs were not only fluorescent, they also showed preserved enzyme activity and regulation by NO. CONCLUSIONS/SIGNIFICANCE: Based on the ability of an amino-terminal fragment of the beta1 subunit to inhibit activity of an heterodimer consisting only of the catalytic domains (alphacatbetacat, Winger and Marletta (Biochemistry 2005, 44:4083-90 have proposed a direct interaction of the amino-terminal region of beta1 with the catalytic domains. In support of such a concept of "trans" regulation of sGC activity by the H-NOX domains our results indicate that the domains within sGC are organized in a way that allows for direct interaction of the amino-terminal regulatory domains with the carboxy-terminal catalytic region. In addition, we constructed "fluorescent-conjoined" sGC's by fusion of the alpha amino-terminus to the beta1 carboxy-terminus leading to a

  4. Lignin-based polyoxyethylene ether enhanced enzymatic hydrolysis of lignocelluloses by dispersing cellulase aggregates.

    Science.gov (United States)

    Lin, Xuliang; Qiu, Xueqing; Yuan, Long; Li, Zihao; Lou, Hongming; Zhou, Mingsong; Yang, Dongjie

    2015-06-01

    Water-soluble lignin-based polyoxyethylene ether (EHL-PEG), prepared from enzymatic hydrolysis lignin (EHL) and polyethylene glycol (PEG1000), was used to improve enzymatic hydrolysis efficiency of corn stover. The glucose yield of corn stover at 72h was increased from 16.7% to 70.1% by EHL-PEG, while increase in yield with PEG4600 alone was 52.3%. With the increase of lignin content, EHL-PEG improved enzymatic hydrolysis of microcrystalline cellulose more obvious than PEG4600. EHL-PEG could reduce at least 88% of the adsorption of cellulase on the lignin film measured by quartz crystal microbalance with dissipation monitoring (QCM-D), while reduction with PEG4600 was 43%. Cellulase aggregated at 1220nm in acetate buffer analyzed by dynamic light scattering. EHL-PEG dispersed cellulase aggregates and formed smaller aggregates with cellulase, thereby, reduced significantly nonproductive adsorption of cellulase on lignin and enhanced enzymatic hydrolysis of lignocelluloses. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. High-value utilization of eucalyptus kraft lignin: Preparation and characterization as efficient dye dispersant.

    Science.gov (United States)

    Zhang, Hui; Yu, Boming; Zhou, Wanpeng; Liu, Xinxin; Chen, Fangeng

    2018-04-01

    The dark color of industrial lignin is the main obstacle for their high value-added use in areas such as dyestuff dispersants. A kind of light-colored lignosulfonate with favorable dispersibility and remarkable stain resistance is prepared using fractionated eucalyptus kraft lignin. The fractionated lignins named as D (insoluble part) and X (soluble part) and sulfonated lignin fractions named as SD and SX are characterized by FTIR spectroscopy, 1 H NMR spectroscopy, GPC and brightness test. The results reveal that fraction X presents a lower molecular weight but a higher hydroxyl content than that of fraction D, which lead to the differences on the SO 3 H content, dispersibility and color performance of SD and SX. The sulfonated fractions perform a similar molecular weight to that of unsulfonated lignins and show light color due to the phenolic hydroxyl blocking of 1,4-BS (1,4-butane sultone) and the postprocessing of sodium borohydride. The SX that performs the best of all exhibits obvious decrease on phenolic hydroxyl groups and increase on brightness value which is improved by 85.8% compared with control sample. The SX reaches the highest level (grade 5) in the dispersibility test and presents remarkable stain resistance on different textiles, especially on the dacron and cotton. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2017-07-01

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

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

    Science.gov (United States)

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

    2013-08-01

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

  8. Lignin recovery and it effects quality of anaerobic treated palm oil mill effluent (AT-POME)

    Science.gov (United States)

    Haqi Ibrahim, Abdul; Fahmi Ridwan, Muhammad; Zulzikrami Azner Abidin, Che; Ong, Soon Ann; Shian Wong, Yee; Wazira Azhari, Ayu; Norruhaidawati Ozir, Siti

    2018-03-01

    Lignin is one of the main structural polymers present in plant tissue. It can also be found as an isolated product of the pulp and paper industry. Palm oil mill effluent (POME) has been known as high strength industrial wastewater that is difficult to treat due to its large variety of inorganic and organic contents. The main purpose of this study is to recover soluble lignin from anaerobically treated palm oil mill effluent (AT-POME) and indirectly improves the quality of AT-POME. AT-POME was adjusted to different pH using different type of acids. Response Surface Methodology (RSM) was utilized to obtain the optimum operating parameters as well as to analyse the interaction between them. Model shows that 74.67 % of lignin can be recovered from AT-POME after 5 minutes reaction time using sulfuric acid (H2S04) at pH 5. Hence from the experiment, it was proved that simple pH adjustment could precipitate the soluble lignin from AT-POME.

  9. Fabrication of Environmentally Biodegradable Lignin Nanoparticles

    NARCIS (Netherlands)

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

    2012-01-01

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

  10. Environmental economics of lignin derived transport fuels

    NARCIS (Netherlands)

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

    2017-01-01

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

  11. Bacterial enzymes involved in lignin degradation

    NARCIS (Netherlands)

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

    2016-01-01

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

  12. Lignin Biodegradation with Laccase-Mediator Systems

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  13. Lignin Biodegradation with Laccase-Mediator Systems

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-03-31

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

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

    Science.gov (United States)

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

    2014-09-24

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

  15. Nitric oxide-soluble guanylyl cyclase-cyclic GMP signaling in the striatum: New targets for the treatment of Parkinson's disease?

    Directory of Open Access Journals (Sweden)

    Anthony R West

    2011-06-01

    Full Text Available Striatal nitric oxide (NO-producing interneurons play an important role in the regulation of corticostriatal synaptic transmission and motor behavior. Striatal NO synthesis is driven by concurrent activation of NMDA and dopamine (DA D1 receptors. NO diffuses into the dendrites of medium-sized spiny neurons (MSNs which contain high levels of NO receptors called soluble guanylyl cyclases (sGC. NO-mediated activation of sGC leads to the synthesis of the second messenger cGMP. In the intact striatum, transient elevations in intracellular cGMP primarily act to increase neuronal excitability and to facilitate glutamatergic corticostriatal transmission. NO-cGMP signaling also functionally opposes the inhibitory effects of DA D2 receptor activation on corticostriatal transmission. Not surprisingly, abnormal striatal NO-sGC-cGMP signaling becomes apparent following striatal DA depletion, an alteration thought to contribute to pathophysiological changes observed in basal ganglia circuits in Parkinson’s disease (PD. Here, we discuss recent developments in the field which have shed light on the role of NO-sGC-cGMP signaling pathways in basal ganglia dysfunction and motor symptoms associated with PD and L-DOPA-induced dyskinesias.

  16. Effect of Bacillus subtilis on phosphorus uptake by cucumber as affected by iron oxides and the solubility of the phosphorus source

    Directory of Open Access Journals (Sweden)

    Ana Maria Garcia-Lopez

    2016-11-01

    Full Text Available In this work, we examined the effects of Bacillus subtilis strain QST713 by assessing plant P uptake from variably P compound .The experiment performed involved three factors: (i P source [KH2PO4 at 100 mg kg–1, and phosphate rock (PR at 100 or 200 mg kg–1]; (ii plant inoculation with QST713 (inoculated and non-inoculated; and (iii Fe oxide (ferrihydrite in the growth medium (0 or 300 mg kg–1 concentration of citrate–ascorbate-extractable Fe. Ferrihydrite decreased dry matter yield in plants by more than 50 %. Inoculation with QST713 increased plant growth, and total accumulation of P and P uptake in plants. Overall, QST713 increased P uptake by 40 %, the effect being independent of the presence of ferrihydrite and P source. The increased P uptake observed can be ascribed to increased solubilization of P and to increased root growth.. Therefore, QST713 improves P nutrition in plants grown on media with a high P adsorption capacity irrespective of the solubility of the P compound.

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

    Science.gov (United States)

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

    2016-03-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-11-10

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

  19. Lignin solubilisation and gentle fractionation in liquid ammonia

    NARCIS (Netherlands)

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

    2015-01-01

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

  20. The Use of Esterified Lignin for Synthesis of Durable Composites

    Science.gov (United States)

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

    2011-01-01

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

  1. Toll-like Receptor 4 Signaling Confers Cardiac Protection Against Ischemic Injury via Inducible Nitric Oxide Synthase- and Soluble Guanylate Cyclase-dependent Mechanisms

    Science.gov (United States)

    Wang, E; Feng, Yan; Zhang, Ming; Zou, Lin; Li, Yan; Buys, Emmanuel S.; Huang, Peigen; Brouckaert, Peter; Chao, Wei

    2011-01-01

    Background Prior administration of a small dose of lipopolysaccharide confers a cardiac protection against ischemia-reperfusion injury. However, the signaling mechanisms that control the protection are incompletely understood. We tested the hypothesis that TLR4 mediates the ability of lipopolysaccharide to protect against cardiac ischemia-reperfusion injury through distinct intracellular pathways involving myeloid differentiation factor 88 (MyD88), TIR-domain-containing adaptor protein inducing interferon-β–mediated transcription-factor (Trif), inducible nitric-oxide synthase (iNOS), and soluble guanylate cyclase (sGC). Methods Wild-type mice and the genetically modified mice, i.e., TLR4-deficient (TLR4-def), TLR2 knockout (TLR2−/−), MyD88−/−, Trif−/−, iNOS−/−, and sGCα1−/−, were treated with normal saline or 0.1 mg/kg of lipopolysaccharide, intraperitoneally. Twenty-four hours later, isolated hearts were perfused in a Langendorff apparatus and subsequently subjected to 30 min of global ischemia and reperfusion for up to 60 min. Left ventricular function and myocardial infarction sizes were examined. Results Compared to saline-treated mice, lipopolysaccharide-treated mice had markedly improved left ventricular developed pressure and dP/dtmax (P < 0.01) and reduced MI sizes (37.2 ± 3.4% vs. 19.8 ± 4.9%, P < 0.01) after ischemia-reperfusion. The cardiac protective effect of lipopolysaccharide was abolished in the TLR4-def and MyD88−/− mice, but remained intact in TLR2−/− or Trif−/− mice. iNOS−/− mice or wild-type mice treated with the iNOS inhibitor 1400W failed to respond to the TLR4-induced nitric oxide production and were not protected by the lipopolysaccharide preconditioning. While sGC 1−/− mice had robust nitric oxide production in response to lipopolysaccharide, they were not protected by the TLR4-elicited cardiac protection. Conclusions TLR4 activation confers a potent cardiac protection against ischemia

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

    NARCIS (Netherlands)

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

    2017-01-01

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

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

    Science.gov (United States)

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

    2007-01-01

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

  4. Influence of Saharan dust outbreaks and carbon content on oxidative potential of water-soluble fractions of PM2.5 and PM10

    Science.gov (United States)

    Chirizzi, Daniela; Cesari, Daniela; Guascito, Maria Rachele; Dinoi, Adelaide; Giotta, Livia; Donateo, Antonio; Contini, Daniele

    2017-08-01

    Exposure to atmospheric particulate matter (PM) leads to adverse health effects although the exact mechanisms of toxicity are still poorly understood. Several studies suggested that a large number of PM health effects could be due to the oxidative potential (OP) of ambient particles leading to high concentrations of reactive oxygen species (ROS). The contribution to OP of specific anthropogenic sources like road traffic, biomass burning, and industrial emissions has been investigated in several sites. However, information about the OP of natural sources are scarce and no data is available regarding the OP during Saharan dust outbreaks (SDO) in Mediterranean regions. This work uses the a-cellular DTT (dithiothreitol) assay to evaluate OP of the water-soluble fraction of PM2.5 and PM10 collected at an urban background site in Southern Italy. OP values in three groups of samples were compared: standard characterised by concentrations similar to the yearly averages; high carbon samples associated to combustion sources (mainly road traffic and biomass burning) and SDO events. DTT activity normalised by sampled air volume (DTTV), representative of personal exposure, and normalised by collected aerosol mass (DTTM), representing source-specific characteristics, were investigated. The DTTV is larger for high PM concentrations. DTTV is well correlated with secondary organic carbon concentration. An increased DTTV response was found for PM2.5 compared to the coarse fraction PM2.5-10. DTTV is larger for high carbon content samples but during SDO events is statistically comparable with that of standard samples. DTTM is larger for PM2.5 compared to PM10 and the relative difference between the two size fractions is maximised during SDO events. This indicates that Saharan dust advection is a natural source of particles having a lower specific OP with respect to the other sources acting on the area (for water-soluble fraction). OP should be taken into account in epidemiological

  5. Animal bioavailability of defined xenobiotic lignin metabolites

    International Nuclear Information System (INIS)

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

    1990-01-01

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

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

    Science.gov (United States)

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

    2016-10-25

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

  7. Anti-HIV and immunomodulation activities of cacao mass lignin-carbohydrate complex.

    Science.gov (United States)

    Sakagami, Hiroshi; Kawano, Michiyo; Thet, May Maw; Hashimoto, Ken; Satoh, Kazue; Kanamoto, Taisei; Terakubo, Shigemi; Nakashima, Hideki; Haishima, Yuji; Maeda, Yuuichi; Sakurai, Koji

    2011-01-01

    Recently, a prominent antiviral and macrophage stimulatory activity of cacao lignin-carbohydrate complex (LCC) has been reported. However, the solubility and sterility of LCC have not been considered yet. In the present study, complete solubilisation and sterilisation was achieved by autoclaving under mild alkaline conditions and the previously reported biological activities were re-examined. LCCs were obtained by 1% NaOH extraction and acid precipitation, and a repeated extraction-precipitation cycle. Nitric oxide (NO) and cytokine productions were assayed by the Griess method and ELISA, respectively. Inducible NO synthase (iNOS) expression was determined by Western blot analysis. Superoxide anion, hydroxyl radical and nitric oxide radical-scavenging activity was determined by ESR spectroscopy. Cacao mass LCC showed reproducibly higher anti-HIV activity than cacao husk LCC. Cacao mass LCC, up to 62.5 μg/ml, did not stimulate mouse macrophage-like cells (RAW264.7 and J774.1) to produce NO, nor did it induce iNOS protein, in contrast to lipopolysaccharide (LPS). Cacao mass LCC and LPS synergistically stimulated iNOS protein expression, suggesting a different point of action. Cacao mass LCC induced tumour necrosis factor-α production markedly less than LPS, and did not induce interleukin-1β, interferon-α or interferon-γ. ESR spectroscopy showed that cacao mass LCC, but not LPS, scavenged NO produced from NOC-7. This study demonstrated several new biological activities of LCCs distinct from LPS and further confirmed the promising antiviral and immunomodulating activities of LCCs.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-15

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

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  10. Lignine als grondstof voor asfalt en dakbedekking

    NARCIS (Netherlands)

    Vliet, D. van

    2014-01-01

    Zet een chemicus en een wegenbouwer bij elkoor en je kunt het onverwachte verwachten. Somen brouwden dr. Ted Sloghek en ing. Dave van Vliet van TNO een type bitumen met verbeterde eigenschoppen. Het basismateriaal: lignine

  11. Composition comprising lignin and antidi arrheal component

    DEFF Research Database (Denmark)

    2008-01-01

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

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

    African Journals Online (AJOL)

    Muzakir

    and properties, lignin offers a perspective for higher value-added ... priority for the development and implementation of the lignocellulosic ... of about 2.5 m and adaptable to most soils. It had ..... in young versus adult Eucalyptus globulus plants.

  13. Molecular evidence for lignin degradation in sulfate-reducing mangrove sediments (Amazônia, Brazil)

    Science.gov (United States)

    Dittmar, Thorsten; Lara, Rubén José

    2001-05-01

    - Molecular lignin analyses have become a powerful quantitative approach for estimating flux and fate of vascular plant organic matter in coastal and marine environments. The use of a specific molecular biomarker requires detailed knowledge of its decomposition rates relative to the associated organic matter and its structural diagenetic changes. To gain insight into the poorly known processes of anaerobic lignin diagenesis, molecular analyses were performed in the sulfate-reducing sediment of a north Brazilian mangrove. Organic matter in samples representing different diagenetic stages (i.e., fresh litter, a sediment core, and percolating water) was characterized by alkaline CuO oxidation for lignin composition, element (C, N), and stable carbon isotope analyses. On the basis of these results and on a balance model, long-term in situ decomposition rates of lignin in sulfate-reducing sediments were estimated for the first time. The half-life ( T1/2) of lignin derived from mangrove leaf litter (mainly Rhizophora mangle) was ˜150 yr in the upper 1.5 m of the sediment. Associated organic carbon from leaf tissue was depleted to ˜75% within weeks, followed by a slow mineralization in the sediment ( T1/2 ≈ 300 yr). Unlike the known pathways of lignin diagenesis, even highly degraded lignin did not show any alterations of the propyl or methoxyl side chains, as evident from stable acid to aldehyde ratios and the proportion of methoxylated phenols (vanillyl and syringyl phenols). Aromatic ring cleavage is probably the principal mechanism for lignin decay in the studied environment. Cinnamyl phenols were highly abundant in mangrove leaves and were rapidly depleted during early diagenesis. Thus, the cinnamyl to vanillyl ratio could be used as a tracer for early diagenesis even under the sulfate-reducing conditions. Syringyl phenols were removed from dissolved organic matter in interstitial water, probably by sorption onto the sediment. Suspended organic matter in a

  14. Lignin and related compounds. VIII. Lignin monomers and dimers from hydrogenolysis of aspen wood using rhodium-on-charcoal catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Sudo, K; Mullord, D J; Pepper, J M

    1981-04-01

    Aspen poplar wood meal has been subjected to catalytic hydrogenolysis in dioxane-water (9:1) at 500 psig initial pressure of hydrogen over a 5% rhodium-on-charcoal catalyst for five hours at 195 plus or minus 5 degrees C. The resulting chloroform-soluble lignin degradation products were separated by cellulose and silica gel column chromatography. The following compounds were isolated and identified: 4-hydroxybenzoic acid, 1-(4-hydroxy-3,4-dimethoxyphenyl)-1-propanone (propiosyringone), 2,2'-dihydroxy-3,3'-dimethoxy- 5,5'-dipropylbiphenyl, 2,3-bis(4-hydroxy-3,5- dimethoxyphenyl)-1-propanol, and a mixture of 3-(4-hydroxy-3,5-dimethoxyphenyl)-2(4-hydroxy- 3-methoxyphenyl)-1-propan and 3-(4-hydroxy-3- methoxyphenyl)-2-(4-hydroxy-3,5-dimethoxyphenyl)-1- propanol. 9 references.

  15. Alkoxyl- and carbon-centered radicals as primary agents for degrading non-phenolic lignin-substructure model compounds.

    Science.gov (United States)

    Ohashi, Yasunori; Uno, Yukiko; Amirta, Rudianto; Watanabe, Takahito; Honda, Yoichi; Watanabe, Takashi

    2011-04-07

    Lignin degradation by white-rot fungi proceeds via free radical reaction catalyzed by oxidative enzymes and metabolites. Basidiomycetes called selective white-rot fungi degrade both phenolic and non-phenolic lignin substructures without penetration of extracellular enzymes into the cell wall. Extracellular lipid peroxidation has been proposed as a possible ligninolytic mechanism, and radical species degrading the recalcitrant non-phenolic lignin substructures have been discussed. Reactions between the non-phenolic lignin model compounds and radicals produced from azo compounds in air have previously been analysed, and peroxyl radical (PR) is postulated to be responsible for lignin degradation (Kapich et al., FEBS Lett., 1999, 461, 115-119). However, because the thermolysis of azo compounds in air generates both a carbon-centred radical (CR) and a peroxyl radical (PR), we re-examined the reactivity of the three radicals alkoxyl radical (AR), CR and PR towards non-phenolic monomeric and dimeric lignin model compounds. The dimeric lignin model compound is degraded by CR produced by reaction of 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH), which under N(2) atmosphere cleaves the α-β bond in 1-(4-ethoxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol to yield 4-ethoxy-3-methoxybenzaldehyde. However, it is not degraded by the PR produced by reaction of Ce(4+)/tert-BuOOH. In addition, it is degraded by AR produced by reaction of Ti(3+)/tert-BuOOH. PR and AR are generated in the presence and absence of veratryl alcohol, respectively. Rapid-flow ESR analysis of the radical species demonstrates that AR but not PR reacts with the lignin model compound. Thus, AR and CR are primary agents for the degradation of non-phenolic lignin substructures.

  16. Decoupling of lignin and total litter decomposition across North American forest soils: a phenomenon to reconcile old and new paradigms of soil organic matter?

    Science.gov (United States)

    Hall, S. J.; Hammel, K.

    2017-12-01

    An "old" paradigm of soil organic matter (SOM) posited that biochemically "recalcitrant" lignin derivatives were a dominant constituent. Over the past decade(s), evidence for a newer paradigm has emerged which suggests that recalcitrance has little long-term impact on the biochemical composition of SOM, and that lignin is relatively unimportant in comparison with dead microbial biomass. Yet, methodological biases have hampered accurate quantification of lignin dynamics in mineral soils, and may have led to systematic underestimates of lignin stocks and turnover. Here, we sought to test this aspect of the "new" SOM paradigm. Synthetic position-specific 13C-labeled lignins provide a robust quantitative method to track the mineralization and fate of lignin moieties in mineral soils. Relatively few microbial taxa are known to depolymerize macromolecular lignin, and lignin derivatives can specifically associate with iron oxide mineral phases. Consequently, we hypothesized that decomposition of lignin is poorly correlated with total litter decomposition across ecosystems, and that lignin may represent a variable but significant component of decadal-cycling SOM. We incubated 10 forest soils spanning diverse North American ecosystems over seven months under laboratory conditions at constant temperature and moisture. Soils were incubated alone, with added C4 grass litter and natural isotope abundance lignin, and with added C4 litter and 13Cß-labeled lignin. These treatments allowed us to partition respiration for each soil from SOM, litter, and the Cß moiety of lignin—which is diagnostic for cleavage of the polymer. Consistent with our hypothesis, we found much greater variability (ten-fold) in cumulative lignin mineralization relative to bulk litter (two-fold) among soils. Multiple-pool first-order decay models implied that mean turnover times for lignin ranged from one to several decades among soils, relative to several years for bulk litter. Our results suggest a

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

    Directory of Open Access Journals (Sweden)

    Run-Cang Sun

    2013-01-01

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

  18. Examining an underappreciated control on lignin decomposition in soils? Effects of reactive manganese species on intact plant cell walls

    Science.gov (United States)

    Keiluweit, M.; Bougoure, J.; Pett-Ridge, J.; Kleber, M.; Nico, P. S.

    2011-12-01

    Lignin comprises a dominant proportion of carbon fluxes into the soil (representing up to 50% of plant litter and roots). Two lines of evidence suggest that manganese (Mn) acts as a strong controlling factor on the residence time of lignin in soil ecosystems. First, Mn content is highly correlated with litter decomposition in temperate and boreal forest soil ecosystems and, second, microbial agents of lignin degradation have been reported to rely on reactive Mn(III)-complexes to specifically oxidize lignin. However, few attempts have been made to isolate the mechanisms responsible for the apparent Mn-dependence of lignin decomposition in soils. Here we tested the hypothesis that Mn(III)-oxalate complexes may act as a perforating 'pretreatment' for structurally intact plant cell walls. We propose that these diffusible oxidizers are small enough to penetrate and react with non-porous ligno-cellulose in cell walls. This process was investigated by reacting single Zinnia elegans tracheary elements with Mn(III)-oxalate complexes in a continuous flow-through microreactor. The uniformity of cultured tracheary elements allowed us to examine Mn(III)-induced changes in cell wall chemistry and ultrastructure on the micro-scale using fluorescence and electron microscopy as well as synchrotron-based infrared and X-ray spectromicroscopy. Our results show that Mn(III)-complexes substantially oxidize specific lignin components of the cell wall, solubilize decomposition products, severely undermine the cell wall integrity, and cause cell lysis. We conclude that Mn(III)-complexes induce oxidative damage in plant cell walls that renders ligno-cellulose substrates more accessible for microbial lignin- and cellulose-decomposing enzymes. Implications of our results for the rate limiting impact of soil Mn speciation and availability on litter decomposition in forest soils will be discussed.

  19. Chapter 1: A Brief Introduction to Lignin Structure

    Energy Technology Data Exchange (ETDEWEB)

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

    2018-04-03

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

  20. Chemical studies on oils derived from aspen poplar wood, cellulose, and an isolated aspen poplar lignin

    Energy Technology Data Exchange (ETDEWEB)

    Eager, R L; Pepper, J M; Roy, J C; Mathews, J F

    1983-01-01

    An initial study has been made of the chemical nature of the oil phase resulting from the conversion of aspen poplar wood, cellulose, and an isolated lignin from the aspen poplar as a result of their interactions with water and carbon monoxide in the presence of sodium carbonate at 360 degrees C. Gas chromatographic analysis of the sodium hydroxide soluble fractions from each substrate revealed similar spectra of alkyl-substituted phenols. The relative abundance of identified low molecular weight phenolic compounds decreased from lignin to wood to cellulose. This was in agreement with the known phenolic nature of lignin. As well, it confirmed the synthesis during reaction of such compounds from a carbohydrate substrate. Gas chromatographic analysis of the whole oils also revealed the presence in each case of several alkyl-substituted cyclopentanones whose relative abundance decreased from cellulose to wood to lignin. Silica gel column separation of the oils, after a charcoal treatment, followed by capillary gas chromatographic - mass spectrometric analyses of the resulting fraction indicated the presence of other higher molecular weight phenols, napthols, cycloalkanols, and polycyclic and long chain alkanes and alkenes.

  1. Systematic Parameterization of Lignin for the CHARMM Force Field

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-07-06

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

  2. Conversion of potash soap and lignin into liquid fuels. Final report; Suovan ja ligniinin jalostaminen polttonesteiksi. Loppuraportti

    Energy Technology Data Exchange (ETDEWEB)

    McKeough, P.; Oasmaa, A.

    1994-12-31

    The main task of the research is to estimate the suitability of catalytic hydration for refining of following rawmaterials into liquid fuels: concentrated black liquor, raw potash soap (especially birch containing mixed potash soap) and organosolv (Milox) lignin. When hydrating the concentrated black liquor catalytically (ammonium heptamolybdate/420 deg C or NiMo-Cr{sub 2}O{sub 3}/450 deg C) it is possible to convert about 30 wt-% of the original organic matter of the black liquor into hexane soluble oils. It is possible to remove the inorganic matter from the product oil by water extraction without reducing the amount of hexane suluble oil. The energy content of the hexane soluble oil is about 60 % of the energy content of the black liquor. The raw potash soap is cracked into oils and gases at 435- 450 deg C. The yield of the hexane soluble oil in nitrogen atmosphere without a catalyst is about 40 % of the organic matter of the potash soap. The calorific value of the oil is 42 MJ/kg, which corresponds to about 45 % energy yield. The presence of a catalyst and hydrogen gas increases the yield of hexane soluble oil (45 wt-%) and effects on the chemical composition of the product by increasing the portion of aliphatic hydrocarbons. It is possible to obtain oil of good quality from Milox lignin by using the catalytic hydration. At 420 deg C with 60 min retention time, at presence of the NiMo- Cr{sub 2}O{sub 3} catalyst and hydrogen gas, oil yield of 53 % and hexane soluble oil yield of 41 % (of organic matter of lignin) are obtained. The calorific value of the oil is 40 MJ/kg (Milox lignin 25 MJ/kg). (3 refs., 3 tabs., 1 fig.)

  3. Understanding the fast pyrolysis of lignin.

    Science.gov (United States)

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

    2011-11-18

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

  4. Effects of laccase on lignin depolymerization and enzymatic hydrolysis of ensiled corn stover.

    Science.gov (United States)

    Chen, Qin; Marshall, Megan N; Geib, Scott M; Tien, Ming; Richard, Tom L

    2012-08-01

    The aim of this study was to explore the synergies of laccase, a ligninolytic enzyme, with cellulose and hemicellulase amendments on ensiled corn stover. Molecular signals of lignin decomposition were observed by tetramethylammonium hydroxide thermochemolysis and gas chromatography-mass spectroscopy (TMAH-GC-MS) analysis. The significant findings suggest that ensilage might provide a platform for biological pretreatment. By partially hydrolyzing cellulose and hemicellulose into soluble sugars, ensilage facilitates laccase penetration into the lignocellulose complex to enhance lignin degradation. Downstream cellulose hydrolysis was improved 7% with increasing laccase loading rate. These results demonstrate the potential of enzymes, either directly amended or expressed by microbes during ensilage, to maximize utilization of corn stover for cellulosic biofuels and other downstream fermentations. Copyright © 2012. Published by Elsevier Ltd.

  5. Biochemical synthesis of water soluble conducting polymers

    Science.gov (United States)

    Bruno, Ferdinando F.; Bernabei, Manuele

    2016-05-01

    An efficient biomimetic route for the synthesis of conducting polymers/copolymers complexed with lignin sulfonate and sodium (polystyrenesulfonate) (SPS) will be presented. This polyelectrolyte assisted PEG-hematin or horseradish peroxidase catalyzed polymerization of pyrrole (PYR), 3,4 ethyldioxithiophene (EDOT) and aniline has provided a route to synthesize water-soluble conducting polymers/copolymers under acidic conditions. The UV-vis, FTIR, conductivity and cyclic voltammetry studies for the polymers/copolymer complex indicated the presence of a thermally stable and electroactive polymers. Moreover, the use of water-soluble templates, used as well as dopants, provided a unique combination of properties such as high electronic conductivity, and processability. These polymers/copolymers are nowadays tested/evaluated for antirust features on airplanes and helicopters. However, other electronic applications, such as photovoltaics, for transparent conductive polyaniline, actuators, for polypyrrole, and antistatic films, for polyEDOT, will be proposed.

  6. Biochemical synthesis of water soluble conducting polymers

    Energy Technology Data Exchange (ETDEWEB)

    Bruno, Ferdinando F., E-mail: Ferdinando-Bruno@uml.edu [US Army Natick Soldier Research, Development and Engineering Center, Natick, MA 01760 (United States); Bernabei, Manuele [ITAF, Test Flight Centre, Chemistry Dept. Pratica di Mare AFB, 00071 Pomezia (Rome), Italy (UE) (Italy)

    2016-05-18

    An efficient biomimetic route for the synthesis of conducting polymers/copolymers complexed with lignin sulfonate and sodium (polystyrenesulfonate) (SPS) will be presented. This polyelectrolyte assisted PEG-hematin or horseradish peroxidase catalyzed polymerization of pyrrole (PYR), 3,4 ethyldioxithiophene (EDOT) and aniline has provided a route to synthesize water-soluble conducting polymers/copolymers under acidic conditions. The UV-vis, FTIR, conductivity and cyclic voltammetry studies for the polymers/copolymer complex indicated the presence of a thermally stable and electroactive polymers. Moreover, the use of water-soluble templates, used as well as dopants, provided a unique combination of properties such as high electronic conductivity, and processability. These polymers/copolymers are nowadays tested/evaluated for antirust features on airplanes and helicopters. However, other electronic applications, such as photovoltaics, for transparent conductive polyaniline, actuators, for polypyrrole, and antistatic films, for polyEDOT, will be proposed.

  7. Biochemical synthesis of water soluble conducting polymers

    International Nuclear Information System (INIS)

    Bruno, Ferdinando F.; Bernabei, Manuele

    2016-01-01

    An efficient biomimetic route for the synthesis of conducting polymers/copolymers complexed with lignin sulfonate and sodium (polystyrenesulfonate) (SPS) will be presented. This polyelectrolyte assisted PEG-hematin or horseradish peroxidase catalyzed polymerization of pyrrole (PYR), 3,4 ethyldioxithiophene (EDOT) and aniline has provided a route to synthesize water-soluble conducting polymers/copolymers under acidic conditions. The UV-vis, FTIR, conductivity and cyclic voltammetry studies for the polymers/copolymer complex indicated the presence of a thermally stable and electroactive polymers. Moreover, the use of water-soluble templates, used as well as dopants, provided a unique combination of properties such as high electronic conductivity, and processability. These polymers/copolymers are nowadays tested/evaluated for antirust features on airplanes and helicopters. However, other electronic applications, such as photovoltaics, for transparent conductive polyaniline, actuators, for polypyrrole, and antistatic films, for polyEDOT, will be proposed.

  8. Smooth model surfaces from lignin derivatives. II. Adsorption of polyelectrolytes and PECs monitored by QCM-D.

    Science.gov (United States)

    Norgren, Magnus; Gärdlund, Linda; Notley, Shannon M; Htun, Myat; Wågberg, Lars

    2007-03-27

    For the first time to the knowledge of the authors, well-defined and stable lignin model surfaces have been utilized as substrates in polyelectrolyte adsorption studies. The adsorption of polyallylamine (PAH), poly(acrylic acid) (PAA), and polyelectrolyte complexes (PECs) was monitored using quartz crystal microgravimetry with dissipation (QCM-D). The PECs were prepared by mixing PAH and PAA at different ratios and sequences, creating both cationic and anionic PECs with different charge levels. The adsorption experiments were performed in 1 and 10 mM sodium chloride solutions at pH 5 and 7.5. The highest adsorption of PAH and cationic PECs was found at pH 7.5, where the slightly negatively charged nature of the lignin substrate is more pronounced, governing electrostatic attraction of oppositely charged polymeric substances. An increase in the adsorption was further found when the electrolyte concentration was increased. In comparison, both PAA and the anionic PEC showed remarkably high adsorption to the lignin model film. The adsorption of PAA was further studied on silica and was found to be relatively low even at high electrolyte concentrations. This indicated that the high PAA adsorption on the lignin films was not induced by a decreased solubility of the anionic polyelectrolyte. The high levels of adsorption on lignin model surfaces found both for PAA and the anionic PAA-PAH polyelectrolyte complex points to the presence of strong nonionic interactions in these systems.

  9. Fiber and lignin analysis in concentrate, forage, and feces

    DEFF Research Database (Denmark)

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

    2006-01-01

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

  10. UJI AKTIVITAS ANTIOKSIDAN HASIL DEGRADASI LIGNIN DARI SERBUK GERGAJI KAYU KALBA (Albizia falcataria DENGAN METODE TBA (Thio Barbituric Acid

    Directory of Open Access Journals (Sweden)

    Undri Rastuti

    2010-11-01

    Full Text Available Antioxidants are compounds that can delay, retard or inhibit the oxidation reaction. Lignin is a natural polymer consisting of monomeric substituted phenols. Wood lignin degradation Kalba (Albizia falcataria yields substituted phenol. The purpose of this study was to test the antioxidant activity of compounds of lignin degradation products Kalba using TBA (Thiobarbituric Acid. Wood lignin degradation products Kalba tested antioxidant activity using the TBA method. Phase test phase of this antioxidant activity is sample preparation, determination of the maximum wavelength, determination of equilibrium time, absorbance measurements and determination of the percentage of inhibition. The wavelength maximum for BHT test solution was obtained at 530 nm. The stability of absorbance achieved after 80 minutes equilibrium time. BHT test solution and sample solution containing the degradation of lignin 0.10% (w/v increased but not as sharp as the absorbance of control, this suggests that the degradation of wood lignin Kalba have activity as an antioxidant, which relative minimize 13,70 % compare with BHT.

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

    Science.gov (United States)

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

    2017-08-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1984-05-01

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

  13. Towards Biomimicking Wood: Fabricated Free-standing Films of Nanocellulose, Lignin, and a Synthetic Polycation

    Science.gov (United States)

    Pillai, Karthik; Navarro Arzate, Fernando; Zhang, Wei; Renneckar, Scott

    2014-01-01

    Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and lignin. Layer-by-layer (LbL) assembly process which relies on the assembly of oppositely charged molecules from aqueous solutions was used to build a freestanding composite film of isolated wood polymers of lignin and oxidized nanofibril cellulose (NFC). To facilitate the assembly of these negatively charged polymers, a positively charged polyelectrolyte, poly(diallyldimethylammomium chloride) (PDDA), was used as a linking layer to create this simplified model cell wall. The layered adsorption process was studied quantitatively using quartz crystal microbalance with dissipation monitoring (QCM-D) and ellipsometry. The results showed that layer mass/thickness per adsorbed layer increased as a function of total number of layers. The surface coverage of the adsorbed layers was studied with atomic force microscopy (AFM). Complete coverage of the surface with lignin in all the deposition cycles was found for the system, however, surface coverage by NFC increased with the number of layers. The adsorption process was carried out for 250 cycles (500 bilayers) on a cellulose acetate (CA) substrate. Transparent free-standing LBL assembled nanocomposite films were obtained when the CA substrate was later dissolved in acetone. Scanning electron microscopy (SEM) of the fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle (PDDA-Lignin-PDDA-NC) was estimated to be 17 nm for two different lignin types used in the study. The data indicates a film with highly controlled architecture where nanocellulose and lignin are spatially deposited on the nanoscale (a polymer-polymer nanocomposites), similar to what is observed in the native cell wall. PMID:24961302

  14. In vitro evaluation of antioxidant and cytotoxic activities of lignin fractions extracted from Acacia nilotica.

    Science.gov (United States)

    Barapatre, Anand; Meena, Avtar Singh; Mekala, Sowmya; Das, Amitava; Jha, Harit

    2016-05-01

    Lignin is one of the most important phytomacromolecule with diverse therapeutic properties such as anticancer, antimicrobial, anti-inflammatory and immune-stimulatory. The present study was carried out to evaluate the in vitro antioxidant, free radical scavenging and anti-proliferative/cytotoxic activities of eleven different lignin fractions, extracted from the wood of Acacia nilotica by pressurized solvent extraction (PSE) and successive solvent extraction (SSE) methods. Results indicate that the PSE fractions have high polyphenolic content and reducing power. However, the antioxidant efficiency examined by DPPH and ABTS radical scavenging assay was higher in SSE fractions. All lignin fractions revealed a significant ability to scavenge nitric oxide, hydroxyl and superoxide radicals. The extracted lignin fractions display high ferric ion reducing capacity and also possess excellent antioxidant potential in the hydrophobic (linoleic acid) system. Fractions extracted by polar solvent has the highest iron (Fe(2+)) chelating activity as compared to other factions, indicating their effect on the redox cycling of iron. Four lignin fractions depicted higher cytotoxic potential (IC50: 2-15 μg/mL) towards breast cancer cell line (MCF-7) but were ineffective (IC50: ≥ 100 μg/mL) against normal primary human hepatic stellate cells (HHSteCs). These findings suggest that the lignin extracts of A. nilotica wood has a remarkable potential to prevent disease caused by the overproduction of radicals and also seem to be a promising candidate as natural antioxidant and anti-cancer agents. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2015-10-30

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

  16. Native lignin for bonding fiber boards - evaluation of bonding mechanisms in boards made from laccase-treated fibers of beech (Fagus sylvatica)

    DEFF Research Database (Denmark)

    Felby, Claus; Thygesen, Lisbeth Garbrecht; Sanadi, Anand

    2004-01-01

    indicate that lignin extractives are precipitated on the fiber surfaces. The improved bonding may be related to several factors, linked to a more lignin rich fiber surface, such as surface molecular entanglements and covalent bonding between fibers through cross-linking of radicals. (C) 2004 Published......The auto-adhesion of beech wood (Fagus sylvatica) fibers can be enhanced by a pretreatment of the fibers with a phenol oxidase enzyme. The mechanism of enzymatic catalyzed bonding is linked to the generation of stable radicals in lignin by oxidation. Fiberboards made from laccase-treated fibers...

  17. The solubility of inorganic compounds in water and steam with particular reference to silica and iron oxides and its deposits in power plant cycles

    International Nuclear Information System (INIS)

    Heitmann, H.G.

    1975-01-01

    The presence of silica in the water-steam cycle can be extremely detrimental to the operation of a high pressure power station. The solubility diagram of silica in water and steam obtained from numerous measurements is presented. The solubility and deposition of corrosion products, particularly iron oxyde, were investigated together with the effect on heat transfer in heated steam generator tubes. The remove corrosion products from feedwater, electromagnetic filters may be employed and their installation in the primary circuits of the PWR type reactors leads to a considerable reduction of the corrosion products and activity levels

  18. Analytical methods for lignin characterization - Differential scanning calorimetry

    NARCIS (Netherlands)

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

    2006-01-01

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

  19. Genetic engineering of syringyl-enriched lignin in plants

    Science.gov (United States)

    Chiang, Vincent Lee; Li, Laigeng

    2004-11-02

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

  20. Advances in the chemical utilization of alkali lignin

    International Nuclear Information System (INIS)

    Van der Klashorst, G.H.

    1985-06-01

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

  1. Thorium oxalate solubility and morphology

    International Nuclear Information System (INIS)

    Monson, P.R. Jr.; Hall, R.

    1981-10-01

    Thorium was used as a stand-in for studying the solubility and precipitation of neptunium and plutonium oxalates. Thorium oxalate solubility was determined over a range of 0.001 to 10.0 in the concentration parameter [H 2 C 2 O 4 ]/[HNO 3 ] 2 . Morphology of thorium oxide made from the oxalate precipitates was characterized by scanning electron microscopy. The different morphologies found for oxalate-lean and oxalate-rich precipitations were in agreement with predictions based on precipitation theory

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

    NARCIS (Netherlands)

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

    2016-01-01

    The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges

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

    DEFF Research Database (Denmark)

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

    2018-01-01

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

  4. 3 and 4 oxidation state element solubilities in borosilicate glasses. Implement to actinides in nuclear glasses; Solubilite des elements aux degres d'oxydation (3) et (4) dans les verres de borosilicate. Application aux actinides dans les verres nucleaires

    Energy Technology Data Exchange (ETDEWEB)

    Cachia, J.N

    2005-12-15

    In order to ensure optimal radionuclides containment, the knowledge of the actinide loading limits in nuclear waste glasses and also the comprehension of the solubilization mechanisms of these elements are essential. A first part of this manuscript deals with the study of the differences in solubility of the tri and tetravalent elements (actinides and surrogates) particularly in function of the melting temperature. The results obtained indicate that trivalent elements (La, Gd, Nd, Am, Cm) exhibit a higher solubility than tetravalent elements (Hf, Th, Pu). Consequently, it was planned to reduce plutonium at the oxidation state (III), the later being essentially tetravalent in borosilicate glasses. An innovating reduction process of multi-valent elements (cerium, plutonium) using silicon nitride has been developed in a second part of this work. Reduced plutonium-bearing glasses synthesized by Si{sub 3}N{sub 4} addition made it possible to double the plutonium solubility from 2 to 4 wt% at 1200 deg C. A structural approach to investigate the differences between tri and tetravalent elements was finally undertaken. These investigations were carried out by X-rays Absorption Spectroscopy (EXAFS) and NMR. Trivalent rare earth and actinide elements seem to behave as network modifiers while tetravalent elements rather present true intermediaries' behaviour. (author)

  5. Paraquat induces oxidative stress, neuronal loss in substantia nigra region and Parkinsonism in adult rats: Neuroprotection and amelioration of symptoms by water-soluble formulation of Coenzyme Q10

    Directory of Open Access Journals (Sweden)

    Sridhar TS

    2009-07-01

    Full Text Available Abstract Background Parkinson's disease, for which currently there is no cure, develops as a result of progressive loss of dopamine neurons in the brain; thus, identification of any potential therapeutic intervention for disease management is of a great importance. Results Here we report that prophylactic application of water-soluble formulation of coenzyme Q10 could effectively offset the effects of environmental neurotoxin paraquat, believed to be a contributing factor in the development of familial PD. In this study we utilized a model of paraquat-induced dopaminergic neurodegeneration in adult rats that received three weekly intra-peritoneal injections of the herbicide paraquat. Histological and biochemical analyses of rat brains revealed increased levels of oxidative stress markers and a loss of approximately 65% of dopamine neurons in the substantia nigra region. The paraquat-exposed rats also displayed impaired balancing skills on a slowly rotating drum (rotorod evidenced by their reduced spontaneity in gait performance. In contrast, paraquat exposed rats receiving a water-soluble formulation of coenzyme Q10 in their drinking water prior to and during the paraquat treatment neither developed neurodegeneration nor reduced rotorod performance and were indistinguishable from the control paraquat-untreated rats. Conclusion Our data confirmed that paraquat-induced neurotoxicity represents a convenient rat model of Parkinsonian neurodegeneration suitable for mechanistic and neuroprotective studies. This is the first preclinical evaluation of a water-soluble coenzyme Q10 formulation showing the evidence of prophylactic neuroprotection at clinically relevant doses.

  6. Chemical Methods for the Determination of Soluble and Insoluble Non-Starch Polysaccharides - Review

    OpenAIRE

    Rodica Căpriţă; Adrian Căpriţă

    2011-01-01

    Polysaccharides are macromolecules of monosaccharides linked by glycosidic bonds. Non-starch polysaccharides(NSP) are principally non-α-glucan polysaccharides of the plant cell wall. They are a heterogeneous group ofpolysaccharides with varying degrees of water solubility, size, and structure. The water insoluble fiber fractioninclude cellulose, galactomannans, xylans, xyloglucans, and lignin, while the water-soluble fibers are the pectins,arabinogalactans, arabinoxylans, and β-(1,3)(1,4)-D-g...

  7. Environmental economics of lignin derived transport fuels.

    Science.gov (United States)

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

    2017-11-01

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

  8. Naturally p-Hydroxybenzoylated Lignins in Palms

    Science.gov (United States)

    Fachuang Lu; Steven D. Karlen; Matt Regner; Hoon Kim; Sally A. Ralph; Run-Cang Sun; Ken-ichi Kuroda; Mary Ann Augustin; Raymond Mawson; Henry Sabarez; Tanoj Singh; Gerardo Jimenez-Monteon; Sarani Zakaria; Stefan Hill; Philip J. Harris; Wout Boerjan; Curtis G. Wilkerson; Shawn D. Mansfield; John Ralph

    2015-01-01

    The industrial production of palm oil concurrently generates a substantial amount of empty fruit bunch (EFB) fibers that could be used as a feedstock in a lignocellulose based biorefinery. Lignin byproducts generated by this process may offer opportunities for the isolation of value-added products, such as p-hydroxybenzoate (pBz),...

  9. Catalytic depolymerization of lignin in supercritical ethanol

    NARCIS (Netherlands)

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

    2014-01-01

    One-step valorization of soda lignin in supercritical ethanol using a CuMgAlOx catalyst results in high monomer yield (23 wt¿%) without char formation. Aromatics are the main products. The catalyst combines excellent deoxygenation with low ring-hydrogenation activity. Almost half of the monomer

  10. Enzymology and molecular biology of lignin degradation

    Science.gov (United States)

    D. Cullen; P.J. Kersten

    2004-01-01

    This review provides an overview of the physiology and genetics of lignin degradation by white rot basidiomycetes. Emphasis is on recent advances and the reader is referred to earlier comprehensive reviews for historical perspective and background (Kirk and Farrell 1987; Gold and Alic 1993; Higuchi 1993; Cullen and Kersten 1996; Cullen 1997). Recent completion of a...

  11. Lignin-blocking treatment of biomass and uses thereof

    Science.gov (United States)

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

    2009-10-20

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

  12. Polymerization of Various Lignins via Immobilized Myceliophthora thermophila Laccase (MtL

    Directory of Open Access Journals (Sweden)

    Daniela Huber

    2016-08-01

    Full Text Available Enzymatic polymerization of lignin is an environmentally-friendly and sustainable method that is investigated for its potential in opening-up new applications of one of the most abundant biopolymers on our planet. In this work, the laccase from Myceliophthora thermophila was successfully immobilized onto Accurel MP1000 beads (67% of protein bound to the polymeric carrier and the biocatalyzed oxidation of Kraft lignin (KL and lignosulfonate (LS were carried out. Fluorescence intensity determination, phenol content analysis and size exclusion chromatography were performed in order to elucidate the extent of the polymerization reaction. The collected results show an 8.5-fold decrease of the LS samples’ fluorescence intensity after laccase-mediated oxidation and a 12-fold increase of the weight average molecular weight was obtained.

  13. Lignin decomposition and microbial community in paddy soils: effects of alternating redox conditions

    Science.gov (United States)

    Cerli, Chiara; Liu, Qin; Hanke, Alexander; Kaiser, Klaus; Kalbitz, Karsten

    2013-04-01

    Paddy soils are characterised by interchanging cycles of anaerobic and aerobic conditions. Such fluctuations cause continuous changes in soil solution chemistry as well as in the composition and physiological responses of the microbial community. Temporary deficiency in oxygen creates conditions favourable to facultative or obligates anaerobic bacteria, while aerobic communities can thrive in the period of water absence. These alterations can strongly affect soil processes, in particular organic matter (OM) accumulation and mineralization. In submerged soils, lignin generally constitutes a major portion of the total OM because of hampered degradation under anoxic conditions. The alternating redox cycles resulting from paddy soil management might promote both degradation and preservation of lignin, affecting the overall composition and reactivity of total and dissolved OM. We sampled soils subjected to cycles of anoxic (rice growing period) and oxic (harvest and growth of other crops) conditions since 700 and 2000 years. We incubated suspended Ap material, sampled from the two paddy plus two corresponding non-paddy control soils under oxic and anoxic condition, for 3 months, interrupted by a short period of three weeks (from day 21 to day 43) with reversed redox conditions. At each sampling time (day 2, 21, 42, 63, 84), we determined lignin-derived phenols (by CuO oxidation) as well as phospholipids fatty acids contents and composition. We aimed to highlight changes in lignin decomposition as related to the potential rapid changes in microbial community composition. Since the studied paddy soils had a long history of wet rice cultivation, the microbial community should be well adapted to interchanging oxic and anoxic cycles, therefore fully expressing its activity at both conditions. In non-paddy soil changes in redox conditions caused modification of quantity and composition of the microbial community. On the contrary, in well-established paddy soils the microbial

  14. Acridine Orange Indicates Early Oxidation of Wood Cell Walls by Fungi

    Science.gov (United States)

    Carl J. Houtman; Peter Kitin; Jon C. D. Houtman; Kenneth E. Hammel; Christopher G. Hunt

    2016-01-01

    Colonization of wood blocks by brown and white rot fungi rapidly resulted in detectable wood oxidation, as shown by a reduced phloroglucinol response, a loss of autofluorescence, and acridine orange (AO) staining. This last approach is shown to provide a novel method for identifying wood oxidation. When lignin was mildly oxidized, the association between AO and lignin...

  15. Reactions of Lignin Model Compounds in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Holladay, John E.; Binder, Joseph B.; Gray, Michel J.; White, James F.; Zhang, Z. Conrad

    2009-09-15

    Lignin, a readily available form of biomass, awaits novel chemistry for converting it to valuable aromatic chemicals. Recent work has demonstrated that ionic liquids are excellent solvents for processing woody biomass and lignin. Seeking to exploit ionic liquids as media for depolymerization of lignin, we investigated reactions of lignin model compounds in these solvents. Using Brønsted acid catalysts in 1-ethyl-3-methylimidazolium triflate at moderate temperatures, we obtained up to 11.6% yield of the dealkylation product guaiacol from the model compound eugenol and cleaved phenethyl phenyl ether, a model for lignin ethers. Despite these successes, acid catalysis failed in dealkylation of the unsaturated model compound 4-ethylguaiacol and did not produce monomeric products from organosolv lignin, demonstrating that further work is required to understand the complex chemistry of lignin depolymerization.

  16. Pure Phase Solubility Limits: LANL

    International Nuclear Information System (INIS)

    C. Stockman

    2001-01-01

    The natural and engineered system at Yucca Mountain (YM) defines the site-specific conditions under which one must determine to what extent the engineered and the natural geochemical barriers will prevent the release of radioactive material from the repository. Most important mechanisms for retention or enhancement of radionuclide transport include precipitation or co-precipitation of radionuclide-bearing solid phases (solubility limits), complexation in solution, sorption onto surfaces, colloid formation, and diffusion. There may be many scenarios that could affect the near-field environment, creating chemical conditions more aggressive than the conditions presented by the unperturbed system (such as pH changes beyond the range of 6 to 9 or significant changes in the ionic strength of infiltrated waters). For an extended period of time, the near-field water composition may be quite different and more extreme in pH, ionic strength, and CO 2 partial pressure (or carbonate concentration) than waters at some distance from the repository. Reducing conditions, high pH (up to 11), and low carbonate concentration may be present in the near-field after reaction of infiltrating groundwater with engineered barrier systems, such as cementitious materials. In the far-field, conditions are controlled by the rock-mass buffer providing a near-neutral, oxidizing, low-ionic-strength environment that controls radionuclide solubility limits and sorption capacities. There is the need for characterization of variable chemical conditions that affect solubility, speciation, and sorption reactions. Modeling of the groundwater chemistry is required and leads to an understanding of solubility and speciation of the important radionuclides. Because experimental studies cannot be performed under the numerous potential chemical conditions, solubility limitations must rely on geochemical modeling of the radionuclide's chemistry. Fundamental thermodynamic properties, such as solubility products

  17. Pure Phase Solubility Limits: LANL

    Energy Technology Data Exchange (ETDEWEB)

    C. Stockman

    2001-01-26

    The natural and engineered system at Yucca Mountain (YM) defines the site-specific conditions under which one must determine to what extent the engineered and the natural geochemical barriers will prevent the release of radioactive material from the repository. Most important mechanisms for retention or enhancement of radionuclide transport include precipitation or co-precipitation of radionuclide-bearing solid phases (solubility limits), complexation in solution, sorption onto surfaces, colloid formation, and diffusion. There may be many scenarios that could affect the near-field environment, creating chemical conditions more aggressive than the conditions presented by the unperturbed system (such as pH changes beyond the range of 6 to 9 or significant changes in the ionic strength of infiltrated waters). For an extended period of time, the near-field water composition may be quite different and more extreme in pH, ionic strength, and CO{sub 2} partial pressure (or carbonate concentration) than waters at some distance from the repository. Reducing conditions, high pH (up to 11), and low carbonate concentration may be present in the near-field after reaction of infiltrating groundwater with engineered barrier systems, such as cementitious materials. In the far-field, conditions are controlled by the rock-mass buffer providing a near-neutral, oxidizing, low-ionic-strength environment that controls radionuclide solubility limits and sorption capacities. There is the need for characterization of variable chemical conditions that affect solubility, speciation, and sorption reactions. Modeling of the groundwater chemistry is required and leads to an understanding of solubility and speciation of the important radionuclides. Because experimental studies cannot be performed under the numerous potential chemical conditions, solubility limitations must rely on geochemical modeling of the radionuclide's chemistry. Fundamental thermodynamic properties, such as solubility

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

    Science.gov (United States)

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

    2013-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Michaël Quentin

    2009-01-01

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

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

    Science.gov (United States)

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

    2009-01-01

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

  1. Metal-Free Aqueous Flow Battery with Novel Ultrafiltered Lignin as Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Mukhopadhyay, Alolika [Department of Mechanical and Industrial Engineering, Northeastern University, 360 Huntington Avenue, 334 Snell Engineering, Boston, Massachusetts 02115, United States; Hamel, Jonathan [Department of Mechanical and Industrial Engineering, Northeastern University, 360 Huntington Avenue, 334 Snell Engineering, Boston, Massachusetts 02115, United States; Katahira, Rui [National Renewable Energy Laboratory, Denver West Parkway, Golden, Colorado 80401, United States; Zhu, Hongli [Department of Mechanical and Industrial Engineering, Northeastern University, 360 Huntington Avenue, 334 Snell Engineering, Boston, Massachusetts 02115, United States

    2018-03-05

    As the number of generation sources from intermittent renewable technologies on the electric grid increases, the need for large-scale energy storage devices is becoming essential to ensure grid stability. Flow batteries offer numerous advantages over conventional sealed batteries for grid storage. In this work, for the first time, we investigated lignin, the second most abundant wood derived biopolymer, as an anolyte for the aqueous flow battery. Lignosulfonate, a water-soluble derivative of lignin, is environmentally benign, low cost and abundant as it is obtained from the byproduct of paper and biofuel manufacturing. The lignosulfonate utilizes the redox chemistry of quinone to store energy and undergoes a reversible redox reaction. Here, we paired lignosulfonate with Br2/Br-, and the full cell runs efficiently with high power density. Also, the large and complex molecular structure of lignin considerably reduces the electrolytic crossover, which ensures very high capacity retention. The flowcell was able to achieve current densities of up to 20 mA/cm2 and charge polarization resistance of 15 ohm cm2. This technology presents a unique opportunity for a low-cost, metal-free flow battery capable of large-scale sustainable energy storage.

  2. Solvothermal conversion of technical lignins over NiMo catalysts

    DEFF Research Database (Denmark)

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

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

  3. Reactivity of lignin and lignin models towards UV-assisted peroxide

    International Nuclear Information System (INIS)

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

    1997-01-01

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

  4. Liquefaction of Biorefinery Lignin for Fuel Production

    DEFF Research Database (Denmark)

    Jensen, Anders

    at higher loadings. The effect of increased reaction time was found to be beneficial for oil yields but also caused an increase in solvent consumption and so there is a trade-off where a compromise has to be found in the event of an up scaled reaction. The reactions that cause solvent consumption during......Lignocellulosic biorefineries can be an important piece of the puzzle in fighting climate change. Present, biorefineries that produce ethanol from lignocellulose are challenged in working on market terms as the two product streams ethanol and lignin are low value products. The aim of this project...... has been to increase the value of the lignin stream. Recent regulations on shipping exhaust gasses in coastal waters dictate lower sulfur emissions which require ships to use low sulfur fuels for propulsion. This opens or expands a very large market for low sulfur fuels because a shift from...

  5. Lignin- and Hemicellulose-derived Biomass Recalcitrance

    DEFF Research Database (Denmark)

    Deralia, Parveen Kumar

    technology bringing the multitude of chemical and physical changes, which govern the level of biomass recalcitrance. The lignocellulosic biomasses in question are wheat straw and poplar and the hydrothermal pretreatment is used as pretreatment technology. The 2D HSQC NMR and wet chemistry chemical...... degree to the biomass surface, giving a proportional increase in the specific surface area opposite to wheat straw, which has a marked increase in the specific surface area. The distinctly different chemistry of lignin and hemicellulose and different lignin migration and reorganization appear...... to be correlative, helping explain differences in enzymatic saccharification performance across the pretreatment severities and between two biomasses. The main contribution of this work to the current state-of-the-art in the field is the revelation of distinct behaviors of generation of different repolymerized...

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

    NARCIS (Netherlands)

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

    2016-01-01

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

  7. Highly selective generation of vanillin by anodic degradation of lignin: a combined approach of electrochemistry and product isolation by adsorption

    Directory of Open Access Journals (Sweden)

    Dominik Schmitt

    2015-04-01

    Full Text Available The oxidative degradation of lignin into a variety of valuable products has been under investigation since the first half of the last century. Especially, the chance to claim this cheap, abundant and renewable source for the production of the important aroma chemical vanillin (1 was one of the major driving forces of lignin research. So far most of the developed methods fail in technical application since no viable concept for work-up is included. This work represents a combined approach of electrochemical conversion of Kraft lignin and product recovery by adsorption on a strongly basic anion exchange resin. Electrolysis conditions are optimized regarding reaction temperatures below 100 °C allowing operation of aqueous electrolytes in simple experimental set-up. Employing ion exchange resins gives rise to a selective removal of low molecular weight phenols from the strongly alkaline electrolyte without acidification and precipitation of remaining lignin. The latter represents a significant advantage compared with conventional work-up protocols of lignin solutions.

  8. Highly selective generation of vanillin by anodic degradation of lignin: a combined approach of electrochemistry and product isolation by adsorption.

    Science.gov (United States)

    Schmitt, Dominik; Regenbrecht, Carolin; Hartmer, Marius; Stecker, Florian; Waldvogel, Siegfried R

    2015-01-01

    The oxidative degradation of lignin into a variety of valuable products has been under investigation since the first half of the last century. Especially, the chance to claim this cheap, abundant and renewable source for the production of the important aroma chemical vanillin (1) was one of the major driving forces of lignin research. So far most of the developed methods fail in technical application since no viable concept for work-up is included. This work represents a combined approach of electrochemical conversion of Kraft lignin and product recovery by adsorption on a strongly basic anion exchange resin. Electrolysis conditions are optimized regarding reaction temperatures below 100 °C allowing operation of aqueous electrolytes in simple experimental set-up. Employing ion exchange resins gives rise to a selective removal of low molecular weight phenols from the strongly alkaline electrolyte without acidification and precipitation of remaining lignin. The latter represents a significant advantage compared with conventional work-up protocols of lignin solutions.

  9. Biodegradation of softwood lignin and guaiacylglycerol-beta-guiacyl ether by extracellular enzyme in shiitake Lentinus edodes (Berk) Sing

    Energy Technology Data Exchange (ETDEWEB)

    Oki, T.; Senba, Y.; Ishikawa, H.

    1982-01-01

    In order to explain the biodegradation of softwood lignin by shiitake (Lentinus edodes Berk. Sing.), akamatsu (Pinus densiflora Sekb. and Zucc.) dioxane lignin (NDL) and guaicylglycerol-beta-guaiacyl ether (I) were degraded by extracellular enzyme from the NDL-contained potato and malt extracts cultures of shiitake TMI-563 and 655 at 25 degrees C for a prolonged period. The main results on the basis of a functional group analysis and gel-filtration of NDL before and after the enzymatic degradation showed that the degraded DL had a higher content of phenolic OH groups than sound lignin, whereas the methoxyl or aromatic aldehyde-yielding group content was lower in the degraded lignin. The main degradation products formed from I in a crude enzyme solution were guaiacol, guaiacylglycerol, guaiacylglycol-beta-guaiacyl ether (II), and guaiacoxyacetoguaiacone (III), although the polymer was formed at pH 4.0, which is the optimum pH of peroxidase and laccase. It also was clarified that the oxidative polymerization of NDL and I occurred preferably in a crude enzyme solution at pH 4.0, and that these compounds were degraded to lower molecular fragments at pH 6.8 under the same conditions. From the above results, it is suggested that softwood lignin is more effectively degraded by the other enzyme than polyphenoloxidase, such as laccase and peroxidase, in a crude enzyme solution of L. edodes. (Refs. 9).

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

    Science.gov (United States)

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

    2016-07-20

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

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

    Science.gov (United States)

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

    2015-11-01

    Biodegradable composite films were prepared using two renewable resources based biopolymers, agar and lignin alkali. The lignin was used as a reinforcing material and agar as a biopolymer matrix. The effect of lignin concentration (1, 3, 5, and 10wt%) on the performance of the composite films was studied. In addition, the mechanical, water vapor barrier, UV light barrier properties, FE-SEM, and TGA of the films were analyzed. The agar/lignin films exhibited higher mechanical and UV barrier properties along with lower water vapor permeability compared to the neat agar film. The FTIR and SEM results showed the compatibility of lignin with agar polymer. The swelling ratio and moisture content of agar/lignin composite films were decreased with increase in lignin content. The thermostability and char content of agar/lignin composite films increased with increased lignin content. The results suggested that agar/lignin films have a potential to be used as a UV barrier food packaging material for maintaining food safety and extending the shelf-life of the packaged food. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Gas solubilities widespread applications

    CERN Document Server

    Gerrard, William

    1980-01-01

    Gas Solubilities: Widespread Applications discusses several topics concerning the various applications of gas solubilities. The first chapter of the book reviews Henr's law, while the second chapter covers the effect of temperature on gas solubility. The third chapter discusses the various gases used by Horiuti, and the following chapters evaluate the data on sulfur dioxide, chlorine data, and solubility data for hydrogen sulfide. Chapter 7 concerns itself with solubility of radon, thoron, and actinon. Chapter 8 tackles the solubilities of diborane and the gaseous hydrides of groups IV, V, and

  13. Mineralisation of 14C-labelled synthetic lignin and ligninolytic enzyme activities of litter-decomposing basidiomycetous fungi.

    Science.gov (United States)

    Steffen, K T; Hofrichter, M; Hatakka, A

    2000-12-01

    Within a screening program, 27 soil litter-decomposing basidiomycetes were tested for ligninolytic enzyme activities using agar-media containing 2,2'-azinobis(3-ethylbenzthiazoline-6-sulphonate), a humic acid or Mn2+ ions as indicator substrates. Most active species were found within the family Strophariaceae (Agrocybe praecox, Stropharia coronilla, S. rugosoannulata) and used for mineralisation experiments with a 14C-ring-labelled synthetic lignin (14C-DHP). The fungi mineralised around 25% of the lignin to 14CO2 within 12 weeks of incubation in a straw environment; about 20% of the lignin was converted to water-soluble fragments. Mn-peroxidase was found to be the predominant ligninolytic enzyme of all three fungi in liquid culture and its production was strongly enhanced in the presence of Mn2+ ions. The results of this study demonstrate that certain ubiquitous litter-decomposing basidiomycetes possess ligninolytic activities similar to the wood-decaying white-rot fungi, the most efficient lignin degraders in nature.

  14. Structural characterization of lignin in the process of cooking of cornstalk with solid alkali and active oxygen.

    Science.gov (United States)

    Yang, Qiulin; Shi, Jianbin; Lin, Lu; Zhuang, Junping; Pang, Chunsheng; Xie, Tujun; Liu, Ying

    2012-05-09

    A novel, efficient, and environmentally friendly technology is used in cornstalk cooking, active oxygen (O₂ and H₂O₂) cooking with solid alkali (MgO). After the cooking, the milled wood lignin in the raw material and pulp and the water-soluble and insoluble lignin in the yellow liquor were all characterized by attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional heteronuclear single-quantum coherence NMR. The results showed that the cooking procedure with solid alkali and active oxygen had a high selectivity for delignification, which could remove 85.5% of the lignin from the raw material. The syringyl (S/S'/S') units could be dissolved preferentially because of their high reactivity, and a novel guaiacyl unit with a carbonyl group (G') was generated in the cooking process. Moreover, during the cooking, the β-O-4' (A/A'/A″) structures as the main side-chain linkages in all the lignins could be partly broken and the β-O-4' (A') with a ring-conjugated structure was readily attacked by oxygen, whereas the H unit and β-5' and β-β' structures were found to stay stable without characteristic reaction.

  15. Removal of Water-Soluble Extractives Improves the Enzymatic Digestibility of Steam-Pretreated Softwood Barks.

    Science.gov (United States)

    Frankó, Balázs; Carlqvist, Karin; Galbe, Mats; Lidén, Gunnar; Wallberg, Ola

    2018-02-01

    Softwood bark contains a large amounts of extractives-i.e., soluble lipophilic (such as resin acids) and hydrophilic components (phenolic compounds, stilbenes). The effects of the partial removal of water-soluble extractives before acid-catalyzed steam pretreatment on enzymatic digestibility were assessed for two softwood barks-Norway spruce and Scots pine. A simple hot water extraction step removed more than half of the water-soluble extractives from the barks, which improved the enzymatic digestibility of both steam-pretreated materials. This effect was more pronounced for the spruce than the pine bark, as evidenced by the 30 and 11% glucose yield improvement, respectively, in the enzymatic digestibility. Furthermore, analysis of the chemical composition showed that the acid-insoluble lignin content of the pretreated materials decreased when water-soluble extractives were removed prior to steam pretreatment. This can be explained by a decreased formation of water-insoluble "pseudo-lignin" from water-soluble bark phenolics during the acid-catalyzed pretreatment, which otherwise results in distorted lignin analysis and may also contribute to the impaired enzymatic digestibility of the barks. Thus, this study advocates the removal of extractives as the first step in the processing of bark or bark-rich materials in a sugar platform biorefinery.

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

    Science.gov (United States)

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

    2013-09-01

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

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

    OpenAIRE

    Amare, Meareg; Aklog, Senait

    2017-01-01

    Lignin film was deposited at the surface of glassy carbon electrode potentiostatically. In contrast to the unmodified glassy carbon electrode, an oxidative peak with an improved current and overpotential for caffeine at modified electrode showed catalytic activity of the modifier towards oxidation of caffeine. Linear dependence of peak current on caffeine concentration in the range 6 ? 10?6 to 100 ? 10?6?mol?L?1 with determination coefficient and method detection limit (LoD = 3?s/slope) of 0....

  18. Increased Levels of Oxidative Stress Markers, Soluble CD40 Ligand, and Carotid Intima-Media Thickness Reflect Acceleration of Atherosclerosis in Male Patients with Ankylosing Spondylitis in Active Phase and without the Classical Cardiovascular Risk Factors

    Directory of Open Access Journals (Sweden)

    Agata Stanek

    2017-01-01

    Full Text Available Objective. The primary aim of the study was to assess levels of oxidative stress markers, soluble CD40 ligand (sCD40L, serum pregnancy-associated plasma protein-A (PAPP-A, and placental growth factor (PlGF as well as carotid intima-media thickness (IMT in patients with ankylosing spondylitis (AS with active phase without concomitant classical cardiovascular risk factors. Material and methods. The observational study involved 96 male subjects: 48 AS patients and 48 healthy ones, who did not differ significantly regarding age, BMI, comorbid disorders, and distribution of classical cardiovascular risk factors. In both groups, we estimated levels of oxidative stress markers, lipid profile, and inflammation parameters as well as sCD40L, serum PAPP-A, and PlGF. In addition, we estimated carotid IMT in each subject. Results. The study showed that markers of oxidative stress, lipid profile, and inflammation, as well as sCD40L, PlGF, and IMT, were significantly higher in the AS group compared to the healthy group. Conclusion. Our results demonstrate that ankylosing spondylitis may be associated with increased risk for atherosclerosis.

  19. Sulphate solubility and sulphate diffusion in oxide glasses: implications for the containment of sulphate-bearing nuclear wastes; Solubilite et cinetiques de diffusion des sulfates dans differents verres d'oxydes: application au conditionnement des dechets nucleaires sulfates

    Energy Technology Data Exchange (ETDEWEB)

    Lenoir, M.

    2009-09-15

    The thesis deals with sulphate solubility and sulphate diffusion in oxide glasses, in order to control sulphate incorporation and sulphate volatilization in nuclear waste glasses. It was conducted on simplified compositions, in the SiO{sub 2}-B{sub 2}O{sub 3}-R{sub 2}O (R = Li, Na, K, Cs), SiO{sub 2}-B{sub 2}O{sub 3}-BaO and V{sub 2}O{sub 5}-B{sub 2}O{sub 3}-BaO systems. These compositions allowed us to study the influence of the nature of network-modifying ions (Li{sup +}, Na{sup +}, K{sup +}, Cs{sup +} or Ba{sup 2+}) and also of former elements (Si, B, V), on structure and properties of glasses. Sulphate volatility is studied in sodium borosilicate melts using an innovative technique of sulphate quantitation with Raman spectroscopy. This technique is useful to obtain kinetic curves of sulphate volatilization. The establishment of a model to fit these curves leads to the determination of diffusion coefficients of sulphate. These diffusion coefficients can thus be compared to diffusion coefficients of other species, determined by other techniques and presented in the literature. They are also linked to diffusion coefficients in relation with the viscosity of the melts. Concerning sulphate solubility in glasses, it depends on glass composition and on the nature of sulphate incorporated. Sulphate incorporation in alkali borosilicate glasses leads to the formation of a sulphate layer floating on top of the melt. Sulphate incorporation in barium borosilicate and boro-vanadate glasses leads to the crystallization of sulphate species inside the vitreous matrix. Moreover, sulphate solubility is higher in these glasses than in alkali borosilicates. Finally, exchanges between cations present in glasses and cations present in the sulphate phase are also studied. (author)

  20. Synthesis of freestanding water-soluble indium oxide nanocrystals capped by alanine nitric acid via ligand exchange for thin film transistors and effects of ligands on the electrical properties

    International Nuclear Information System (INIS)

    Choi, Jin-Kyu; Koh, Ye-Seul; Jeong, Hyun-Dam

    2015-01-01

    We demonstrate synthesis of freestanding water-soluble indium oxide nanocrystals (In 2 O 3 NCs) by ligand exchange to β-alanine nitric acid (Ala·HNO 3 ) and its application for active channel layer in thin film transistors (TFTs), with investigation of the effect of curing temperatures on the TFT properties in terms of thermal behaviour of the ligand molecules at 150, 300, and 350 °C. After ligand exchange from long alkyl ligand (myristic acid, MA) to short Ala·HNO 3 , the mobility of NC TFTs cured at 150 °C increased by over 1 order of magnitude, from 1.3 × 10 −4 cm 2 V -1 s −1 to 4.5 × 10 −3 cm 2 V -1 s −1 , due to enhanced tunnelling rate (Γ) between adjective NCs. Higher curing temperatures such as 300 and 350 °C, inducing thermal decomposition of the organic ligands, led to further enhancement of the mobility, particularly up to 2.2 cm 2 V -1 s −1 for the In 2 O 3 NC-Ala·HNO 3 TFT cured at 350 °C. It is also found that the ligand exchange of In 2 O 3 NC in acidic condition (e.g. HNO 3 ) would be simple and effective to reduce the surface defects by surface etching, which may lead to better device performances. - Graphical abstract: Display Omitted - Highlights: • Freestanding water-soluble In 2 O 3 nanocrystals (NCs) were synthesized by ligand exchange. • Thin film transistors (TFTs) of colloidal NCs were fabricated by spin-coating method. • Water-soluble In 2 O 3 NC TFTs showed higher mobilities due to shorter ligand length. • Surface defects of NCs were notably reduced by surface etching during ligand exchange

  1. Improved lignin polyurethane properties with Lewis acid treatment.

    Science.gov (United States)

    Chung, Hoyong; Washburn, Newell R

    2012-06-27

    Chemical modification strategies to improve the mechanical properties of lignin-based polyurethanes are presented. We hypothesized that treatment of lignin with Lewis acids would increase the concentration of hydroxyl groups available to react with diisocyanate monomers. Under the conditions used, hydrogen bromide-catalyzed modification resulted in a 28% increase in hydroxyl group content. Associated increases in hydrophilicity of solvent-cast thin films were also recorded as evidenced by decreases in water contact angle. Polyurethanes were then prepared by first preparing a prepolymer based on mixtures of toluene-2,4-diisocyanate (TDI) and unmodified or modified lignin, then polymerization was completed through addition of polyethylene glycol (PEG), resulting in mass ratios of TDI:lignin:PEG of 43:17:40 in the compositions investigated here. The mixture of TDI and unmodified lignin resulted in a lignin powder at the bottom of the liquid, suggesting it did not react directly with TDI. However, a homogeneous solution resulted when TDI and the hydrogen bromide-treated lignin were mixed, suggesting demethylation indeed increased reactivity and resulted in better integration of lignin into the urethane network. Significant improvements in mechanical properties of modified lignin polyurethanes were observed, with a 6.5-fold increase in modulus, which were attributed to better integration of the modified lignin into the covalent polymer network due to the higher concentration of hydroxyl groups. This research indicates that chemical modification strategies can lead to significant improvements in the properties of lignin-based polymeric materials using a higher fraction of an inexpensive lignin monomer from renewable resources and a lower fraction an expensive, petroleum-derived isocyanate monomer to achieve the required material properties.

  2. Biodegradation of alkaline lignin by Bacillus ligniniphilus L1

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Daochen; Zhang, Peipei; Xie, Changxiao; Zhang, Weimin; Sun, Jianzhong; Qian, Wei-Jun; Yang, Bin

    2017-02-21

    Background: Lignin is the most abundant aromatic biopolymer in the biosphere and it comprises up to 30% of plant biomass. Although lignin is the most recalcitrant component of the plant cell wall, still there are microorganisms able to decompose it or degrade it. Fungi are recognized as the most widely used microbes for lignin degradation. However, bacteria have also been known to be able to utilize lignin as a carbon or energy source. Bacillus ligniniphilus L1 was selected in this study due to its capability to utilize alkaline lignin as a single carbon or energy source and its excellent ability to survive in extreme environments. Results: To investigate the aromatic metabolites of strain L1 decomposing alkaline lignin, GC-MS analyze was performed and fifteen single phenol ring aromatic compounds were identified. The dominant absorption peak included phenylacetic acid, 4-hydroxy-benzoicacid, and vanillic acid with the highest proportion of metabolites resulting in 42%. Comparison proteomic analysis were carried out for further study showed that approximately 1447 kinds of proteins were produced, 141 of which were at least 2-fold up-regulated with alkaline lignin as the single carbon source. The up-regulated proteins contents different categories in the biological functions of protein including lignin degradation, ABC transport system, environmental response factors, protein synthesis and assembly, etc. Conclusions: GC-MS analysis showed that alkaline lignin degradation of strain L1 produced 15 kinds of aromatic compounds. Comparison proteomic data and metabolic analysis showed that to ensure the degradation of lignin and growth of strain L1, multiple aspects of cells metabolism including transporter, environmental response factors, and protein synthesis were enhanced. Based on genome and proteomic analysis, at least four kinds of lignin degradation pathway might be present in strain L1, including a Gentisate pathway, the benzoic acid pathway and the

  3. Radiation carbonization of cellulose, wood and lignin in the presence of air

    International Nuclear Information System (INIS)

    Rudnev, A.V.; Loginova, L.A.; Val'ter, A.I.

    1986-01-01

    The process of radiaton carbonization of wood and its separate components (cellulose and lignin) under the effect of γ-radiation is studied. In the process of cellulose and wood meal irradiation a decrease in hydrogen content with the growth of irradiation dose is observed. Simultaneously with hydrogen loss the dose of ∼ 100 kGy an increase in carbon content and a decrease in oxygen content are observed. In wood meal carbon content decreases, oxygen content increases. In lignin the observed changes in the element composition do not exceed experimental error. The results obtained are considered from the viewpoint of dehydration of radicals, formed in the process of irradiation, as well as their oxidation by the air oxygen

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

    Science.gov (United States)

    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

  5. Isolation and Characterization of Gramineae and Fabaceae Soda Lignins.

    Science.gov (United States)

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

    2017-02-04

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

  6. Dissolution of lignin in green urea aqueous solution

    Science.gov (United States)

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

    2017-12-01

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

  7. Valorization of lignin from biorefineries for fuels and chemicals

    DEFF Research Database (Denmark)

    Nielsen, Joachim Bachmann

    Direct lignin liquefaction is a promising process for lignin valorization in which ligninis treated in a solvent at elevated temperature and pressure. Liquefaction of sulfur freelignin obtained as a waste product from 2nd generation bio-ethanol production canprovide a sulfur free bio-oil which may...... substitute fossil fuel.In this Ph.D. study the direct liquefaction of a biorefinery lignin (hydrothermallypretreated enzymatic hydrolysis lignin) is explored. The goal is to provide a bio-crude which can substitute marine diesel as the engines found aboard large ships are adapted to more crude fuels. A novel...

  8. Kraft Lignin Depolymerization in an Ionic Liquid without a Catalyst

    Directory of Open Access Journals (Sweden)

    Amadou Diop

    2015-06-01

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

  9. Preparation and Characterization of Modified Soda Lignin with Polyethylene Glycol

    Directory of Open Access Journals (Sweden)

    Fangda Zhang

    2016-10-01

    Full Text Available Soda lignin does not have thermal flowing characteristics and it is impossible for it to be further thermally molded. To achieve the fusibility of soda lignin for fiber preparation by melt-spinning, an effective method for soda lignin modification was conducted by cooking it with polyethylene glycol (PEG 400 at various ratios. The higher the ratio of PEG that was used, the more PEG molecular chains were grafted at the alpha carbon of the soda lignin through ether bonds, resulting in lower thermal transition temperatures and more excellent fusibility. The modified soda lignin with a weight ratio of lignin to PEG of 1:4 exhibited a relative thermal stability of molten viscosity at selected temperatures. Thereafter, the resultant fusible soda lignin was successfully melt-spun into filaments with an average diameter of 33 ± 5 μm, which is smaller than that of some industrial lignins. Accordingly, it is possible to utilize soda lignin to produce fibrous carbonaceous materials.

  10. Isolation and Characterization of Gramineae and Fabaceae Soda Lignins

    Science.gov (United States)

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

    2017-01-01

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

  11. Isolation and Characterization of Gramineae and Fabaceae Soda Lignins

    Directory of Open Access Journals (Sweden)

    Juan Domínguez-Robles

    2017-02-01

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

  12. Progress in lignin hydrogels and nanocomposites for water purification

    DEFF Research Database (Denmark)

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

    2017-01-01

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

  13. Effective Release of Lignin Fragments from Lignocellulose by Lewis Acid Metal Triflates in the Lignin-First Approach.

    Science.gov (United States)

    Huang, Xiaoming; Zhu, Jiadong; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

    2016-12-08

    Adding value to lignin, the most complex and recalcitrant fraction in lignocellulosic biomass, is highly relevant to costefficient operation of biorefineries. We report the use of homogeneous metal triflates to rapidly release lignin from biomass. Combined with metal-catalyzed hydrogenolysis, the process separates woody biomass into few lignin-derived alkylmethoxyphenols and cellulose under mild conditions. Model compound studies show the unique catalytic properties of metal triflates in cleaving lignin-carbohydrate interlinkages. The lignin fragments can then be disassembled by hydrogenolysis. The tandem process is flexible and allows obtaining good aromatic monomer yields from different woods (36-48 wt %, lignin base). The cellulose-rich residue is an ideal feedstock for established biorefining processes. The highly productive strategy is characterized by short reaction times, low metal triflate catalyst requirement, and leaving cellulose largely untouched. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Utility of soluble lectin-like oxidized low-density lipoprotein receptor-1 (sLOX-1) in the postmortem diagnosis of ischemic heart disease.

    Science.gov (United States)

    Takasu, Shojiro; Matsumoto, Sari; Kanto, Yuko; Iwadate, Kimiharu

    2018-04-01

    Ischemic heart disease (IHD) is a major cause of death in developed countries. Postmortem IHD diagnosis using biochemical markers is difficult because of the postmortem changes. In the present study, we investigated the utility of soluble lectin-like low-density lipoprotein receptor-1 (sLOX-1) in body fluids obtained from forensic autopsy cases. We measured pericardial fluid, urine, and serum sLOX-1 levels; these samples were obtained from medicolegal autopsy cases (n = 149, postmortem interval fluid and urine of patients with acute IHD had higher sLOX-1 levels (p fluid and urine samples obtained postmortem are useful markers of acute IHD. Copyright © 2018 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

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

    NARCIS (Netherlands)

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

    2016-01-01

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

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

    NARCIS (Netherlands)

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

    2016-01-01

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

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

    Science.gov (United States)

    Eudes, Aymerick; George, Anthe; Mukerjee, Purba; Kim, Jin S; Pollet, Brigitte; Benke, Peter I; Yang, Fan; Mitra, Prajakta; Sun, Lan; Cetinkol, Ozgül P; Chabout, Salem; Mouille, Grégory; Soubigou-Taconnat, Ludivine; Balzergue, Sandrine; Singh, Seema; Holmes, Bradley M; Mukhopadhyay, Aindrila; Keasling, Jay D; Simmons, Blake A; Lapierre, Catherine; Ralph, John; Loqué, Dominique

    2012-06-01

    Lignocellulosic biomass is utilized as a renewable feedstock in various agro-industrial activities. Lignin is an aromatic, hydrophobic and mildly branched polymer integrally associated with polysaccharides within the biomass, which negatively affects their extraction and hydrolysis during industrial processing. Engineering the monomer composition of lignins offers an attractive option towards new lignins with reduced recalcitrance. The presented work describes a new strategy developed in Arabidopsis for the overproduction of rare lignin monomers to reduce lignin polymerization degree (DP). Biosynthesis of these 'DP reducers' is achieved by expressing a bacterial hydroxycinnamoyl-CoA hydratase-lyase (HCHL) in lignifying tissues of Arabidopsis inflorescence stems. HCHL cleaves the propanoid side-chain of hydroxycinnamoyl-CoA lignin precursors to produce the corresponding hydroxybenzaldehydes so that plant stems expressing HCHL accumulate in their cell wall higher amounts of hydroxybenzaldehyde and hydroxybenzoate derivatives. Engineered plants with intermediate HCHL activity levels show no reduction in total lignin, sugar content or biomass yield compared with wild-type plants. However, cell wall characterization of extract-free stems by thioacidolysis and by 2D-NMR revealed an increased amount of unusual C₆C₁ lignin monomers most likely linked with lignin as end-groups. Moreover the analysis of lignin isolated from these plants using size-exclusion chromatography revealed a reduced molecular weight. Furthermore, these engineered lines show saccharification improvement of pretreated stem cell walls. Therefore, we conclude that enhancing the biosynthesis and incorporation of C₆C₁ monomers ('DP reducers') into lignin polymers represents a promising strategy to reduce lignin DP and to decrease cell wall recalcitrance to enzymatic hydrolysis. © 2012 The Authors. Plant Biotechnology Journal © 2012 Society for Experimental Biology, Association of Applied

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

    OpenAIRE

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

    2012-01-01

    Lignocellulosic biomass is utilized as a renewable feedstock in various agro-industrial activities. Lignin is an aromatic, hydrophobic and mildly branched polymer integrally associated with polysaccharides within the biomass, which negatively affects their extraction and hydrolysis during industrial processing. Engineering the monomer composition of lignins offers an attractive option towards new lignins with reduced recalcitrance. The presented work describes a new strategy developed in Arab...

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

    OpenAIRE

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

    2015-01-01

    Pyrolysis is a promising approach that is being investigated to convert lignin into higher value products including biofuels and phenolic chemicals. In this study, fast pyrolysis of four types of lignin, including milled Amur linden wood lignin (MWL), enzymatic hydrolysis corn stover lignin (EHL), wheat straw alkali lignin (AL) and wheat straw sulfonate lignin (SL), were performed using pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS). Thermogravimetric analysis (TGA) showed that the...

  20. Solubility database for TILA-99

    Energy Technology Data Exchange (ETDEWEB)

    Vuorinen, U.; Carlsson, T. [VTT Chemical Technology, Espoo (Finland); Kulmala, S.; Hakanen, M. [Helsinki Univ. (Finland). Lab. of Radiochemistry; Ahonen, L. [Geological Survey of Finland, Espoo (Finland)

    1998-11-01

    The safety assessment of spent fuel disposal requires solubility values for several elements estimated in Finnish disposal conditions. In Finland four sites (Haestholmen, Kivetty, Olkiluoto and Romuvaara) are investigated for the disposal of spent fuel. Haestholmen and OLkiluoto are onshore sites, while Kivetty and Romuvaara are inland sites. Based on groundwater analysis and classification according to salinity at the planned disposal depth mainly fresh groundwater is encountered at Kivetty and Romuvaara, while brackish and saline water-types are met at Haestholmen and Olkiluoto. Very saline, almost brine-type water ({approx}70 g/l) has been found in the deepest parts of the investigated bedrock at one of the sites (Olkiluoto). The reference waters and conditions were chosen according to the water-types. The considered reference conditions incorporated both the near- and far-field, and both oxidizing and reducing conditions were considered. In the reference conditions, the changes in solubilities were also estimated as caused by possible variations in the pH, carbonate content and redox conditions. Uranium, which is the main component of spent fuel is dealt with in a separate report presenting the solubility of uranium and spent fuel dissolution. In this work the solubilities of all the other elements of concern (Am, Cu, Nb, Np, Pa, Pd, Pu, Ra, Se, Sn, Tc, Zr, Cm, Ni, Sr, Th, C, Cl, Cs, Fe, Ho, I, and Sm) in the safety assessment are considered. Some discussion on the corrosion of the spent fuel canister is also presented. For the estimation of solubilities of the elements in question, literature data was collected that mainly comprised experimentally measured concentrations. The sources used were spent fuel experiments, concentrations measured in solubility measurements, natural concentrations and concentrations from natural analogue sites (especially Palmottu and Hyrkkoelae in Finland) as well as the concentrations measured at the Finnish investigation sites

  1. Solubility database for TILA-99

    International Nuclear Information System (INIS)

    Vuorinen, U.; Carlsson, T.; Kulmala, S.; Hakanen, M.

    1998-11-01

    The safety assessment of spent fuel disposal requires solubility values for several elements estimated in Finnish disposal conditions. In Finland four sites (Haestholmen, Kivetty, Olkiluoto and Romuvaara) are investigated for the disposal of spent fuel. Haestholmen and OLkiluoto are onshore sites, while Kivetty and Romuvaara are inland sites. Based on groundwater analysis and classification according to salinity at the planned disposal depth mainly fresh groundwater is encountered at Kivetty and Romuvaara, while brackish and saline water-types are met at Haestholmen and Olkiluoto. Very saline, almost brine-type water (∼70 g/l) has been found in the deepest parts of the investigated bedrock at one of the sites (Olkiluoto). The reference waters and conditions were chosen according to the water-types. The considered reference conditions incorporated both the near- and far-field, and both oxidizing and reducing conditions were considered. In the reference conditions, the changes in solubilities were also estimated as caused by possible variations in the pH, carbonate content and redox conditions. Uranium, which is the main component of spent fuel is dealt with in a separate report presenting the solubility of uranium and spent fuel dissolution. In this work the solubilities of all the other elements of concern (Am, Cu, Nb, Np, Pa, Pd, Pu, Ra, Se, Sn, Tc, Zr, Cm, Ni, Sr, Th, C, Cl, Cs, Fe, Ho, I, and Sm) in the safety assessment are considered. Some discussion on the corrosion of the spent fuel canister is also presented. For the estimation of solubilities of the elements in question, literature data was collected that mainly comprised experimentally measured concentrations. The sources used were spent fuel experiments, concentrations measured in solubility measurements, natural concentrations and concentrations from natural analogue sites (especially Palmottu and Hyrkkoelae in Finland) as well as the concentrations measured at the Finnish investigation sites. The

  2. Characterization of Lignin Precipitated From The Soda Black Liquor of Oil Palm Empty Fruit Bunch Fibers by Various Mineral Acids

    Directory of Open Access Journals (Sweden)

    M.N Mohamad Ibrahim

    2017-10-01

    Full Text Available Soda lignin from oil palm empty fruit bunch was directly isolated by various mineral acids i.e. sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid at three levels of concentration (20% v/v, 60%v/v and concentrated. A comparison study was performed through physicochemical properties and structural features using FT-IR, UV, 13C-NMR and nitrobenzene oxidation. The FT-IR results showed that there is no significant difference between the main structures of the lignin isolated by various acids. However, low concentration of phosphoric acid is preferable because of its highest yield. The S: V: H ratio of 7-15:6-11:1 as evaluated by the nitrobenzene oxidation procedure suggests that soda lignin can be classified as belonging to either the cereal straw on grass type. The UV results indicate that phosphoric acid consistently gave the highest absorbance value among the four acids tested in this study regardless of its concentration level. The C13-FTNMR spectra, suggest that the lignin structure is independent of the type of acid used for precipitation.

  3. Neptunium (IV) oxalate solubility

    International Nuclear Information System (INIS)

    Luerkens, D.W.

    1983-07-01

    The equilibrium solubility of neptunium (IV) oxalate in nitric/oxalic acid solutions was determined at 22 0 C, 45 0 C, and 60 0 C. The concentrations of nitric/oxalic acid solutions represented a wide range of free oxalate ion concentration. A mathematical solubility model was developed which is based on the formation of the known complexes of neptunium (IV) oxalate. the solubility model uses a simplified concentration parameter which is proportional to the free oxalate ion concentration. The solubility model can be used to estimate the equilibrium solubility of neptunium (IV) oxalate over a wide range of oxalic and nitric acid concentrations at each temperature

  4. Liquefaction of kraft lignin by hydrocracking with simultaneous use of a novel dual acid-base catalyst and a hydrogenation catalyst.

    Science.gov (United States)

    Wang, Jindong; Li, Wenzhi; Wang, Huizhen; Ma, Qiaozhi; Li, Song; Chang, Hou-Min; Jameel, Hasan

    2017-11-01

    In this study, a novel catalyst, S 2 O 8 2- -KNO 3 /TiO 2 , which has active acidic and basic sites, was prepared and used in lignin hydrocracking with a co-catalyst, Ru/C. Ru/C is an efficient hydrogenation catalyst and S 2 O 8 2- -KNO 3 /TiO 2 is a dual catalyst, which could efficiently degrade lignin. This catalytic hydrogenation system can reduce solid products to less than 1%, while giving a high liquid product yield of 93%. Catalytic hydrocracking of kraft lignin at 320°C for 6h gave 93% liquid product with 0.5% solid product. Most of this liquid product was soluble in petroleum ether (60% of 93%), which is a clear liquid and comprises mainly of monomeric and dimeric degradation products. These results demonstrated that the combination of the two catalysts is an efficient catalyst for liquefaction of lignin, with little char formation (∼1%). This concept has the potential to produce valuable chemicals and fuels from lignin under moderate conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Sources and oxidative potential of water-soluble humic-like substances (HULISWS in fine particulate matter (PM2.5 in Beijing

    Directory of Open Access Journals (Sweden)

    Y. Ma

    2018-04-01

    Full Text Available Water-soluble humic-like substances (HULISWS are a major redox-active component of ambient fine particulate matter (PM2.5; however, information on their sources and associated redox activity is limited. In this study, HULISWS mass concentration, various HULISWS species, and dithiothreitol (DTT activity of HULISWS were quantified in PM2.5 samples collected during a 1-year period in Beijing. Strong correlation was observed between HULISWS and DTT activity; both exhibited higher levels during the heating season than during the nonheating season. Positive matrix factorization analysis of both HULISWS and DTT activity was performed. Four combustion-related sources, namely coal combustion, biomass burning, waste incineration, and vehicle exhausts, and one secondary factor were resolved. In particular, waste incineration was identified as a source of HULISWS for the first time. Biomass burning and secondary aerosol formation were the major contributors ( >  59 % to both HULISWS and associated DTT activity throughout the year. During the nonheating season, secondary aerosol formation was the most important source, whereas during the heating season, the predominant contributor was biomass burning. The four combustion-related sources accounted for  >  70 % of HULISWS and DTT activity, implying that future reduction in PM2.5 emissions from combustion activities can substantially reduce the HULISWS burden and their potential health impact in Beijing.

  6. Sources and oxidative potential of water-soluble humic-like substances (HULISWS) in fine particulate matter (PM2.5) in Beijing

    Science.gov (United States)

    Ma, Yiqiu; Cheng, Yubo; Qiu, Xinghua; Cao, Gang; Fang, Yanhua; Wang, Junxia; Zhu, Tong; Yu, Jianzhen; Hu, Di

    2018-04-01

    Water-soluble humic-like substances (HULISWS) are a major redox-active component of ambient fine particulate matter (PM2.5); however, information on their sources and associated redox activity is limited. In this study, HULISWS mass concentration, various HULISWS species, and dithiothreitol (DTT) activity of HULISWS were quantified in PM2.5 samples collected during a 1-year period in Beijing. Strong correlation was observed between HULISWS and DTT activity; both exhibited higher levels during the heating season than during the nonheating season. Positive matrix factorization analysis of both HULISWS and DTT activity was performed. Four combustion-related sources, namely coal combustion, biomass burning, waste incineration, and vehicle exhausts, and one secondary factor were resolved. In particular, waste incineration was identified as a source of HULISWS for the first time. Biomass burning and secondary aerosol formation were the major contributors ( > 59 %) to both HULISWS and associated DTT activity throughout the year. During the nonheating season, secondary aerosol formation was the most important source, whereas during the heating season, the predominant contributor was biomass burning. The four combustion-related sources accounted for > 70 % of HULISWS and DTT activity, implying that future reduction in PM2.5 emissions from combustion activities can substantially reduce the HULISWS burden and their potential health impact in Beijing.

  7. Near-field solubility studies

    International Nuclear Information System (INIS)

    Thomason, H.P.; Williams, S.J.

    1992-02-01

    Experimental determinations of the solubilities of americium, plutonium, neptunium, protactinium, thorium, radium, lead, tin, palladium and zirconium are reported. These elements have radioactive isotopes of concern in assessments of radioactive waste disposal. All measurements were made under the highly alkaline conditions typical of the near field of a radioactive waste repository which uses cementitious materials for many of the immobilisation matrices, the backfill and the engineered structures. Low redox potentials, typical of those resulting from the corrosion of iron and steel, were simulated for those elements having more than one accessible oxidation state. The dissolved concentrations of the elements were defined using ultrafiltration. In addition, the corrosion of iron and stainless steel was shown to generate low redox potentials in solution and the solubility of iron(II) at high pH was measured and found to be sufficient for it to act as a redox buffer with respect to neptunium and plutonium. (author)

  8. The Phenylpropanoid Pathway and Lignin in Defense against Ganoderma boninense Colonized Root Tissues in Oil Palm (Elaeis guineensis Jacq.

    Directory of Open Access Journals (Sweden)

    Nisha T. Govender

    2017-08-01

    Full Text Available Basal stem rot, caused by the basidiomycete fungus, Ganoderma boninense, is an economically devastating disease in Malaysia. Our study investigated the changes in lignin content and composition along with activity and expression of the phenylpropanoid pathway enzymes and genes in oil palm root tissues during G. boninense infection. We sampled control (non-inoculated and infected (inoculated seedlings at seven time points [1, 2, 3, 4, 8, and 12 weeks post-inoculation (wpi] in a randomized design. The expression profiles of phenylalanine ammonia lyase (PAL, cinnamyl alcohol dehydrogenase (CAD, and peroxidase (POD genes were monitored at 1, 2, and 3 wpi using real-time quantitative polymerase chain reaction. Seedlings at 4, 8, and 12 wpi were screened for lignin content, lignin composition, enzyme activities (PAL, CAD, and POD, growth (weight and height, and disease severity (DS. Gene expression analysis demonstrated up-regulation of PAL, CAD, and POD genes in the infected seedlings, relative to the control seedlings at 1, 2, and 3 wpi. At 2 and 3 wpi, CAD showed highest transcript levels compared to PAL and POD. DS increased progressively throughout sampling, with 5, 34, and 69% at 4, 8, and 12 wpi, respectively. Fresh weight and height of the infected seedlings were significantly lower compared to the control seedlings at 8 and 12 wpi. Lignin content of the infected seedlings at 4 wpi was significantly higher than the control seedlings, remained elicited with no change at 8 wpi, and then collapsed with a significant reduction at 12 wpi. The nitrobenzene oxidation products of oil palm root lignin yielded both syringyl and guaiacyl monomers. Accumulation of lignin in the infected seedlings was in parallel to increased syringyl monomers, at 4 and 8 wpi. The activities of PAL and CAD enzymes in the infected seedlings at DS = 5–34% were significantly higher than the control seedlings and thereafter collapsed at DS = 69%.

  9. The Phenylpropanoid Pathway and Lignin in Defense against Ganoderma boninense Colonized Root Tissues in Oil Palm (Elaeis guineensis Jacq.).

    Science.gov (United States)

    Govender, Nisha T; Mahmood, Maziah; Seman, Idris A; Wong, Mui-Yun

    2017-01-01

    Basal stem rot, caused by the basidiomycete fungus, Ganoderma boninense , is an economically devastating disease in Malaysia. Our study investigated the changes in lignin content and composition along with activity and expression of the phenylpropanoid pathway enzymes and genes in oil palm root tissues during G. boninense infection. We sampled control (non-inoculated) and infected (inoculated) seedlings at seven time points [1, 2, 3, 4, 8, and 12 weeks post-inoculation (wpi)] in a randomized design. The expression profiles of phenylalanine ammonia lyase (PAL), cinnamyl alcohol dehydrogenase (CAD), and peroxidase (POD) genes were monitored at 1, 2, and 3 wpi using real-time quantitative polymerase chain reaction. Seedlings at 4, 8, and 12 wpi were screened for lignin content, lignin composition, enzyme activities (PAL, CAD, and POD), growth (weight and height), and disease severity (DS). Gene expression analysis demonstrated up-regulation of PAL, CAD, and POD genes in the infected seedlings, relative to the control seedlings at 1, 2, and 3 wpi. At 2 and 3 wpi, CAD showed highest transcript levels compared to PAL and POD. DS increased progressively throughout sampling, with 5, 34, and 69% at 4, 8, and 12 wpi, respectively. Fresh weight and height of the infected seedlings were significantly lower compared to the control seedlings at 8 and 12 wpi. Lignin content of the infected seedlings at 4 wpi was significantly higher than the control seedlings, remained elicited with no change at 8 wpi, and then collapsed with a significant reduction at 12 wpi. The nitrobenzene oxidation products of oil palm root lignin yielded both syringyl and guaiacyl monomers. Accumulation of lignin in the infected seedlings was in parallel to increased syringyl monomers, at 4 and 8 wpi. The activities of PAL and CAD enzymes in the infected seedlings at DS = 5-34% were significantly higher than the control seedlings and thereafter collapsed at DS = 69%.

  10. Oxidative stress and damage in liver, but not in brain, of Fischer 344 rats subjected to dietary iron supplementation with lipid-soluble[(3,5,5-Trimethylhexanoyl)ferrocene

    DEFF Research Database (Denmark)

    Lykkesfeldt, Jens; Morgan, Evan; Christen, Stephan

    2007-01-01

    Accumulation of iron probably predisposes the aging brain to progressive neuronal loss. We examined various markers of oxidative stress and damage in the brain and liver of 3- and 24-month old rats following supplementationwith the lipophilic iron derivative [(3,5,5-trimethylhexanoyl)ferrocene] (......, they also demonstrated that the brain is well protected against dietary iron overload by using iron in a lipid-soluble formulation.......Accumulation of iron probably predisposes the aging brain to progressive neuronal loss. We examined various markers of oxidative stress and damage in the brain and liver of 3- and 24-month old rats following supplementationwith the lipophilic iron derivative [(3,5,5-trimethylhexanoyl......)ferrocene] (TMHF), which is capable of crossing the blood-brain barrier. At both ages, iron concentration increased markedly in the liver but failed to increase in the brain. In the liver of TMHF-treated young rats, levels of a- and ¿-tocopherols and glutathione (GSH) were also higher. In contrast, the brain...

  11. The investigation of wood hydrolysis lignin ability for uranium sorption

    International Nuclear Information System (INIS)

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

    2001-01-01

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

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

    African Journals Online (AJOL)

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

  13. Effect of periodate on lignin for wood adhesive application

    NARCIS (Netherlands)

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

    2011-01-01

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

  14. Metal Triflates for the Production of Aromatics from Lignin

    NARCIS (Netherlands)

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

    2016-01-01

    The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields under mild reaction conditions. The methodology

  15. Characterisation and application of NovaFiber lignin

    NARCIS (Netherlands)

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

    2004-01-01

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

  16. Participation of hippocampal nitric oxide synthase and soluble guanylate cyclase in the modulation of behavioral responses elicited by the rat forced swimming test.

    Science.gov (United States)

    Sales, Amanda J; Hiroaki-Sato, Vinícius A; Joca, Sâmia R L

    2017-02-01

    Systemic or hippocampal administration of nitric oxide (NO) synthase inhibitors induces antidepressant-like effects in animals, implicating increased hippocampal levels of NO in the neurobiology of depression. However, the role played by different NO synthase in this process has not been clearly defined. As stress is able to induce neuroinflammatory mechanisms and trigger the expression of inducible nitric oxide synthase (iNOS) in the brain, as well as upregulate neuronal nitric oxide synthase (nNOS) activity, the aim of the present study was to investigate the possible differential contribution of hippocampal iNOS and nNOS in the modulation of the consequences of stress elicited by the forced swimming test. Male Wistar rats received intrahippocampal injections, immediately after the pretest or 1 h before the forced swimming test, of selective inhibitors of nNOS (N-propyl-L-arginine), iNOS (1400W), or sGC (ODQ), the main pharmacological target for NO. Stress exposure increased nNOS and phospho-nNOS levels at all time points, whereas iNOS expression was increased only 24 h after the pretest. All drugs induced an antidepressant-like effect. However, whereas the nNOS inhibitor was equally effective when injected at different times, the iNOS inhibitor was more effective 24 h after the pretest. These results suggest that hippocampal nNOS and iNOS contribute to increase in NO levels in response to stress, although with a differential time course after stress exposure.

  17. H2O2 can Increase Lignin Disintegration and Decrease Cellulose Decomposition in the Process of Solid-State Fermentation (SSF) by Aspergillus oryzae Using Corn Stalk as Raw Materials

    OpenAIRE

    Zhicai Zhang; Jun Jia; Ming Li; Qiaoxia Pang

    2014-01-01

    H2O2 is both bactericidal and the main oxidant responsible for lignin degradation reaction catalyzed by manganese peroxidase (MnP) and lignin peroxidase (LiP). Thus, H2O2 treatment of corn stalk and the implementation of solid-substrate fermentation (SSF) is possible to increase the removal rate of lignin from stalk in the process of SSF and after SSF, while avoiding the need to sterilize the raw materials. To demonstrate this approach, SSF was initially carried out using corn stalk pretreate...

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

    Directory of Open Access Journals (Sweden)

    Jianxin Jiang

    2011-02-01

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

  19. Process for conversion of lignin to reformulated hydrocarbon gasoline

    Science.gov (United States)

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

    1999-09-28

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

  20. Influence of Reaction Conditions on Lignin Hydrothermal Treatment

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-04-01

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

  1. A novel soluble immune-type receptor (SITR in teleost fish: carp SITR is involved in the nitric oxide-mediated response to a protozoan parasite.

    Directory of Open Access Journals (Sweden)

    Carla M S Ribeiro

    2011-01-01

    Full Text Available The innate immune system relies upon a wide range of germ-line encoded receptors including a large number of immunoglobulin superfamily (IgSF receptors. Different Ig-like immune receptor families have been reported in mammals, birds, amphibians and fish. Most innate immune receptors of the IgSF are type I transmembrane proteins containing one or more extracellular Ig-like domains and their regulation of effector functions is mediated intracellularly by distinct stimulatory or inhibitory pathways.Carp SITR was found in a substracted cDNA repertoire from carp macrophages, enriched for genes up-regulated in response to the protozoan parasite Trypanoplasma borreli. Carp SITR is a type I protein with two extracellular Ig domains in a unique organisation of a N-proximal V/C2 (or I- type and a C-proximal V-type Ig domain, devoid of a transmembrane domain or any intracytoplasmic signalling motif. The carp SITR C-proximal V-type Ig domain, in particular, has a close sequence similarity and conserved structural characteristics to the mammalian CD300 molecules. By generating an anti-SITR antibody we could show that SITR protein expression was restricted to cells of the myeloid lineage. Carp SITR is abundantly expressed in macrophages and is secreted upon in vitro stimulation with the protozoan parasite T. borreli. Secretion of SITR protein during in vivo T. borreli infection suggests a role for this IgSF receptor in the host response to this protozoan parasite. Overexpression of carp SITR in mouse macrophages and knock-down of SITR protein expression in carp macrophages, using morpholino antisense technology, provided evidence for the involvement of carp SITR in the parasite-induced NO production.We report the structural and functional characterization of a novel soluble immune-type receptor (SITR in a teleost fish and propose a role for carp SITR in the NO-mediated response to a protozoan parasite.

  2. Oxidative potential of ambient water-soluble PM2.5 in the southeastern United States: contrasts in sources and health associations between ascorbic acid (AA and dithiothreitol (DTT assays

    Directory of Open Access Journals (Sweden)

    T. Fang

    2016-03-01

    Full Text Available The ability of certain components of particulate matter to induce oxidative stress through the generation of reactive oxygen species (ROS in vivo may be one mechanism accounting for observed linkages between ambient aerosols and adverse health outcomes. A variety of assays have been used to measure this so-called aerosol oxidative potential. We developed a semi-automated system to quantify oxidative potential of filter aqueous extracts utilizing the dithiothreitol (DTT assay and report here the development of a similar semi-automated system for the ascorbic acid (AA assay. Approximately 500 PM2.5 filter samples collected in contrasting locations in the southeastern US were analyzed for a host of aerosol species, along with AA and DTT activities. We present a detailed contrast in findings from these two assays. Water-soluble AA activity was higher in summer and fall than in winter, with highest levels near heavily trafficked highways, whereas DTT activity was higher in winter compared to summer and fall and more spatially homogeneous. AA activity was nearly exclusively correlated with water-soluble Cu (r  =  0.70–0.94 at most sites, whereas DTT activity was correlated with organic and metal species. Source apportionment models, positive matrix factorization (PMF and a chemical mass balance method with ensemble-averaged source impact profiles (CMB-E, suggest a strong contribution from traffic emissions and secondary processes (e.g., organic aerosol oxidation or metals mobilization by secondary acids to both AA and DTT activities in urban Atlanta. In contrast, biomass burning was a large source for DTT activity, but insignificant for AA. AA activity was not correlated with PM2.5 mass, while DTT activity co-varied strongly with mass (r  =  0.49–0.86 across sites and seasons. Various linear models were developed to estimate AA and DTT activities for the central Atlanta Jefferson Street site, based on the CMB-E sources. The

  3. High-throughput continuous hydrothermal flow synthesis of Zn-Ce oxides: unprecedented solubility of Zn in the nanoparticle fluorite lattice.

    Science.gov (United States)

    Kellici, Suela; Gong, Kenan; Lin, Tian; Brown, Sonal; Clark, Robin J H; Vickers, Martin; Cockcroft, Jeremy K; Middelkoop, Vesna; Barnes, Paul; Perkins, James M; Tighe, Christopher J; Darr, Jawwad A

    2010-09-28

    High-throughput continuous hydrothermal flow synthesis has been used as a rapid and efficient synthetic route to produce a range of crystalline nanopowders in the Ce-Zn oxide binary system. High-resolution powder X-ray diffraction data were obtained for both as-prepared and heat-treated (850 degrees C for 10 h in air) samples using the new robotic beamline I11, located at Diamond Light Source. The influence of the sample composition on the crystal structure and on the optical and physical properties was studied. All the nanomaterials were characterized using Raman spectroscopy, UV-visible spectrophotometry, Brunauer-Emmett-Teller surface area and elemental analysis (via energy-dispersive X-ray spectroscopy). Initially, for 'as-prepared' Ce(1-x)Zn(x)O(y), a phase-pure cerium oxide (fluorite) structure was obtained for nominal values of x=0.1 and 0.2. Biphasic mixtures were obtained for nominal values of x in the range of 0.3-0.9 (inclusive). High-resolution transmission electron microscopy images revealed that the phase-pure nano-CeO(2) (x=0) consisted of ca 3.7 nm well-defined nanoparticles. The nanomaterials produced herein generally had high surface areas (greater than 150 m(2) g(-1)) and possessed combinations of particle properties (e.g. bandgap, crystallinity, size, etc.) that were unobtainable or difficult to achieve by other more conventional synthetic methods.

  4. Wood chemistry symposium: from muka to lignin

    Energy Technology Data Exchange (ETDEWEB)

    MacLeod, M.

    1979-01-01

    The Canadian Wood Chemistry Symposium held during September, 1979, is reviewed. The chemical and physical explanations of delignification were debated. Problems of mechanical pulping include insufficient brightness, yellowing, and low strength relative to energy consumption. A session on chemicals, energy, and food from wood began with criteria for a viable project, which included adequate return on investment, modest capital investment requirements, identified pre-existing markets, and favorable thermodynamic balances. The pulp and paper industry should improve its methods of using bark and wood waste in direct combustion (by pre-drying wastes and improving furnace efficiency) rather than supporting oil-from-wood projects, since using a waste for fuel will free fossil fuels for uses in synthetic fibers and thermoplastics. In the area of food, there are modest successes with cellulose fiber additives to bread and snack food and single cell protein (which, though made from wastes, cannot compete with soy protein). However, making monomeric sugars from wood polysaccharides is not an efficient process, and muka, animal feed supplement from foliage, is successful only in Russia. In Canada it cannot compete with agricultural products. Alpha cellulose is a major wood chemical product. Promising uses include cellulose derived thermoplastics and lignosulphonates for secondary oil recovery. Instead of breaking wood polysaccharides and lignin into monomers and then repolymerizing them, it is possible to use the pre-built polymers; such an approach is illustrated by use of lignin in polyurethane foams, adhesives, and coatings.

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

    DEFF Research Database (Denmark)

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

    2017-01-01

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

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

    NARCIS (Netherlands)

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

    2016-01-01

    Adding value to lignin, the most complex and recalcitrant fraction in lignocellulosic biomass, is highly relevant to costefficient operation of biorefineries. We report the use of homogeneous metal triflates to rapidly release lignin from biomass. Combined with metal-catalyzed hydrogenolysis, the

  7. Uranium solubility and speciation in ground water

    International Nuclear Information System (INIS)

    Ollila, K.

    1985-04-01

    The purpose of this study has been to assess the solubility and possible species of uranium in groundwater at the disposal conditions of spent fuel. The effects of radiolysis and bentonite are considered. The assessment is based on the theoretical calculations found in the literature. The Finnish experimental results are included. The conservative estimate for uranium solubility under the oxidizing conditions caused by alpha radiolysis is based on the oxidation of uranium to the U(VI) state and formation of carbonate complex. For the groundwater with the typical carbonate content of 275 mg/l and the high carbonate content of 485 mg/l due to bentonite, the solubility values of 360 mg u/l and 950 mg U/l, are obtained, respectively. The experimental results predict considerably lower values, 0.5-20 mg U/l. The solubility of uranium under the undisturbed reducing conditions may be calculated based on the hydrolysis, carbonate complexation and redox reactions. The results vary considerably depending on the thermodynamic data used. The wide ranges of the most important groundwater parameters are seen in the solubility values. The experimental results show the same trends. As a conservative value for the solubility in reducing groundwater 50-500 μg U/l is estimated. (author)

  8. Synthesis of freestanding water-soluble indium oxide nanocrystals capped by alanine nitric acid via ligand exchange for thin film transistors and effects of ligands on the electrical properties

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jin-Kyu; Koh, Ye-Seul; Jeong, Hyun-Dam, E-mail: hdjeong@chonnam.ac.kr

    2015-07-15

    We demonstrate synthesis of freestanding water-soluble indium oxide nanocrystals (In{sub 2}O{sub 3} NCs) by ligand exchange to β-alanine nitric acid (Ala·HNO{sub 3}) and its application for active channel layer in thin film transistors (TFTs), with investigation of the effect of curing temperatures on the TFT properties in terms of thermal behaviour of the ligand molecules at 150, 300, and 350 °C. After ligand exchange from long alkyl ligand (myristic acid, MA) to short Ala·HNO{sub 3}, the mobility of NC TFTs cured at 150 °C increased by over 1 order of magnitude, from 1.3 × 10{sup −4} cm{sup 2}V{sup -1}s{sup −1} to 4.5 × 10{sup −3} cm{sup 2}V{sup -1}s{sup −1}, due to enhanced tunnelling rate (Γ) between adjective NCs. Higher curing temperatures such as 300 and 350 °C, inducing thermal decomposition of the organic ligands, led to further enhancement of the mobility, particularly up to 2.2 cm{sup 2}V{sup -1}s{sup −1} for the In{sub 2}O{sub 3} NC-Ala·HNO{sub 3} TFT cured at 350 °C. It is also found that the ligand exchange of In{sub 2}O{sub 3} NC in acidic condition (e.g. HNO{sub 3}) would be simple and effective to reduce the surface defects by surface etching, which may lead to better device performances. - Graphical abstract: Display Omitted - Highlights: • Freestanding water-soluble In{sub 2}O{sub 3} nanocrystals (NCs) were synthesized by ligand exchange. • Thin film transistors (TFTs) of colloidal NCs were fabricated by spin-coating method. • Water-soluble In{sub 2}O{sub 3} NC TFTs showed higher mobilities due to shorter ligand length. • Surface defects of NCs were notably reduced by surface etching during ligand exchange.

  9. Fatty acid composition, fat soluble vitamin concentrations and oxidative stability in bovine milk produced on two pastures with different botanical composition

    DEFF Research Database (Denmark)

    Adler, S A; Dahl, A V; Jensen, Søren Krogh

    2013-01-01

    to oxidation. Two groups of 8 multiparous Norwegian Red dairy cows [mean (standard deviation); 599 (45.1) kg body weight, 73 (15.0) d in milk, 29.9 (2.90) kg milk/d at experiment start] grazed either a short-term pasture (SP) or a long-term pasture (LP). Both pastures were organically managed, meaning......Previous research has shown that grazing pastures compared to feeding preserved forages has large impact on milk fatty acid (FA) composition, but differences between grazing red clover (Trifolium pratense L.) or white clover (Trifolium repens L.) are small, whereas the herbage proportions...... of dicotyledon botanical families is positively correlated with the milk-fat proportions of total polyunsaturated FA when grazing pastures in the Alps. The objective of the present study was to investigate the influence of botanically different pastures on bovine milk composition and milk susceptibility...

  10. Effects of calcium oxide treatment of dry and modified wet corn distillers grains plus solubles on growth performance, carcass characteristics, and apparent digestibility of feedlot steers.

    Science.gov (United States)

    Schroeder, A R; Duckworth, M J; Shike, D W; Schoonmaker, J P; Felix, T L

    2014-10-01

    The objectives of this study were to determine the effects of feeding dried corn distillers grains (DDGS) or modified wet corn distillers grains (MDGS) with or without CaO treatment to feedlot steers on 1) growth performance and carcass characteristics and 2) diet digestibility, pattern of intake, and meal distribution. In Exp. 1, steers (n = 139; average initial BW = 336 ± 75 kg) were used in a randomized complete block design. Treatments were arranged in a 2 × 2 factorial design, and pens were randomly allotted to 1 of the 4 dietary treatments (DM basis): 1) 50% DDGS untreated, 2) 48.8% DDGS treated with 1.2% CaO, 3) 50% MDGS untreated, or 4) 48.8% MDGS treated with 1.2% CaO. The remainder of the diet was corn husklage, dry rolled corn, and vitamin and mineral supplement. In Exp. 2, fistulated steers (n = 8; average initial BW = 540 ± 250 kg) were used in a replicated 4 × 4 Latin square design with the same dietary treatments as in Exp. 1. There was no interaction (P ≥ 0.14) between distillers grains plus solubles (DGS) and CaO inclusion for DMI, ADG, final BW, or USDA yield and quality grades. However, steers fed CaO-treated DGS had decreased (P < 0.01) DMI, regardless of DGS type. Because CaO treatment decreased DMI without affecting (P = 0.66) ADG, steers fed CaO-treated DGS had increased (P < 0.01) G:F compared to steers not fed CaO. The variation in DMI found in this experiment could be explained by differences in meal size and distribution. Steers fed CaO-treated DGS ate a similar (P = 0.36) number of meals but ate smaller (P < 0.01) meals. No effects (P ≥ 0.55) of CaO treatment or its interaction with DGS type were found for apparent total tract DM or NDF digestibility. However, steers fed MDGS had increased (P < 0.01) NDF digestibility compared to steers fed DDGS. In conclusion, CaO treatment of DGS improved feed efficiency when DGS-based diets were fed but did not improve digestibility.

  11. Biochemical Properties of Soluble and Bound Peroxidases from Artichoke Heads and Leaves

    Directory of Open Access Journals (Sweden)

    Angela Cardinali

    2009-01-01

    Full Text Available Soluble (SP, ionically bound (IBP and covalently bound (CBP peroxidases (POD from artichoke leaves and heads have been characterized for the main biochemical parameters. The three PODs, in both leaves and heads, showed the major apparent catalytic efficiency (vmax,app/Km,app towards ferulic acid, even though, in some cases, they showed higher affinity (Km,app for other substrates. In leaves, SP and IBP showed higher Km,app for ferulic and chlorogenic acids, and CBP for ferulic and caffeic acids. In heads, SP showed higher Km,app for chlorogenic acid, IBP for caffeic and ferulic acids, and CBP for ferulic acid. It was shown that pH optimum for PODs ranged between 5.0 and 6.0 in leaves. In heads, pH optimum for SP and IBP was 5.5, while CBP presented a very low activity in a wide pH range. All PODs showed high thermal stability but different ability to regenerate: the bound forms were more able to regenerate than the soluble one. The results obtained show that (i CBP from heads is able to work under very different cellular conditions, (ii all PODs, in both tissues, have a high apparent catalytic efficiency for ferulic acid, which could explain the effective involvement of POD in lignin biosynthesis, (iii in heads, high Km,app of SP for chlorogenic acid, particularly abundant in artichoke, could justify the possible involvement of PODs in browning mechanism, and (iv in heat-processed artichoke, the ability of PODs to regenerate could contribute to oxidation and loss of product quality.

  12. Catabolic fate of Streptomyces viridosporus T7A-Produced, acid precipitable polymeric lignin upon incubation with ligninolytic Streptomyces species and Phanerochaete chrysosporium

    International Nuclear Information System (INIS)

    Pometto, A.L. III; Crawford, D.L.

    1986-01-01

    Degradation of ground and hot-water-extracted corn stover (Zea mays) lignocellulose by Streptomyces viridosporus T7A generates a water-soluble lignin degradation intermediate termed acid-precipitable polymeric lignin (APPL). The further catabolism of T7A-APPL by S. viridosporus T7A, S. badius 252, and S. setonii75Vi2 was followed for 3 weeks. APPL catabolism by Phanerochaete chrysosporium was followed in stationary cultures in a low-nitrogen medium containing 1% (wt/vol) glucose and 0.05% (wt/vol) T7A-APPL. Metabolism of the APPL was followed by turbidometric assay (600 nm) and by direct measurement of APPL recoverable from the medium. Accumulation and disappearance of soluble low-molecular-weight products of APPL catabolism were followed by gas-liquid chromatography and by high-pressure liquid chromatography, utilizing a diode array detector. Mineralization of a [ 14 C-lignin]APPL was also followed. The percent 14 C recovered as 14 CO 2 , 14 C-APPL, 14 C-labeled water-soluble products, and cell mass-associated radioactivity, were determined for each microorganism after 1 and 3 weeks of incubation in bubbler tube cultures at 37 0 C. P. chrysosporium evolved the most 14 CO 2 , and S. viridosporus gave the greatest decrease in recoverable 14 C-APPL. The results show that S. badius was not able to significantly degrade the APPL, while the other microorganisms demonstrated various APPL-degrading abilities

  13. Effects of feeding dry or modified wet distillers grains with solubles with or without supplemental calcium oxide on ruminal metabolism and microbial enzymatic activity of beef cattle.

    Science.gov (United States)

    Schroeder, A R; Iakiviak, M; Felix, T L

    2014-09-01

    The objectives of this study were to determine the interaction of feeding dry (DDGS) or modified wet (MDGS) distillers grains with solubles (DGS) with or without supplemental CaO on in situ DM and NDF disappearance; ruminal pH, VFA, and methane concentration; and cellulase and xylanase activity. Fistulated steers (n = 8; average initial BW = 540 ± 250 kg) were used in a replicated 4 × 4 Latin square design. Treatments were arranged in a 2 × 2 factorial, and steers were randomly allotted to 1 of 4 dietary treatments: 1) 50% DDGS with 0% CaO, 2) 48.8% DDGS supplemented with 1.2% CaO, 3) 50% MDGS with 0% CaO, or 4) 48.8% MDGS supplemented with 1.2% CaO (DM basis). The remainder of the diet was husklage, dry-rolled corn, and vitamin and mineral supplement. There were no interactions (P ≥ 0.12) of DGS type and CaO addition on any parameters measured. Steers fed DDGS had a 17% increase (P < 0.01) in DMI compared to steers fed MDGS; however, CaO supplementation reduced (P = 0.03) DMI by 12%, regardless of DGS type. As expected, addition of CaO increased the pH of the diet by 1.82 pH units. This caused a time by CaO interaction (P = 0.05) for ruminal pH. Regardless of DGS type, steers supplemented with CaO tended to have increased (P = 0.09) ruminal pH at 1.5 h and had increased (P = 0.03) ruminal pH at 3 h postfeeding; however, ruminal pH did not differ (P ≥ 0.24) for the remainder of the day. There was no difference (P = 0.46) in ruminal cellulase activity when comparing type of DGS fed. However, there was a time by CaO interaction (P < 0.01); cattle fed 1.2% CaO diets had 28% greater ruminal cellulase activity only at 0 h postfeeding when compared to cattle fed 0% CaO. Furthermore, feeding supplemental CaO increased (P = 0.04) acetate to propionate ratio (A:P) regardless of type of DGS fed. Increased initial ruminal pH and cellulase activity from supplemental CaO did not increase (P = 0.48) in situ NDF disappearance. No differences (P ≥ 0.48) in ruminal methane

  14. Effect of calcium oxide inclusion in beef feedlot diets containing 60% dried distillers grains with solubles on ruminal fermentation, diet digestibility, performance, and carcass characteristics.

    Science.gov (United States)

    Nuñez, A J C; Felix, T L; Lemenager, R P; Schoonmaker, J P

    2014-09-01

    Two experiments were conducted to determine the effect of increasing dietary CaO on ruminal fermentation, diet digestibility, performance, and carcass characteristics of feedlot steers fed 60% dried distillers grains with solubles ( DDGS: ). In Exp. 1, 120 steers were allotted by weight (355 ± 7.9 kg) to 1 of 4 treatments containing 60% DDGS, 20% corn silage, 13.5 to 14.4% ground corn, 4% supplement, and 0 to 2.5% limestone on DM basis to determine the effects of CaO on performance and carcass characteristics. Treatments consisted of 0, 0.8, 1.6, or 2.4% CaO inclusion in the diet (DM basis), with CaO replacing limestone. Steers were slaughtered at a target BW of approximately 641 kg. In Exp. 2, 4 steers (initial BW = 288 ± 3 kg) were randomly allotted to the same diets in a 4 × 4 Latin square design (14-d periods) to determine the effects of CaO on ruminal pH, VFA, and nutrient digestibility. Statistical analyses were conducted using the MIXED procedure of SAS. Inclusion of CaO at 0.8, 1.6, and 2.4% increased ADG by 5.0, 3.9, and 0%, respectively, compared to 0% CaO (quadratic; P = 0.03). Intake was linearly decreased (P = 0.04) and G:F was linearly increased (P = 0.02) by CaO inclusion. Dressing percentage increased as CaO increased from 0 to 1.6% and then decreased for 2.4% CaO (quadratic; P < 0.01). In Exp. 2, steers fed 0% CaO had the greatest prefeeding ruminal pH, steers fed 0 and 0.8% CaO exhibited the most rapid postfeeding decline in ruminal pH, and steers fed 2.4% CaO exhibited a relatively stable ruminal pH throughout the 24-h period (treatment × time; P ≤ 0.01). Acetate, butyrate, and total VFA concentrations increased linearly (P ≤ 0.05) at 0, 3, 6, and 12 h postfeeding with increasing CaO. Propionate at 3 h postfeeding increased from 0 to 1.6% CaO and decreased from 1.6 to 2.4% CaO (quadratic; P = 0.10). Urine pH increased linearly (P ≤ 0.01) while urine output and urine ammonia decreased linearly (P ≤ 0.05) as CaO inclusion increased

  15. Adsorption of cellulase on cellulolytic enzyme lignin from lodgepole pine.

    Science.gov (United States)

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

    2009-09-09

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Simo Sarkanen

    2002-02-04

    This project constituted an intensive effort devoted to producing, from the white-rot fungus Tramets Cingulata, a lignin degrading enzyme (lignin depolymerase) that is directly able to biobleach or delignify softwood kraft pulp brownstock. To this end, the solutions in which T. cingulata was grown contained dissolved kraft lignin which fulfilled two functions; it behaved as a lignin deploymerase substrate and it also appeared to act as an inducer of enzyme expression. However, the lignin depolymerase isoenzymes (and other extracellular T. cingulata enzymes) interacted very strongly with both the kraft lignin components and the fungal hypae, so the isolating these proteins from the culture solutions proved to be unexpectedly difficult. Even after extensive experimentation with a variety of protein purification techniques, only one approach appeared to be capable of purifying lignin depolymerases to homogeneity. Unfortunately the procedure was extremely laborious; it involved the iso electric focusing of concentrated buffer-exchanged culture solutions followed by electro-elution of the desired protein bands from the appropriate polyacrylamide gel segments

  17. Characterization of the lignin polymer in Brassicaceae family

    Directory of Open Access Journals (Sweden)

    S. Hemmati

    2017-04-01

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

  18. Multienzyme Immobilized Polymeric Membrane Reactor for the Transformation of a Lignin Model Compound

    Directory of Open Access Journals (Sweden)

    Rupam Sarma

    2018-04-01

    Full Text Available We have developed an integrated, multienzyme functionalized membrane reactor for bioconversion of a lignin model compound involving enzymatic catalysis. The membrane bioreactors were fabricated through the layer-by-layer assembly approach to immobilize three different enzymes (glucose oxidase, peroxidase and laccase into pH-responsive membranes. This novel membrane reactor couples the in situ generation of hydrogen peroxide (by glucose oxidase to oxidative conversion of a lignin model compound, guaiacylglycerol-β-guaiacyl ether (GGE. Preliminary investigation of the efficacy of these functional membranes towards GGE degradation is demonstrated under convective flow mode. Over 90% of the initial feed could be degraded with the multienzyme immobilized membranes at a residence time of approximately 22 s. GGE conversion product analysis revealed the formation of oligomeric oxidation products upon reaction with peroxidase, which may be a potential hazard to membrane bioreactors. These oxidation products could further be degraded by laccase enzymes in the multienzymatic membranes, explaining the potential of multi enzyme membrane reactors. The multienzyme incorporated membrane reactors were active for more than 30 days of storage time at 4 °C. During this time span, repetitive use of the membrane reactor was demonstrated involving 5–6 h of operation time for each cycle. The membrane reactor displayed encouraging performance, losing only 12% of its initial activity after multiple cycles of operation.

  19. Catalytic depolymerization of lignin and woody biomass in supercritical Ethanol: influence of reaction temperature and feedstock : Influence of reaction temperature and feedstock

    NARCIS (Netherlands)

    Huang, X.; Atay, C.; Zhu, J.; Palstra, S.W.L.; Korányi, T.I.; Boot, M.D.; Hensen, E.J.M.

    2017-01-01

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

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

    Science.gov (United States)

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

    2010-01-01

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

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

    DEFF Research Database (Denmark)

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

    2016-01-01

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

  2. Synthesis of novel ionic liquids from lignin-derived compounds

    Science.gov (United States)

    Socha, Aaron; Singh, Seema; Simmons, Blake A.; Bergeron, Maxime

    2017-09-19

    Methods and compositions are provided for synthesizing ionic liquids from lignin derived compounds comprising: contacting a starting material comprising lignin with a depolymerization agent to depolymerize the lignin and form a mixture of aldehyde containing compounds; contacting the mixture of aldehyde containing compounds with an amine under conditions suitable to convert the mixture of aldehyde containing compounds to a mixture of amine containing compounds; and contacting the mixture of amine containing compounds with an acid under conditions suitable to form an ammonium salt, thereby preparing the ionic liquid.

  3. Radiolysis of lignin: Prospective mechanism of high-temperature decomposition

    Science.gov (United States)

    Ponomarev, A. V.

    2017-12-01

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

  4. Cellobiose Dehydrogenase Inhibition of Polymerization of Phenolic Compounds and Enhancing Lignin Degradation by Lignina.

    Science.gov (United States)

    Fang, Jing; Liu, Wen; Gao, Pei-Ji

    1999-01-01

    The kinetic behavior of cellobiose dehydrogenase (CDH) was investigated by steady-state initial velocity studies. Variation in the concentration of one substrate led to changes in K(m) and V(max) of the other substrate. The results were consistent with a ping-pong mechanism. In the presence of cellobiose, CDH could reduce many oxidized products catalyzed by soybean hull peroxidase (SHP). The oxidation product of 1-hydroxybenzotriazole (HBT) catalyzed by SHP inactivated the enzyme itself however, CDH could prevent SHP from inactivation by reducing the oxidation product of HBT. CDH could also inhibit the polymerization of phenolic compounds catalyzed by SHP. It was found that the addition of CDH could enhance kraft pulp lignin degradation by ligninases.

  5. H2O2 can Increase Lignin Disintegration and Decrease Cellulose Decomposition in the Process of Solid-State Fermentation (SSF by Aspergillus oryzae Using Corn Stalk as Raw Materials

    Directory of Open Access Journals (Sweden)

    Zhicai Zhang

    2014-04-01

    Full Text Available H2O2 is both bactericidal and the main oxidant responsible for lignin degradation reaction catalyzed by manganese peroxidase (MnP and lignin peroxidase (LiP. Thus, H2O2 treatment of corn stalk and the implementation of solid-substrate fermentation (SSF is possible to increase the removal rate of lignin from stalk in the process of SSF and after SSF, while avoiding the need to sterilize the raw materials. To demonstrate this approach, SSF was initially carried out using corn stalk pretreated with different concentrations of H2O2 as a substrate. A. oryzae was found to grow well in the 3% H2O2-pretreated corn stalk. H2O2-pretreated corn stalk showed increased MnP and LiP synthesis and disintegration of lignin, but inhibited cellulase synthesis and cellulose degradation. Production of the SSF (200 g on the 10th day was hydrolyzed in the presence of additional 600 mL different concentration of H2O2 aqueous solution. The total removal of lignin (73.15% of hydrolysis for 10 h at 3% H2O2 solution was highest and far higher than that at the 12th day, as achieved by conventional SSF. Applying this strategy in practice may shorten the time of lignin degradation, increase the removal of lignin, and decrease the loss of cellulose. Thus, this study has provided a foundation for further study saccharification of corn stalk.

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

    OpenAIRE

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

    2016-01-01

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

  7. Alkali-treated kraft lignin as a component in flakeboard eesins

    Science.gov (United States)

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

    1991-01-01

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

  8. Synthesis and application of nano-, meso- and macroporous sorbents based on lignin for detoxication of biological fluids

    Science.gov (United States)

    Chopabayeva, Nazira N.; Mukanov, Kanatbek N.; Tasmagambet, Amandyk T.

    2014-05-01

    Novel nano-, meso- and macroporous sorbents based on hydrolysis lignin have been synthesized by catalytic o-alkylation of biolpolymer with epoxy resin ED-20 and subsequent amination of formed α-oxyde derivative. Composition, structure, morphology and physical, chemical properties of ion-exchangers were investigated by FTIR, SEM, TEM, porosimetry and potentiometric titration method. It has been established that alkaline activated lignin shows an increase of SBET to 20.9 m2/g while modification leads to decrease of SBET more than double (from 9.2 to 5.2 m2/g) that of an untreared sample (14.5 m2/g). Synthesized sorbents are characterized by approximately identical mesoporous structure and mainly contained a pore size of 10-14 nm. The results clearly demonstrate the efficiency of lignin based sorbents for the removal of water and lipid soluble toxic metabolites from blood serum of diabetic retinopathy patients. Samples reduced the high level of total cholesterol, including its most atherogenic fractions (LDL-C, VLDL-C), triglyceride to the level of optimum compensated diabetes without significant removal of HDL-C. Concentration of glucose was decreased to physiological norms.

  9. Nano-lignin filled natural rubber composites: Preparation and characterization

    Directory of Open Access Journals (Sweden)

    C. Jiang

    2013-05-01

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

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

    Directory of Open Access Journals (Sweden)

    Daniel Humpert

    2016-09-01

    Full Text Available Utilization of renewable resources is becoming increasingly important, and only sustainable processes that convert such resources into useful products can achieve environmentally beneficial economic growth. Wastewater from the pulp and paper industry is an unutilized resource offering the potential to recover valuable products such as lignin, pigments, and water [1]. The recovery of lignin is particularly important because it has many applications, and membrane technology has been investigated as the basis of innovative recovery solutions. The concentration of lignin can be increased from 62 to 285 g∙L−1 using membranes and the recovered lignin is extremely pure. Membrane technology is also scalable and adaptable to different waste liquors from the pulp and paper industry.

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

    Science.gov (United States)

    Humpert, Daniel; Ebrahimi, Mehrdad; Czermak, Peter

    2016-01-01

    Utilization of renewable resources is becoming increasingly important, and only sustainable processes that convert such resources into useful products can achieve environmentally beneficial economic growth. Wastewater from the pulp and paper industry is an unutilized resource offering the potential to recover valuable products such as lignin, pigments, and water [1]. The recovery of lignin is particularly important because it has many applications, and membrane technology has been investigated as the basis of innovative recovery solutions. The concentration of lignin can be increased from 62 to 285 g∙L−1 using membranes and the recovered lignin is extremely pure. Membrane technology is also scalable and adaptable to different waste liquors from the pulp and paper industry. PMID:27608047

  12. Removal of oil palm trunk lignin in ammonium hydroxide pretreatment

    Science.gov (United States)

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

    2018-04-01

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

  13. Analytical protocols for characterisation of sulphur-free lignin

    NARCIS (Netherlands)

    Gosselink, R.J.A.; Abächerli, A.; Semke, H.; Malherbe, R.; Käuper, P.; Nadif, A.; Dam, van J.E.G.

    2004-01-01

    Interlaboratory tests for chemical characterisation of sulphur-free lignins were performed by five laboratories to develop useful analytical protocols, which are lacking, and identify quality-related properties. Protocols have been established for reproducible determination of the chemical

  14. Biological and Catalytic Conversion of Sugars and Lignin | Bioenergy | NREL

    Science.gov (United States)

    Sugars and Lignin Our research group, comprised of staff scientists, postdoctoral associates, students synthase enzyme, represented as "surfaces" or "blobs," embedded in a lipid bilayer "blobs," embedded in a lipid bilayer, represented as yellow multi-jointed strands. Above this

  15. Fast Pyrolysis of Lignin Using a Pyrolysis Centrifuge Reactor

    DEFF Research Database (Denmark)

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

    2013-01-01

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

  16. Genes encoding enzymes of the lignin biosynthesis pathway in Eucalyptus

    Directory of Open Access Journals (Sweden)

    Ricardo Harakava

    2005-01-01

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

  17. Transcription factors for modification of lignin content in plants

    Science.gov (United States)

    Wang, Huanzhong; Chen, Fang; Dixon, Richard A.

    2015-06-02

    The invention provides methods for modifying lignin, cellulose, xylan, and hemicellulose content in plants, and for achieving ectopic lignification and, for instance, secondary cell wall synthesis in pith cells, by altered regulation of a WRKY transcription factor. Nucleic acid constructs for altered WRKY-TF expression are described. Transgenic plants are provided that comprise modified pith cell walls, and lignin, cellulose, and hemicellulose content. Plants described herein may be used, for example, as improved biofuel feedstock and as highly digestible forage crops.

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

    Science.gov (United States)

    Zhao, Qiao; Chen, Fang; Dixon, Richard A.

    2014-08-05

    The invention provides methods for decreasing lignin content and for increasing the level of fermentable carbohydrates in plants by down-regulation of the NST transcription factor. Nucleic acid constructs for down-regulation of NST are described. Transgenic plants are provided that comprise reduced lignin content. Plants described herein may be used, for example, as improved biofuel feedstock and as highly digestible forage crops. Methods for processing plant tissue and for producing ethanol by utilizing such plants are also provided.

  19. Lignin chemical degradation using redistribution mechanism and its biomass applications

    OpenAIRE

    Nanayakkara, Sepa Yasandrika

    2017-01-01

    Lignin is one of the most abundant renewable raw materials available on earth and it has the potential to yield valuable low molecular weight aromatic compounds if it can be depolymerized selectively. Despite its unique characteristics as a natural product with multiple chemical and biophysical functionalities, it is largely under-exploited, because of the lack of available methods that effect depolymerization in a selective manner. One of the dominant linkages in lignin has a similar ary...

  20. Improved Lignin Polyurethane Properties with Lewis Acid Treatment

    OpenAIRE

    Chung, Hoyong; Washburn, Newell R.

    2012-01-01

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

  1. Chemical reactivity of alkali lignin modified with laccase

    International Nuclear Information System (INIS)

    Sun, Yong; Qiu, Xueqing; Liu, Yunquan

    2013-01-01

    The modification of alkali lignin with laccase was investigated. The structural change of lignin was analyzed. The sulfonation reactivity was measured by the content of sulfonic group. The results showed the sulfonation reactivity increased to some extent under the condition of atmosphere pressure, but decreased under the condition of 0.3 MPa oxygen pressure. The analysis of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) showed the cleavage of various ether linkages and demethylation took place in the structure of lignin to certain extent during modification with laccase, which contributed to the improvement of sulfonation reactivity. Under the condition of 0.3 MPa oxygen pressure, the ratio of s/g (guaiacyl/syringyl) increased after modification, which reduced the sulfonation reactivity of lignin. Simultaneously partial polymerization reaction, such as 4-O-5′, β-5, 5-5 and other reaction in the aromatic ring decreased the activity sites of C 2 , C 5 and C 6 . Abundant polymerization reaction of α-O increased steric hindrance of C 2 and C 6 in aromatic ring, resulting in low sulfonation reactivity of lignin. -- Highlights: ► The modification of alkali lignin with laccase was investigated. ► The sulfonation reactivity increased under the condition of atmosphere pressure. ► More content of guaiacyl and hydroxy, the less content of methoxyl, syringyl can enhance the sulfonation reactivity of lignin. ► Partial moieties polymerized each other with α-O linkgages during treatment with laccase under oxygen pressure. ► The steric hindrance on C 2 and C 6 in aromatic ring resulted in low sulfonation reaction reactivity of lignin

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

    Science.gov (United States)

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

    2014-01-13

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

  3. Density functional theory study of spirodienone stereoisomers in lignin

    Science.gov (United States)

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

    2017-01-01

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

  4. Decoding how a soil bacterium extracts building blocks and metabolic energy from ligninolysis provides road map for lignin valorization

    Science.gov (United States)

    Varman, Arul M.; He, Lian; Follenfant, Rhiannon; Wu, Weihua; Wemmer, Sarah; Wrobel, Steven A.; Tang, Yinjie J.; Singh, Seema

    2016-01-01

    Sphingobium sp. SYK-6 is a soil bacterium boasting a well-studied ligninolytic pathway and the potential for development into a microbial chassis for lignin valorization. An improved understanding of its metabolism will help researchers in the engineering of SYK-6 for the production of value-added chemicals through lignin valorization. We used 13C-fingerprinting, 13C metabolic flux analysis (13C-MFA), and RNA-sequencing differential expression analysis to uncover the following metabolic traits: (i) SYK-6 prefers alkaline conditions, making it an efficient host for the consolidated bioprocessing of lignin, and it also lacks the ability to metabolize sugars or organic acids; (ii) the CO2 release (i.e., carbon loss) from the ligninolysis-based metabolism of SYK-6 is significantly greater than the CO2 release from the sugar-based metabolism of Escherichia coli; (iii) the vanillin catabolic pathway (which is the converging point of majority of the lignin catabolic pathways) is coupled with the tetrahydrofolate-dependent C1 pathway that is essential for the biosynthesis of serine, histidine, and methionine; (iv) catabolic end products of lignin (pyruvate and oxaloacetate) must enter the tricarboxylic acid (TCA) cycle first and then use phosphoenolpyruvate carboxykinase to initiate gluconeogenesis; and (v) 13C-MFA together with RNA-sequencing differential expression analysis establishes the vanillin catabolic pathway as the major contributor of NAD(P)H synthesis. Therefore, the vanillin catabolic pathway is essential for SYK-6 to obtain sufficient reducing equivalents for its healthy growth; cosubstrate experiments support this finding. This unique energy feature of SYK-6 is particularly interesting because most heterotrophs rely on the transhydrogenase, the TCA cycle, and the oxidative pentose phosphate pathway to obtain NADPH. PMID:27634497

  5. Soluble CD40 ligand stimulates CD40-dependent activation of the β2 integrin Mac-1 and protein kinase C zeda (PKCζ in neutrophils: implications for neutrophil-platelet interactions and neutrophil oxidative burst.

    Directory of Open Access Journals (Sweden)

    Rong Jin

    Full Text Available Recent work has revealed an essential involvement of soluble CD40L (sCD40L in inflammation and vascular disease. Activated platelets are the major source of sCD40L, which has been implicated in platelet and leukocyte activation, although its exact functional impact on leukocyte-platelet interactions and the underlying mechanisms remain undefined. We aimed to determine the impact and the mechanisms of sCD40L on neutrophils. We studied neutrophil interactions with activated, surface-adherent platelets as a model for leukocyte recruitment to the sites of injury. Our data show that CD40L contributes to neutrophil firm adhesion to and transmigration across activated surface-adherent platelets, possibly through two potential mechanisms. One involves the direct interaction of ligand-receptor (CD40L-CD40, i.e., platelet surface CD40L interaction with neutrophil CD40; another involves an indirect mechanism, i.e. soluble CD40L stimulates activation of the leukocyte-specific β2 integrin Mac-1 in neutrophils and thereby further promotes neutrophil adhesion and migration. Activation of the integrin Mac-1 is known to be critical for mediating neutrophil adhesion and migration. sCD40L activated Mac-1 in neutrophils and enhanced neutrophil-platelet interactions in wild-type neutrophils, but failed to elicit such responses in CD40-deficient neutrophils. Furthermore, our data show that the protein kinase C zeta (PKCζ is critically required for sCD40L-induced Mac-1 activation and neutrophil adhesive function. sCD40L strongly stimulated the focal clustering of Mac-1 (CD11b and the colocalization of Mac-1 with PKCζ in wild-type neutrophils, but had minimal effect in CD40-deficient neutrophils. Blocking PKCζ completely inhibited sCD40L-induced neutrophil firm adhesion. Moreover, sCD40L strongly stimulates neutrophil oxidative burst via CD40-dependent activation of PI3K/NF-KB, but independent of Mac-1 and PKCζ. These findings may contribute to a better

  6. Characterization of anaerobic consortia coupled lignin depolymerization with biomethane generation.

    Science.gov (United States)

    Wu, Yi-Rui; He, Jianzhong

    2013-07-01

    Two sediment-free microbial consortia (LI3 and LP3) were established to depolymerize lignin under anaerobic conditions. During depolymerizing high molecular weight lignin to low molecular weight molecules, the two cultures produced biomethane up to 151.7 and 113.0 mL g(-1) total lignin. Furthermore, LI3 and LP3 could also utilize the biomass - oil palm empty fruit bunch fiber (OPEFB) to produce 190.6 and 195.6 mL methaneg(-1) total lignin in OPEFB, and at the same time improve the bioavailability of lignocellulosic matters for further enzymatic hydrolysis. The microbial community analysis by denature gradient gel electrophoresis (DGGE) and the high-density 16S rDNA gene microarray (PhyloChip) exhibited that Methanomethylovorans sp. (LI3) and Methanoculleus sp. (LP3) were the main methanogens present, and phylum Firmicutes and Bacteroidetes were mainly involved in the lignin depolymerization. The established microbial consortia with both lignin depolymerization and biomethane production provide profound application on the environmental friendly pretreatment of lignocellulosic materials. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Abundance and reactivity of dibenzodioxocins in softwood lignin.

    Science.gov (United States)

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

    2002-02-13

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

  8. Metal Triflates for the Production of Aromatics from Lignin.

    Science.gov (United States)

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

    2016-10-20

    The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields under mild reaction conditions. The methodology relies on the use of catalytic amounts of easy-to-handle metal triflates (M(OTf) x ). Initially, we evaluated the reactivity of a broad range of metal triflates using simple lignin model compounds. More advanced lignin model compounds were also used to study the reactivity of different lignin linkages. The product aromatic monomers were either phenolic C2-acetals obtained by stabilization of the aldehyde cleavage products by reaction with ethylene glycol or methyl aromatics obtained by catalytic decarbonylation. Notably, when the method was ultimately tested on lignin, especially Fe(OTf) 3 proved very effective and the phenolic C2-acetal products were obtained in an excellent, 19.3±3.2 wt % yield. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Signatures of cinnamyl alcohol dehydrogenase deficiency in poplar lignins.

    Science.gov (United States)

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

    2004-02-01

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

  10. System analyse cellulose ethanol in combines - Combustion characterisation of lignin from cellulose based ethanol production; Systemanalys foer cellulosabaserad etanol i kombinat - Foerbraenningskarakterisering av lignin fraan cellulosabaserad etanolproduktion

    Energy Technology Data Exchange (ETDEWEB)

    Lindstedt, Jan; Wingren, Anders; Magnusson, Staffan; Wiinikka, Henrik; Westbom, Urban; Lidman, Marcus; Groenberg, Carola

    2012-02-15

    In this work 3 different hydrolysed lignin fractions produced from Sugarcane Bagasse, Spruce and Wheat Straw were burned in a 150 kW horizontal furnace equipped with a powder burner to assess the combustion behaviour of hydrolysed lignin fuels. The combustion experiments showed that the feeding properties of all three lignin fractions were better compared to ordinary wood powder

  11. The reactivity of phenolic and non-phenolic residual kraft lignin model compounds with Mn(II)-peroxidase from Lentinula edodes.

    Science.gov (United States)

    Crestini, C; D'Annibale, A; Sermanni, G G; Saladino, R

    2000-02-01

    Three phenolic model compounds representing bonding patterns of residual kraft lignin were incubated with manganese peroxidase from Lentinula edodes. Extensive degradation of all the phenolic models, mainly occurring via side-chain benzylic oxidation, was observed. Among the tested model compounds the diphenylmethane alpha-5 phenolic model was found to be the most reactive, yielding several products showing oxidation and fragmentation at the bridging position. The non-phenolic 5-5' biphenyl and 5-5' diphenylmethane models were found unreactive.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-17

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

  13. Use of Hesperaloe funifera for the production of paper and extraction of lignin for synthesis and fuel gases

    International Nuclear Information System (INIS)

    Sanchez, R.; Rodriguez, A.; Navarro, E.; Conesa, J.A.; Jimenez, L.

    2010-01-01

    In this work, we characterized Hesperaloe funifera; pulp and paper obtained by subjecting the plant raw material to soda, soda-anthraquinone, ethanolamine, ethyleneglycol and diethyleneglycol cooking. In addition, the solid fractions extracted by acidifying the cooking liquors, rich in lignin, were used to obtain synthesis and fuel gases. The contents in lignin, α-cellulose, holocellulose, hemicellulose, ethanol-benzene extractives, hot water solubles, 1% NaOH solubles and ash of H. funifera were found to be 7.3%, 40.9%, 76.5%, 35.6%, 4.0%, 13.5%, 29.5% and 5.9%, respectively. The mean fibre length, 4.19 mm, exceeds those for some non-wood materials. Hesperaloe pulp obtained by cooking with 10% NaOH and 1% anthraquinone at 155 o C for 30 min exhibited good values of yield (48.3%), viscosity (737 mL g -1 ), Kappa number (15.2), tensile index (83.6 Nm g -1 ), stretch (3.8%), burst index (7.34 kN g -1 ) and tear index (3.20 mNm 2 g -1 ). Acidification to pH 6 of the liquor resulting from the soda pulping of 500 g of plant raw material provided an amount of 13.90 g of lignin-rich solids pyrolysis of which gave a gas mixture containing 1.13% H 2 , 31.79% CO and 1.86% CH 4 by weight. Gasification of the same sample provided a mixture containing 0.18% H 2 , 24.50% CO and 17.75% CH 4 , also by weight.

  14. Fate of lignin, cutin and suberin in soil organic matter fractions - an incubation experiment

    Science.gov (United States)

    Mueller, Carsten W.; Mueller, Kevin E.; Freeman, Katherine H.; Ingrid, Kögel-Knabner

    2010-05-01

    The turnover of soil organic matter (SOM) is controlled by its chemical composition, its spatial accessibility and the association with the mineral phase. Separation of bulk soils by physical fractionation and subsequent chemical analysis of these fractions should give insights to how compositional differences in SOM drive turnover rates of different size-defined carbon pools. The main objective of this study was to elucidate the relative abundance and recalcitrance of lignin, cutin and suberin in aggregated bulk soils and SOM fractions in the course of SOM decomposition. Bulk soils and physically-separated size fractions (sand, silt and clay) of the Ah horizon of a forest soil (under Picea abies L.Karst) were parallel incubated over a period of one year. In order to differentiate between particulate OM (POM) and mineral-associated SOM the particle size fractions were additionally separated by density after the incubation experiment. We used solid-state 13C-CPMAS NMR spectroscopy and GC-MS (after copper oxide oxidation and solvent extraction) to analyze the composition of the incubated samples. The abundance and isotopic composition (including 13C and 14C) of the respired CO2 further enabled us to monitor the dynamics of SOM mineralization. This approach allowed for differentiating between C stabilization of soil fractions due to accessibility/aggregation and to biochemical recalcitrance at different scales of resolution (GC-MS, NMR). We found a relative enrichment of alkyl C and decreasing lignin contents in the order of sand particulate OM (POM). For the fresh particulate OM (POM) of the sand fraction a clear decay of lignin was observed in the course of the incubation experiment, indicated by decreasing C/V and increasing ac/alV ratios. A relative decrease of aliphatic C in the incubated fractions compared to the incubated bulk soils showed the preferential mineralization of less recalcitrant C compounds that were spatially inaccessible in aggregates of the bulk

  15. Aerobic Oxidation of Veratryl Alcohol to Veratraldehyde with Heterogeneous Ruthenium Catalysts

    DEFF Research Database (Denmark)

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

    2015-01-01

    Lignin is a complex polymeric molecule constituting various linkages between aromatic moieties. Typically, the β-O-4 linkage accounts for more than half of the linkage structures present in lignin. The current study focuses on the oxidative transformation of veratryl alcohol (VA)—a compound that ...

  16. The catalytic ozonization of model lignin compounds in the presence of Fe(III) ions

    Science.gov (United States)

    Ben'ko, E. M.; Mukovnya, A. V.; Lunin, V. V.

    2007-05-01

    The ozonization of several model lignin compounds (guaiacol, 2,6-dimethoxyphenol, phenol, and vanillin) was studied in acid media in the presence of iron(III) ions. It was found that Fe3+ did not influence the initial rate of the reactions between model phenols and ozone but accelerated the oxidation of intermediate ozonolysis products. The metal concentration dependences of the total ozone consumption and effective rate constants of catalytic reaction stages were determined. Data on reactions in the presence of oxalic acid as a competing chelate ligand showed that complex formation with Fe3+ was the principal factor that accelerated the ozonolysis of model phenols at the stage of the oxidation of carboxylic dibasic acids and C2 aldehydes formed as intermediate products.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  18. Coconut coir pith lignin: A physicochemical and thermal characterization.

    Science.gov (United States)

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

    2018-07-01

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

  19. Lignin as a facilitator, not a barrier, during saccharification by brown rot fungi

    Energy Technology Data Exchange (ETDEWEB)

    Schilling, Jonathan S. [Univ. of Minnesota, Minneapolis, MN (United States); Tschirner, Ulrike [Univ. of Minnesota, Minneapolis, MN (United States); Blanchette, Robert A [Univ. of Minnesota, Minneapolis, MN (United States); Filley, Timothy [Purdue Univ., West Lafayette, IN (United States)

    2012-11-28

    This research focused on the biology of a group of wood-degrading fungi that cause brown rot in wood, with particular attention to the potential to mimic this biological approach ex situ for bioprocessing lignocellulosic biomass. Supported by the long-standing theory that these fungi use a two-step oxidative/enzymatic approach during brown rot, our team’s objectives were as follows: 1) to determine the discrete timing of lignin modifications, 2) to correlate these alterations with biocatalyst efficiency and ingress into plant cell walls, and 3) to reproduce modifications prior to saccharification for efficient bioprocessing. The core findings of our research were that 1) lignin modifications occur nearly coincident with enzyme secretion during brown rot and 2) there is no specificity to the benefit that a brown rot pretreatment has on the efficacy of cellulases – it is a general enhancement best predicted by chemical changes to lignin and side-chain hemicellulose sugars. In our work, this meant we could attain and predict broad improvements in saccharification using commercial cellulase cocktails, in some cases more than three-fold of that in untreated biomass. This project was completed with minimal variance from the original project management plan (PMP), resulting in fourteen presentations and posters, four peer-reviewed publications, and one additional publication now in review. The publications have been valuable to other scientists working toward similar goals and have been cited in thirteen peer-reviewed publications written by others since 2010. We are working with ADM to advance application options for industry, building on the lessons learned during this DOE award period.

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

    Science.gov (United States)

    Bunzel, Mirko; Ralph, John

    2006-10-18

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

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

    Science.gov (United States)

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

    2014-07-01

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

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

    Science.gov (United States)

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

    2012-09-01

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

  3. Reactivity improvement of cellulolytic enzyme lignin via mild hydrothermal modification.

    Science.gov (United States)

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

    2017-12-01

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

  4. Selective Photooxidation Reactions using Water-Soluble Anthraquinone Photocatalysts

    NARCIS (Netherlands)

    Zhang, W.; Gacs, Jenő; Arends, I.W.C.E.; Hollmann, F.

    2017-01-01

    The aerobic organocatalytic oxidation of alcohols was achieved by using water-soluble sodium anthraquinone sulfonate. Under visible-light activation, this catalyst mediated the aerobic oxidation of alcohols to aldehydes and ketones. The photo-oxyfunctionalization of alkanes was also possible

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

    Directory of Open Access Journals (Sweden)

    Cassie Marie Welker

    2015-07-01

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

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

    NARCIS (Netherlands)

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

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

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

    International Nuclear Information System (INIS)

    Bonnarme, P.; Jeffries, T.W.

    1990-01-01

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

  8. Electron-beam mediated dry distillation of lignin

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  9. Conversion of kraft lignin over hierarchical MFI zeolite.

    Science.gov (United States)

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

    2014-03-01

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

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

  11. Structural variations and physical properties of lignin coke

    International Nuclear Information System (INIS)

    Otani, C.

    1986-01-01

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

  12. Soluble CD163

    DEFF Research Database (Denmark)

    Møller, Holger J

    2012-01-01

    CD163 is an endocytic receptor for haptoglobin-hemoglobin complexes and is expressed solely on macrophages and monocytes. As a result of ectodomain shedding, the extracellular portion of CD163 circulates in blood as a soluble protein (sCD163) at 0.7-3.9 mg/l in healthy individuals. The function o...

  13. Solubility Part 1

    NARCIS (Netherlands)

    Tantra, Ratna; Bolea, Eduardo; Bouwmeester, H.; Rey-Castro, Carlos; David, C.A.A.; Dogné, Jean Michel; Laborda, Francisco; Laloy, Julie; Robinson, Kenneth N.; Undas, A.K.; Zande, van der M.

    2016-01-01

    This chapter gives an overview of different methods that can potentially be used to determine the solubility of nanomaterials. In general, the methods presented can be broadly divided into four categories: separation methods, methods to quantify free ions, methods to quantify total dissolved

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

    Science.gov (United States)

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

    2012-05-14

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

  15. Seed Nutrition and Quality, Seed Coat Boron and Lignin Are Influenced by Delayed Harvest in Exotically-Derived Soybean Breeding Lines under High Heat.

    Science.gov (United States)

    Bellaloui, Nacer; Smith, James R; Mengistu, Alemu

    2017-01-01

    The timing of harvest is a major factor affecting seed quality in soybean, particularly in Midsouthern USA, when rain during harvest period is not uncommon. The objective of this research was to evaluate the effects of time of harvest on soybean seed quality (seed composition, germination, seed coat boron, and lignin) in high germinability (HG) breeding lines (50% exotic) developed under high heat. The hypothesis was that seeds of HG lines possess physiological and genetic traits for a better seed quality at harvest maturity and delayed harvest. A 2-year field experiment was conducted under irrigated conditions. Results showed that, at harvest maturity, the exotic HG lines had higher seed protein, oleic acid, sugars, seed coat boron, and seed coat lignin, but lower seed oil compared with the non-exotic checks (Control), confirming our hypothesis. At 28 days after harvest maturity (delayed harvest), the content of seed protein, oleic acid, sugars, seed coat boron, and seed coat lignin were higher in some of the HG lines compared with the checks, indicating a possible involvement of these seed constituents, especially seed coat boron and seed coat lignin, in maintaining seed coat integrity and protecting seed coat against physical damage. Highly significant positive correlations were found between germination and seed protein, oleic acid, sugars, and seed coat boron and seed coat lignin. Highly significant negative correlation was found between germination and oil, linoleic acid, seed coat wrinkling, shattering, and hard seed. Yields of some HG lines were competitive with checks. This research demonstrated that time of harvesting is an important factor influencing seed protein and oil production. Also, since high oleic acid is desirable for oxidative stability, shelf-life and biodiesel properties, using HG lines could positively influence these important traits. This result should suggest to breeders of some of the advantages of selecting for high seed coat boron and

  16. Solubility of plutonium dioxide aerosols, in vitro

    International Nuclear Information System (INIS)

    Newton, G.J.; Kanapilly, G.M.

    1976-01-01

    Solubility of plutonium aerosols is an important parameter in establishing risk estimates for industrial workers who might accidentally inhale these materials and in evaluating environmental health impacts associated with Pu. In vitro solubility of industrial plutonium aerosols in a simulated lung fluid is compared to similar studies with ultrafine aerosols from laser ignition of delta phase plutonium metal and laboratory-produced spherical particles of 238 PuO 2 and 239 PuO 2 . Although relatively insoluble, industrial plutonium-mixed oxide aerosols were much more soluble than laboratory-produced plutonium dioxide particles. Chain agglomerate aerosols from laser ignition of metallic Pu indicated in vitro dissolution half-times of 10 and 50 days for activity median aerodynamic diameter (AMAD) of 0.7 and 2.3 μm, respectively. Plutonium-containing mixed oxide aerosols indicated dissolution half-times of 40 to 500 days for particles formed by industrial powder comminution and blending. Centerless grinding of fuel pellets yielded plutonium-containing aerosols with dissolution half-times of 1200 to 8000 days. All mixed oxide particles were in the size range 1.0 μm to 2.5 μm AMAD

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

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

    OpenAIRE

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

    2012-01-01

    Wood is a major pool of organic carbon that is highly resistant to decay, owing largely to the presence of lignin. The only organisms capable of substantial lignin decay are white rot fungi in the Agaricomycetes, which also contains non?lignin-degrading brown rot and ectomycorrhizal species. Comparative analyses of 31 fungal genomes (12 generated for this study) suggest that lignin-degrading peroxidases expanded in the lineage leading to the ancestor of the Agaricomycetes, which is reconstruc...

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

    OpenAIRE

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

    2017-01-01

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

  20. EVALUATION OF ENDOGLUCANASE, EXOGLUCANASE, LACCASE, AND LIGNIN PEROXIDASE ACTIVITIES ON TEN WHITE-ROT FUNGI

    Directory of Open Access Journals (Sweden)

    Sandra Montoya B

    2014-12-01

    Full Text Available This paper presents a way of tracking the production of lignocellulolytic enzymes in ten species of white rot fungi: Lentinula edodes, Schizophyllum commune, Trametes trogii, Coriolus versicolor, Pycnoporus sanguineus, Ganoderma applanatum, Ganoderma lucidum, Grifola frondosa, Pleurotus ostreatus and Auricularia delicata. These species were first screened on solid culture media containing carboxymethyl cellulose, crystalline cellulose, ABTS (2,2´-azino-bis(3-ethylbenzothiazoline-6-sulphonate and azure B, which showed the production of endoglucanase, exoglucanase, laccase and lignin peroxidase (LiP enzymes. Cellulolytic activities were detected after five days of incubation with congo red indicator, forming a clear-white halo in areas where cellulose was degraded. For ligninases, the tracking consisted of the monitoring in the formation of green halos due to ABTS oxidation for laccase, and decolorization halos on azure B for LiP during 14 days of incubation. From this qualitative screening, four strains were selected (G. lucidum, L. edodes, C. versicolor and T. trogii as the best producers of cellulolytic and ligninolytic enzymes. These four species were inoculated on a substrate of sawdust oak, yielding 51,8% of lignin degraded by L. edodes and 22% of cellulose degraded by C. versicolor.