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Sample records for non-phenolic beta-o-4 lignin

  1. 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...

  2. Selective defunctionalization by TiO2 of monomeric phenolics from lignin pyrolysis into simple phenols.

    Science.gov (United States)

    Mante, Ofei D; Rodriguez, Jose A; Babu, Suresh P

    2013-11-01

    This study is focused on defunctionalizing monomeric phenolics from lignin into simple phenols for applications such as phenol/formaldehyde resins, epoxidized novolacs, adhesives and binders. Towards this goal, Titanium dioxide (TiO2) was used to selectively remove hydroxyl, methoxy, carbonyl and carboxyl functionalities from the monomeric phenolic compounds from lignin to produce mainly phenol, cresols and xylenols. The results showed that anatase TiO2 was more selective and active compared to rutile TiO2. Catechols were found to be the most reactive phenolics and 4-ethylguaiacol the least reactive with anatase TiO2. An overall conversion of about 87% of the phenolics was achieved at 550°C with a catalyst-to-feed ratio of 5 w/w. Over 97% conversion of phenolics is achievable at moderate temperatures (550°C or ≤ 600°C) and a moderate catalyst-to-feed ratio of 6.5:1. The reactivity of catechols on TiO2 suggests that titania is a promising catalyst in the removal of hydroxyl moiety. Published by Elsevier Ltd.

  3. 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.

  4. 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.

  5. 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...

  6. 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.

  7. 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.

  8. A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis.

    Science.gov (United States)

    Bu, Quan; Lei, Hanwu; Zacher, Alan H; Wang, Lu; Ren, Shoujie; Liang, Jing; Wei, Yi; Liu, Yupeng; Tang, Juming; Zhang, Qin; Ruan, Roger

    2012-11-01

    Catalytic hydrodeoxygenation (HDO) of lignin-derived phenols which are the lowest reactive chemical compounds in biomass pyrolysis oils has been reviewed. The hydrodeoxygenation (HDO) catalysts have been discussed including traditional HDO catalysts such as CoMo/Al(2)O(3) and NiMo/Al(2)O(3) catalysts and transition metal catalysts (noble metals). The mechanism of HDO of lignin-derived phenols was analyzed on the basis of different model compounds. The kinetics of HDO of different lignin-derived model compounds has been investigated. The diversity of bio-oils leads to the complexities of HDO kinetics. The techno-economic analysis indicates that a series of major technical and economical efforts still have to be investigated in details before scaling up the HDO of lignin-derived phenols in existed refinery infrastructure. Examples of future investigation of HDO include significant challenges of improving catalysts and optimum operation conditions, further understanding of kinetics of complex bio-oils, and the availability of sustainable and cost-effective hydrogen source. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-04

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-04

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

  12. Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4-O-5 Linkage in Lignin Models.

    Science.gov (United States)

    Zeng, Huiying; Cao, Dawei; Qiu, Zihang; Li, Chao-Jun

    2018-03-26

    Lignin is the second most abundant organic matter on Earth, and is an underutilized renewable source for valuable aromatic chemicals. For future sustainable production of aromatic compounds, it is highly desirable to convert lignin into value-added platform chemicals instead of using fossil-based resources. Lignins are aromatic polymers linked by three types of ether bonds (α-O-4, β-O-4, and 4-O-5 linkages) and other C-C bonds. Among the ether bonds, the bond dissociation energy of the 4-O-5 linkage is the highest and the most challenging to cleave. To date, 4-O-5 ether linkage model compounds have been cleaved to obtain phenol, cyclohexane, cyclohexanone, and cyclohexanol. The first example of direct formal cross-coupling of diaryl ether 4-O-5 linkage models with amines is reported, in which dual C(Ar)-O bond cleavages form valuable nitrogen-containing derivatives. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2-ZrO2 catalysts.

    Science.gov (United States)

    Zhang, Xinghua; Zhang, Qi; Wang, Tiejun; Ma, Longlong; Yu, Yuxiao; Chen, Lungang

    2013-04-01

    Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2016-07-25

    Lignin is the largest source of renewable material with an aromatic skeleton. However, due to the recalcitrant and heterogeneous nature of the lignin polymer, it has been a challenge to effectively depolymerize lignin and produce high-value chemicals with high selectivity. In this study, a highly efficient lignin-to-monomeric phenolic compounds (MPC) conversion method based on peracetic acid (PAA) treatment was reported. PAA treatment of two biorefinery lignin samples, diluted acid pretreated corn stover lignin (DACSL) and steam exploded spruce lignin (SESPL), led to complete solubilization and production of selective hydroxylated monomeric phenolic compounds (MPC-H) and monomeric phenolic acid compounds (MPC-A) including 4-hydroxy-2-methoxyphenol, p-hydroxybenzoic acid, vanillic acid, syringic acid, and 3,4-dihydroxybenzoic acid. The maximized MPC yields obtained were 18 and 22 % based on the initial weight of the lignin in SESPL and DACSL, respectively. However, we found that the addition of niobium pentoxide catalyst to PAA treatment of lignin can significantly improve the MPC yields up to 47 %. The key reaction steps and main mechanisms involved in this new lignin-to-MPC valorization pathway were investigated and elucidated. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Non-phenolic antioxidant compounds from Buddleja asiatica.

    Science.gov (United States)

    el-Sayed, Mortada M; Abdel-Hameed, El-Sayed S; Ahmed, Wafaa S; el-Wakil, Eman A

    2008-01-01

    The methanol extract of the leaves of Buddleja asiatica Lour. (Loganiaceae) showed antioxidant activity toward the well known in vitro antioxidant tests such as total antioxidant capacity by the phosphomolybdenum method, free radical scavenging activity by the 1,1-diphenyl-2-picrylhydrazyl scavenging assay (DPPH assay) and hydrogen peroxide scavenging methods. Due to the high scavenging activity of the n-butanol successive fraction toward DPPH and H2O2 (SC50 = 11.99 and 18.54 microg/ml, respectively), this extract was subjected to chromatographic separation and isolation. Four non-phenolic compounds were isolated and identified on the basis of spectroscopic and chemical analyses: 1-O-beta-D-glucopyranosyl-2-methoxy-3-(2-hydroxy-triaconta-3,12-dienoate)-glycerol (1), 3-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-beta-D-fucopyranosyl-olean-11,13(18)-diene-3 beta,23,28-triol (2), 3-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->3)]-beta-D-fucopyranosyl-olean-11,13(18)-diene-3,23,28-triol (3), and 3-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->3)]-[beta-D-xylopyranosyl-(1-->2)]-beta-D-glucuronopyranosyl-acid-olean-11,13(18)-diene-3 beta,23,28-triol (4). The four compounds were evaluated as antioxidant agents using the three antioxidant bioassay tests.

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

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    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.

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

    Science.gov (United States)

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

    2010-04-01

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

  18. 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.

  19. Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

    Science.gov (United States)

    Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy

    2017-05-22

    Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Wang, Guanhua; Chen, Hongzhang

    2014-06-01

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

  1. 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.

  2. Selective nickel-catalyzed conversion of model and lignin-derived phenolic compounds to cyclohexanone-based polymer building blocks.

    Science.gov (United States)

    Schutyser, Wouter; Van den Bosch, Sander; Dijkmans, Jan; Turner, Stuart; Meledina, Maria; Van Tendeloo, Gustaaf; Debecker, Damien P; Sels, Bert F

    2015-05-22

    Valorization of lignin is essential for the economics of future lignocellulosic biorefineries. Lignin is converted into novel polymer building blocks through four steps: catalytic hydroprocessing of softwood to form 4-alkylguaiacols, their conversion into 4-alkylcyclohexanols, followed by dehydrogenation to form cyclohexanones, and Baeyer-Villiger oxidation to give caprolactones. The formation of alkylated cyclohexanols is one of the most difficult steps in the series. A liquid-phase process in the presence of nickel on CeO2 or ZrO2 catalysts is demonstrated herein to give the highest cyclohexanol yields. The catalytic reaction with 4-alkylguaiacols follows two parallel pathways with comparable rates: 1) ring hydrogenation with the formation of the corresponding alkylated 2-methoxycyclohexanol, and 2) demethoxylation to form 4-alkylphenol. Although subsequent phenol to cyclohexanol conversion is fast, the rate is limited for the removal of the methoxy group from 2-methoxycyclohexanol. Overall, this last reaction is the rate-limiting step and requires a sufficient temperature (>250 °C) to overcome the energy barrier. Substrate reactivity (with respect to the type of alkyl chain) and details of the catalyst properties (nickel loading and nickel particle size) on the reaction rates are reported in detail for the Ni/CeO2 catalyst. The best Ni/CeO2 catalyst reaches 4-alkylcyclohexanol yields over 80 %, is even able to convert real softwood-derived guaiacol mixtures and can be reused in subsequent experiments. A proof of principle of the projected cascade conversion of lignocellulose feedstock entirely into caprolactone is demonstrated by using Cu/ZrO2 for the dehydrogenation step to produce the resultant cyclohexanones (≈80 %) and tin-containing beta zeolite to form 4-alkyl-ε-caprolactones in high yields, according to a Baeyer-Villiger-type oxidation with H2 O2 . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Nour Eddine El Mansouri

    2011-05-01

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

  4. 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.

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

    Directory of Open Access Journals (Sweden)

    Jiongjiong Li

    2017-09-01

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

  6. 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...

  7. 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).

  8. Exploring the potential of high resolution mass spectrometry for the investigation of lignin-derived phenol substitutes in phenolic resin syntheses.

    Science.gov (United States)

    Dier, Tobias K F; Fleckenstein, Marco; Militz, Holger; Volmer, Dietrich A

    2017-05-01

    Chemical degradation is an efficient method to obtain bio-oils and other compounds from lignin. Lignin bio-oils are potential substitutes for the phenol component of phenol formaldehyde (PF) resins. Here, we developed an analytical method based on high resolution mass spectrometry that provided structural information for the synthesized lignin-derived resins and supported the prediction of their properties. Different model resins based on typical lignin degradation products were analyzed by electrospray ionization in negative ionization mode. Utilizing enhanced mass defect filter techniques provided detailed structural information of the lignin-based model resins and readily complemented the analytical data from differential scanning calorimetry and thermogravimetric analysis. Relative reactivity and chemical diversity of the phenol substitutes were significant determinants of the outcome of the PF resin synthesis and thus controlled the areas of application of the resulting polymers. Graphical abstract ᅟ.

  9. Thermal Decomposition Mechanisms of Lignin Model Compounds: From Phenol to Vanillin

    Science.gov (United States)

    Scheer, Adam Michael

    Lignin is a complex, aromatic polymer abundant in cellulosic biomass (trees, switchgrass etc.). Thermochemical breakdown of lignin for liquid fuel production results in undesirable polycyclic aromatic hydrocarbons that lead to tar and soot byproducts. The fundamental chemistry governing these processes is not well understood. We have studied the unimolecular thermal decomposition mechanisms of aromatic lignin model compounds using a miniature SiC tubular reactor. Products are detected and characterized using time-of-flight mass spectrometry with both single photon (118.2 nm; 10.487 eV) and 1 + 1 resonance-enhanced multiphoton ionization (REMPI) as well as matrix isolation infrared spectroscopy. Gas exiting the heated reactor (300 K--1600 K) is subject to a free expansion after a residence time of approximately 100 micros. The expansion into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. By understanding the unimolecular fragmentation patterns of phenol (C6H5OH), anisole (C6H 5OCH3) and benzaldehyde (C6H5CHO), the more complicated thermocracking processes of the catechols (HO-C 6H4-OH), methoxyphenols (HO-C6H4-OCH 3) and hydroxybenzaldehydes (HO-C6H4-CHO) can be interpreted. These studies have resulted in a predictive model that allows the interpretation of vanillin, a complex phenolic ether containing methoxy, hydroxy and aldehyde functional groups. This model will serve as a guide for the pyrolyses of larger systems including lignin monomers such as coniferyl alcohol. The pyrolysis mechanisms of the dimethoxybenzenes (H3C-C 6H4-OCH3) and syringol, a hydroxydimethoxybenzene have also been studied. These results will aid in the understanding of the thermal fragmentation of sinapyl alcohol, the most complex lignin monomer. In addition to the model compound work, pyrolyisis of biomass has been studied via the pulsed laser ablation of poplar wood. With the REMPI scheme, aromatic lignin decomposition

  10. Inhibition and kinetic studies of lignin degrading enzymes of Ganoderma boninense by naturally occurring phenolic compounds.

    Science.gov (United States)

    Surendran, Arthy; Siddiqui, Yasmeen; Saud, Halimi Mohd; Ali, Nusaibah Syd; Manickam, Sivakumar

    2018-05-22

    Lignolytic (Lignin degrading) enzyme, from oil palm pathogen Ganoderma boninense Pat. (Syn G. orbiforme (Ryvarden), is involved in the detoxification and the degradation of lignin in the oil palm and is the rate-limiting step in the infection process of this fungus. Active inhibition of lignin degrading enzymes secreted by G. boninense by various naturally occurring phenolic compounds and estimation of efficiency on pathogen suppression was aimed at. In our work, ten naturally occurring phenolic compounds were evaluated for their inhibitory potential towards the lignolytic enzymes of G.boninense. Additionally, the lignin degrading enzymes were characterised. Most of the peholic compounds exhibited an uncompetitive inhibition towards the lignin degrading enzymes. Benzoic acid was the superior inhibitor to the production of lignin degrading enzymes, when compared between the ten phenolic compounds. The inhibitory potential of the phenolic compounds toward the lignin degrading enzymes are higher than that of the conventional metal ion inhibitor. The lignin degrading enzymes were stable in a wide range of pH but were sensitive to higher to temperature. The study demonstrated the inhibitor potential of ten naturally occurring phenolic compounds toward the lignin degrading enzymes of G. boninense with different efficacies. The study has shed a light towards a new management strategy to control BSR in oil palm. It serves as replacement for the existing chemical control. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  11. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-03-30

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

  13. 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.

  14. 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.

  15. 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...

  16. Understanding the degree of condensation of phenolic and etherified C-9 units of in situ lignins.

    Science.gov (United States)

    Nanayakkara, Bernadette; Manley-Harris, Merilyn; Suckling, Ian D

    2011-12-14

    A novel approach for the quantification of the degree of condensation at the C(5) position of etherified and phenolic phenylpropane (C-9) units of in situ lignin is described. This is achieved by degrading unmethylated and methylated wood by thioacidolysis and analyzing the resultant product mixtures by quantitative (31)P NMR spectroscopy. Applying this new method to compression wood and normal wood from Pinus radiata showed that, whereas 41-47% of etherified guaiacyl C-9 units are condensed at the C(5) position, almost all phenolic guaiacyl C-9 units exist as uncondensed moieties. Analysis of milled wood lignin (MWL) isolated from the same wood by (31)P NMR spectroscopy before and after thioacidolysis showed that the phenolic guaiacyl C-9 units were more condensed than those in the in situ lignin. This is likely due to partial cleavage of the more condensed etherified linkages during the lignin isolation, leading to a relative increase in condensed phenolic guaiacyl C-9 units.

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

    Science.gov (United States)

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

    2017-05-01

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

  18. 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.

  19. Utilização de ligninas em resinas fenólicas: 1. Preparação de novolacas a partir de lignossulfonatos Use of lignins in phenolic resins: 1. Preparation of novolacs from lignosulfonates 49

    Directory of Open Access Journals (Sweden)

    Fernando dos Santos

    1999-01-01

    Full Text Available Este trabalho descreve uma utilização mais nobre para a lignina obtida de processos industriais de polpação. Foram preparadas resinas fenólicas tipo novolaca, utilizando-se lignossulfonato de amônio e lignossulfonato de sódio (com diferentes teores de açúcares residuais como correagentes, em substituição parcial ao fenol. As resinas foram preparadas mantendo-se o processo utilizado industrialmente. As resinas foram caracterizadas por análises químicas, quanto à distribuição de massa molar e análises térmicas. As resinas preparadas com lignossulfonatos apresentaram maior reatividade com hexametilenotetramina (agente de reticulação. Isto é uma vantagem, pois pode-se ter ciclos de moldagem de peças mais curtos, o que economicamente é favorável.This work describes the production of high value products using lignins obtained from industrial pulping processes. Novolac phenolic resins were prepared employing ammonium lignosulfonates and sodium lignosulfonates (with different residual sugar contents in a partial replacement of phenol. The resins were prepared using the same conditions employed in the industrial phenolic resins production. The lignin based resins were characterized by chemical analysis, molecular weight distribution and thermal analysis. The resins prepared using lignosulfonates showed higher reactivity with hexamethylenetetramine (crosslink agent. This behavior lead to another economic advantage as consequence of the reduction in the expended time for molding cycles.

  20. Lignin-derived oak phenolics: a theoretical examination of additional potential health benefits of red wine.

    Science.gov (United States)

    Setzer, William N

    2011-08-01

    Lignin-derived phenolic compounds can be extracted from oak barrels during the aging of red wine, and it is hypothesized that these compounds may contribute to the health benefits of red wine by their antioxidant, radical-scavenging, or chemopreventive activities. Density functional calculations (B3LYP/6-311++G) support the radical-scavenging abilities of the oak phenolics. Sinapaldehyde, syringaldehyde, syringol, and syringylacetone all have bond dissociation energies that are lower than resveratrol and comparable to the flavonoid catechin. Molecular docking studies of the oak phenolics with known resveratrol protein targets also show that these compounds dock favorably to the protein targets. Thus, lignin-derived oak phenolics, although found in small concentrations, may contribute to the beneficial antioxidant, chemopreventive, and cardioprotective effects of red wine.

  1. Birches against mineral oils. Lignin - a renewable resource for the alternative production of phenols; Birke contra Erdoel. Lignin - ein nachwachsender Rohstoff zur alternativen Gewinnung von Phenolen

    Energy Technology Data Exchange (ETDEWEB)

    Zehnpfund, C.; Bormann, J.; Wehrkamp zu Hoene, F. [Gymnasium Bersenbrueck (Germany)

    1998-02-01

    We wanted to offer an alternative for the `After-mineral oil time` with our work when we attempted to isolate phenols, which are won up to now from mineral oil, of a growing raw material. Phenols are economic important substances for production of epoxies, herbicides, artificial resins, dyes and drugs (e.g. aspirin or Paracetamol). We managed to isolate phenols with normal conditions of lignin, a component of wood. (orig.) [Deutsch] Wir wollten mit unserer Arbeit eine Alternative fuer die `Nach-Erdoel-Zeit` bieten, indem wir versuchten, Phenole, die bisher aus Erdoel gewonnen werden, aus einem nachwachsenden Rohstoff zu isolieren. Phenole sind volkswirtschaftlich bedeutsame Substanzen zur Herstellung von Kunststoffen, Herbiziden, Kunstharzen, Farbstoffen und Arzneimitteln (z.B. Aspirin oder Paracetamol). Es gelang uns, Phenole unter Normalbedingungen aus Lignin, einem Bestandteil des Holzes, zu isolieren. (orig.)

  2. 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.

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

    Science.gov (United States)

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

    2018-03-01

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

  4. Characterization and genomic analysis of kraft lignin biodegradation by the beta-proteobacterium Cupriavidus basilensis B-8

    Directory of Open Access Journals (Sweden)

    Shi Yan

    2013-01-01

    Full Text Available Abstract Background Lignin materials are abundant and among the most important potential sources for biofuel production. Development of an efficient lignin degradation process has considerable potential for the production of a variety of chemicals, including bioethanol. However, lignin degradation using current methods is inefficient. Given their immense environmental adaptability and biochemical versatility, bacterial could be used as a valuable tool for the rapid degradation of lignin. Kraft lignin (KL is a polymer by-product of the pulp and paper industry resulting from alkaline sulfide treatment of lignocellulose, and it has been widely used for lignin-related studies. Results Beta-proteobacterium Cupriavidus basilensis B-8 isolated from erosive bamboo slips displayed substantial KL degradation capability. With initial concentrations of 0.5–6 g L-1, at least 31.3% KL could be degraded in 7 days. The maximum degradation rate was 44.4% at the initial concentration of 2 g L-1. The optimum pH and temperature for KL degradation were 7.0 and 30°C, respectively. Manganese peroxidase (MnP and laccase (Lac demonstrated their greatest level of activity, 1685.3 U L-1 and 815.6 U L-1, at the third and fourth days, respectively. Many small molecule intermediates were formed during the process of KL degradation, as determined using GC-MS analysis. In order to perform metabolic reconstruction of lignin degradation in this bacterium, a draft genome sequence for C. basilensis B-8 was generated. Genomic analysis focused on the catabolic potential of this bacterium against several lignin-derived compounds. These analyses together with sequence comparisons predicted the existence of three major metabolic pathways: β-ketoadipate, phenol degradation, and gentisate pathways. Conclusion These results confirmed the capability of C. basilensis B-8 to promote KL degradation. Whole genomic sequencing and systematic analysis of the C. basilensis B-8 genome

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

    Science.gov (United States)

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

    2013-01-01

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

  6. Hydrodeoxygenation of phenols as lignin models under acid-free conditions with carbon-supported platinum catalysts.

    Science.gov (United States)

    Ohta, Hidetoshi; Kobayashi, Hirokazu; Hara, Kenji; Fukuoka, Atsushi

    2011-11-28

    Carbon-supported Pt catalysts are highly active and reusable for the aqueous-phase hydrodeoxygenation of phenols as lignin models without adding any acids. It is suggested that Pt/carbon facilitates the hydrogenation of phenols and the hydrogenolysis of the resulting cyclohexanols.

  7. Predicting dissolved lignin phenol concentrations in the coastal ocean from chromophoric dissolved organic matter (CDOM absorption coefficients

    Directory of Open Access Journals (Sweden)

    Cédric G. Fichot

    2016-02-01

    Full Text Available Dissolved lignin is a well-established biomarker of terrigenous dissolved organic matter (DOM in the ocean, and a chromophoric component of DOM. Although evidence suggests there is a strong linkage between lignin concentrations and chromophoric DOM (CDOM absorption coefficients in coastal waters, the characteristics of this linkage and the existence of a relationship that is applicable across coastal oceans remain unclear. Here, 421 paired measurements of dissolved lignin concentrations (sum of 9 lignin phenols and CDOM absorption coefficients (ag(λ were used to examine their relationship along the river-ocean continuum (0-37 salinity and across contrasting coastal oceans (sub-tropical, temperate, high-latitude. Overall, lignin concentrations spanned four orders of magnitude and revealed a strong, non-linear relationship with ag(λ. The characteristics of the relationship (shape, wavelength dependency, lignin-composition dependency and evidence from degradation indicators were all consistent with lignin being an important driver of CDOM variability in coastal oceans, and suggested physical mixing and long-term photodegradation were important in shaping the relationship. These observations were used to develop two simple empirical models for estimating lignin concentrations from ag(λ with a +/- 20% error relative to measured values. The models are expected to be applicable in most coastal oceans influenced by terrigenous inputs.

  8. Early diagenesis of mangrove leaves in a tropical estuary: Molecular-level analyses of neutral sugars and lignin-derived phenols

    Science.gov (United States)

    Benner, Ronald; Weliky, Karen; Hedges, John I.

    1990-07-01

    Leaves of the red mangrove, Rhizophora mangle, were collected from trees and submerged sediments in a tropical mangrove swamp in the Bahamas. Weight-to-area measurements indicated that the most highly degraded black-colored leaves had undergone a 36% loss in ash-free dry weight (AFDW). Green leaves were characterized by an abundance of cyclitols (8.5% AFDW), glucose-rich aldose mixtures (20% AFDW) and relatively low yields of lignin-derived phenols (2% AFDW). Cyclitols were rapidly lost from senescing and submerged decomposing leaves, whereas the overall yields of aldoses and lignin-derived phenols remained fairly constant throughout the various stages of leaf decay. Decomposition patterns were therefore unusual in that lignin was lost at about the same rate as polysaccharides. Variable loss rates were observed within the individual aldoses, indicating the following stability series (most to least stable) for submerged leaves: hemicelluloses > cellulose > pectins and gums. Compositional patterns of lignin-derived phenols remained fairly constant throughout decomposition and were characterized by unusually high acid-to-aldehyde ratios (0.4) in all leaf samples. A laboratory leaching experiment was conducted with senescent leaf material to estimate the contribution of leaching to the observed compositional patterns. Assuming the amounts and patterns of materials leached in the laboratory experiment were similar to those for field degraded leaves, we estimated that leaching could account for 58% of the mass loss, 97% of the cyclitol loss, 46% of the aldose polysaccharide loss and 74% of the lignin loss. Microbial degradation appeared to be responsible for about half of the overall mass and polysaccharide loss. Vanillyl phenols were leached in preference to syringyl phenols and the vanillic acid-to-vanillin ratio for the leachate was very high (0.7). These results indicate that high acid-to-aldehyde ratios are not necessarily indicative of microbial oxidation and

  9. Microbial degradation of plant leachate alters lignin phenols and trihalomethane precursors

    Science.gov (United States)

    Pellerin, Brian A.; Hernes, Peter J.; Saraceno, John Franco; Spencer, Robert G.M.; Bergamaschi, Brian A.

    2010-01-01

    Although the importance of vascular plant-derived dissolved organic carbon (DOC) in freshwater systems has been studied, the role of leached DOC as precursors of disinfection byproducts (DBPs) during drinking water treatment is not well known. Here we measured the propensity of leachates from four crops and four aquatic macrophytes to form trihalomethanes (THMs)—a regulated class of DBPs—before and after 21 d of microbial degradation. We also measured lignin phenol content and specific UV absorbance (SUVA254) to test the assumption that aromatic compounds from vascular plants are resistant to microbial degradation and readily form DBPs. Leaching solubilized 9 to 26% of total plant carbon, which formed 1.93 to 6.72 mmol THM mol C-1 However, leachate DOC concentrations decreased by 85 to 92% over the 21-d incubation, with a concomitant decrease of 67 to 92% in total THM formation potential. Carbon-normalized THM yields in the residual DOC pool increased by 2.5 times on average, consistent with the preferential uptake of nonprecursor material. Lignin phenol concentrations decreased by 64 to 96% over 21 d, but a lack of correlation between lignin content and THM yields or SUVA254 suggested that lignin-derived compounds are not the source of increased THM precursor yields in the residual DOC pool. Our results indicate that microbial carbon utilization alters THM precursors in ecosystems with direct plant leaching, but more work is needed to identify the specific dissolved organic matter components with a greater propensity to form DBPs and affect watershed management, drinking water quality, and human health.

  10. Production of oil palm (Elaeis guineensis) fronds lignin-derived non-toxic aldehyde for eco-friendly wood adhesive.

    Science.gov (United States)

    Hazwan Hussin, M; Samad, Noraini Abdul; Latif, Nur Hanis Abd; Rozuli, Nurul Adilla; Yusoff, Siti Baidurah; Gambier, François; Brosse, Nicolas

    2018-07-01

    Lignocellulosic materials can significantly contribute to the development of eco-friendly wood adhesives. In this work, glyoxal-phenolic resins for plywood were prepared using organosolv lignin, which was isolated from black liquor recovered from organosolv pulping of oil palm fronds (OPF) and considered to be an alternative to phenol. Glyoxal, which is a dialdehyde obtained from several natural resources, was used as substitute for formaldehyde. The structure of organosolv lignin and the resins were characterized by FTIR and NMR, and for thermal stability by TGA and DSC. The resins were further studied for their viscosity, pH, solids content and gel times. The resins performance as wood adhesive was further established from mechanical test in terms of tensile strength and modulus of elasticity (MOE) to obtain the optimum ratios of organosolv lignin, which replaces phenol in organosolv lignin phenol glyoxal (OLPG) resins. The adhesive composition having 50% (w/w) of phenol substituted by organosolv lignin, termed as 50% OLPG showed highest adhesive strength compared to phenol formaldehyde (PF) commercial adhesive. Copyright © 2018 Elsevier B.V. All rights reserved.

  11. 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...

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

    Science.gov (United States)

    Li, Dongbing; Briens, Cedric; Berruti, Franco

    2015-01-01

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

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

    Science.gov (United States)

    Hill Bembenic, Meredith A.

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

  14. 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.

  15. 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.

  16. 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.

  17. 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...

  18. Direct rate assessment of laccase catalysed radical formation in lignin by electron paramagnetic resonance spectroscopy

    DEFF Research Database (Denmark)

    Munk, Line; Andersen, Mogens Larsen; Meyer, Anne S.

    2017-01-01

    Laccases (EC 1.10.3.2) catalyse removal of an electron and a proton from phenolic hydroxyl groups, including phenolic hydroxyls in lignins, to form phenoxy radicals during reduction of O2. We employed electron paramagnetic resonance spectroscopy (EPR) for real time measurement of such catalytic...... to suspensions of the individual lignin samples produced immediate time and enzyme dose dependent increases in intensity in the EPR signal with g-values in the range 2.0047–2.0050 allowing a direct quantitative monitoring of the radical formation and thus allowed laccase enzyme kinetics assessment on lignin...... for the radical formation rate in organosolv lignin was determined by response surface methodology to pH 4.8, 33 °C and pH 5.8, 33 °C for the Tv laccase and the Mt laccase, respectively. The results verify direct radical formation action of fungal laccases on lignin without addition of mediators and the EPR...

  19. The minor wall-networks between monolignols and interlinked-phenolics predominantly affect biomass enzymatic digestibility in Miscanthus.

    Directory of Open Access Journals (Sweden)

    Zhengru Li

    Full Text Available Plant lignin is one of the major wall components that greatly contribute to biomass recalcitrance for biofuel production. In this study, total 79 representative Miscanthus germplasms were determined with wide biomass digestibility and diverse monolignol composition. Integrative analyses indicated that three major monolignols (S, G, H and S/G ratio could account for lignin negative influence on biomass digestibility upon NaOH and H2SO4 pretreatments. Notably, the biomass enzymatic digestions were predominately affected by the non-KOH-extractable lignin and interlinked-phenolics, other than the KOH-extractable ones that cover 80% of total lignin. Furthermore, a positive correlation was found between the monolignols and phenolics at p<0.05 level in the non-KOH-extractable only, suggesting their tight association to form the minor wall-networks against cellulases accessibility. The results indicated that the non-KOH-extractable lignin-complex should be the target either for cost-effective biomass pretreatments or for relatively simply genetic modification of plant cell walls in Miscanthus.

  20. 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.

  1. The minor wall-networks between monolignols and interlinked-phenolics predominantly affect biomass enzymatic digestibility in Miscanthus.

    Science.gov (United States)

    Li, Zhengru; Zhao, Chunqiao; Zha, Yi; Wan, Can; Si, Shengli; Liu, Fei; Zhang, Rui; Li, Fengcheng; Yu, Bin; Yi, Zili; Xu, Ning; Peng, Liangcai; Li, Qing

    2014-01-01

    Plant lignin is one of the major wall components that greatly contribute to biomass recalcitrance for biofuel production. In this study, total 79 representative Miscanthus germplasms were determined with wide biomass digestibility and diverse monolignol composition. Integrative analyses indicated that three major monolignols (S, G, H) and S/G ratio could account for lignin negative influence on biomass digestibility upon NaOH and H2SO4 pretreatments. Notably, the biomass enzymatic digestions were predominately affected by the non-KOH-extractable lignin and interlinked-phenolics, other than the KOH-extractable ones that cover 80% of total lignin. Furthermore, a positive correlation was found between the monolignols and phenolics at pnetworks against cellulases accessibility. The results indicated that the non-KOH-extractable lignin-complex should be the target either for cost-effective biomass pretreatments or for relatively simply genetic modification of plant cell walls in Miscanthus.

  2. 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

  3. New techniques for the characterization of lignins

    International Nuclear Information System (INIS)

    Javor, T.

    2001-09-01

    In the present work new techniques for the characterization of lignins, ligninsulfonates as well as lignin degradation products with capillary electrophoresis (CE), size exclusion chromatography (SEC) and mass spectrometry (ESI-MS, APCI-MS and MALDI-MS) are described. After an overview on wood and wood pulping the development of microemulsion electrokinetic chromatography (MEEKC) for the investigation of low-molecular-mass lignin degradation compounds is described. This method is suited for the analysis of phenolic compounds as well as for non-phenolic compounds in this kind of samples. Using a carrier electrolyte system consisting of 1-butanol/n-heptane/sodiumdodeylsulfate (SDS)/20 mM borate (6.61/0.81/1.66/90,29 % (w/w)) pH 9.2 it was possible to separate 14 lignin degradation compounds (2-methoxyphenol, 3,4,5-trimethoxyphenol, 2,6-dimethoxyphenol, 3,4-dimethoxybenzaldehyde, 3,4-dimethoxyacetophenone, 3,4,5-trimethoxybenzaldehyde, 3,4,5-trimethoxyacetophenone, 3-(3,4-dimethoxyphenyl)-2-propen-1-ol, 4-methoxyacetophenone, 3,5-Dimethoxy-4-hydroxyacetophenone, acetovanillone, syringaldehyde, vanillin, 4-hydroxybenzaldehyde and 1-(3-methoxy-4-hydroxyphenyl)-2-(2-methoxyphenoxy)-ethanol). In addition the advantages and disadvantages of microemulsions are discussed in comparison with carrier electrolytes containing micelles. Subsequently, the results from size exclusion chromatographic measurements are presented. SEC using modern high-performance poly(styrene-divinylbenzene) gels as stationary phase and 0.1 M NaOH as mobile phase allows efficient separations and good characterization of lignins and ligninsulfonates. Adsorption effects are practical negligible. SEC yields results which are independent of the charge of lignins or ligninsulfonates, so that this technique looks complementary to capillary electrophoresis. For the characterization of intact lignins and ligninsulfonates by capillary zone electrophoretic techniques, carrier electrolytes in the the pH range 10

  4. 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

  5. Study of the interactions between Eu(III) and Al2O3 particles in the presence of phenolic acids

    International Nuclear Information System (INIS)

    Moreau, P.

    2012-01-01

    In the framework of environmental pollution by radionuclides, this work was focused on the interactions occurring in systems containing europium(III) - as a chemical analogue for the actinides Am(III) and Cm(III) -, phenolic acids - lignin degradation products and anti-fungi, naturally occurring in soils, and alumina - representative of sorption sites found in the environment. This study was conducted at different scales of description: the macroscopic scale - to quantify Eu(III) and/or phenolic acids adsorption onto the mineral surface -, and the microscopic scale - to study the chemical environment of Eu(III) using Time-Resolved Luminescence Spectroscopy (TRLS). First, the binary systems, i.e. systems containing only two entities among the three previously cited, were characterized. Complexation constants of Eu(III) by three phenolic acids (4-hydroxybenzoic, 3,4-dihydroxybenzoic, and 3,4,5-trihydroxybenzoic acids) were determined and quantum calculations (DFT) were carried out on La(III)-acid complex analogues. Sorption of the acids onto aluminol sites was modelled using surface complexation concepts. Analyses of two ternary systems (containing 4-hydroxybenzoic and 3,4-dihydroxybenzoic acids) revealed synergistic processes for Eu(III) and phenolic acids sorption onto Al 2 O 3 . A spectral fingerprint of ternary complex involving Eu(III)/4-hydroxybenzoic acid/Al 2 O 3 surface sites was evidenced. (author) [fr

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

    Directory of Open Access Journals (Sweden)

    Wen Hua

    2016-01-01

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

  7. Lignin conversion to high-octane fuel additives

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-07-01

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

  8. 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

  9. 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

  10. 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...

  11. 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

  12. 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

  13. 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.

  14. A new antifungal phenolic glycoside derivative, iridoids and lignans from Alibertia sessilis (vell.) K. Schum. (Rubiaceae)

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Viviane C. da; Bolzani, Vanderlan da S.; Lopes, Marcia N. [UNESP, Araraquara, SP (Brazil). Inst. de Quimica. Dept. de Quimica Organica]. E-mail: mnlopes@iq.unesp.br; Young, Maria C.M. [Instituto de Botanica, Sao Paulo, SP (Brazil). Secao de Fisiologia e Bioquimica de Plantas

    2007-07-01

    A new antifungal phenolic glycoside, 3,4,5-trimethoxyphenyl-1-O-{beta}-D-(5-O-syringoyl)apiofuranosyl-(1 {yields} 6)-{beta}-D-glucopyranoside (1), together with four known iridoids, geniposidic acid (2), geniposide (3), 6{alpha}-hydroxygeniposide (4) and 6{beta}-hydroxygeniposide (5); two lignans, (+)-lyoniresinol-3{alpha}-O-{beta}-D-glucopyranoside (6), (-)-lyoniresinol-3{alpha}-O-{beta}-D-glucopyranoside (7); and two phenolic acids, chlorogenic (8) and salicylic acids (9) and D-manitol (10), were isolated from the ethanolic extract of the stems of Alibertia sessilis. Structures of 1 and of the known compounds were determined by spectroscopic analysis. All compounds isolated were evaluated for their antifungal activities against two phytopathogenic fungi strains Cladosporium cladosporioides and C. sphaerospermum by direct bioautography. (author)

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

    Directory of Open Access Journals (Sweden)

    Ramos Rose Lucia Braz

    2001-01-01

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

  16. 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.

  17. 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.

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

    Directory of Open Access Journals (Sweden)

    Lu Fachuang

    2010-06-01

    of ester group hydroxylation. Conclusion Overall, monolignol substitutes improved the inherent degradability of non-pretreated cell walls by restricting lignification or possibly by reducing lignin hydrophobicity or cross-linking to structural polysaccharides. Furthermore some monolignol substitutes, chiefly readily cleaved bi-phenolic conjugates like epigallocatechin gallate or diferuloyl polyol esters, are expected to greatly boost the enzymatic degradability of cell walls following chemical pretreatment. In ongoing work, we are characterizing the enzymatic saccharification of intact and chemically pretreated cell walls lignified by these and other monolignol substitutes to identify promising genetic engineering targets for improving plant fiber utilization.

  19. Aromatic products from reaction of lignin model compounds with UV-alkaline peroxide

    International Nuclear Information System (INIS)

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

    1997-01-01

    A series of guaiacyl and syringyl lignin model compounds and their methylated analogues were reacted with alkaline hydrogen peroxide while irradiating with UV light at 254 nm. The aromatic products obtained were investigated by gas chromatography-mass spectrometry (GC-MS). Guaiacol, syringol and veratrol gave no detectable aromatic products. However, syringol methyl ether gave small amounts of aromatic products, resulting from ring substitution and methoxyl displacement by hydroxyl radicals. Reaction of vanillin and syringaldehyde gave the Dakin reaction products, methoxy-1,4-hydroquinones, while reaction of their methyl ethers yielded benzoic acids. Acetoguaiacone, acetosyringone and their methyl ethers afforded several hydroxylated aromatic products, but no aromatic products were identified in the reaction mixtures from guaiacylpropane and syringylpropane. In contrast, veratrylpropane gave a mixture from which 17 aromatic hydroxylated compounds were identified. It is concluded that for phenolic lignin model compounds, particularly those possessing electrondonating aromatic ring substituents, ring-cleavage reactions involving superoxide radical anions are dominant, whereas for non-phenolic lignin models, hydroxylation reactions through attack of hydroxyl radicals prevail

  20. Significance of Lignin S/G Ratio in Biomass Recalcitrance of Populus trichocarpa Variants for Bioethanol Production

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Chang Geun [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; UT−ORNL; Dumitrache, Alexandru [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; Muchero, Wellington [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; Natzke, Jace [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; Akinosho, Hannah [School; Li, Mi [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; UT−ORNL; Sykes, Robert W. [National Renewable Energy Laboratory, U.S. Department of Energy, 15013 Denver West Parkway, Golden, Colorado 80401, United States; Brown, Steven D. [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; Davison, Brian [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; Tuskan, Gerald A. [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; Pu, Yunqiao [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; UT−ORNL; Ragauskas, Arthur J. [BioEnergy; amp, Center for BioEnergy Innovation, Biosciences; UT−ORNL; Department; amp, Center for Renewable

    2017-12-27

    Lignin S/G ratio has been investigated as an important factor in biomass recalcitrance to bioethanol production. Because of the complexity and variety of biomass, recalcitrance was also reportedly influenced by several other factors, such as total lignin content, degree of cellulose polymerization, etc. In addition, the effect of S/G ratio on biomass conversion is not uniform across plant species. Herein, 11 Populus trichocarpa natural variants grown under the same conditions with similar total lignin content were selected to minimize the effects of other factors. The lignin S/G ratio of the selected P. trichocarpa natural variants showed negative correlations with p-hydroxybenzoate (PB) and ..beta..-5 linkage contents, while it had positive ones with ..beta..-O-4 linkage, lignin molecular weight, and ethanol production. This study showed the importance of lignin S/G ratio as an independent recalcitrance factor that may aid future energy crop engineering and biomass conversion strategies.

  1. Bio-inspired MOF-based Catalysts for Lignin Valorization.

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-09-01

    for the C-O bond hydrogenolysis in model compounds, which mimic the b-O-4, a-O-4, and 4-O-5 linkages of natural lignin. The versatile IRMOF-74(n) series is proposed as a platform for creating efficient hydrogenolysis catalysts as it not only displays tunable pore sizes, but also has the required thermal and chemical stability. The catalytic C-O bond cleavage occurs at 10 bar hydrogen pressure and temperatures as low as 120 degC. The conversion efficiency of the aromatic ether substrates into the corresponding hydrocarbons and phenols varies as PhCH 2 CH 2 OPh > PhCH 2 OPh > PhOPh (Ph = phenyl), while the catalytic activity generally follows the following trend Ni@IRMOF-74>Ti@IRMOF-74>IRMOF-74. Conversions as high as 80%, coupled with good selectivity for hydrogenolysis vs. hydrogenation, highlight the potential of MOF-based catalysts for the selective cleavage of recalcitrant aryl-ether bonds found in lignin and other biopolymers. This project supports the DOE Integrated Biorefinery Program goals, the objective of which is to convert biomass to fuels and high-value chemicals, by addressing an important technology gap: the lack of low-temperature catalysts suitable for industrial lignin degradation. Biomass, which is %7E30 wt% lignin, constitutes a potentially major source of platform chemicals that could improve overall profitability and productivity of all energy-related products, thereby benefiting consumers and reducing national dependence on imported oil. Additionally, DoD has a strong interest in low-cost drop-in fuels (Navy Biofuel Initiative) and has signed a Memorandum of Understanding with DOE and USDA to develop a sustainable biofuels industry.

  2. Structural Alterations of Lignins in Transgenic Poplars with Depressed Cinnamyl Alcohol Dehydrogenase or Caffeic Acid O-Methyltransferase Activity Have an Opposite Impact on the Efficiency of Industrial Kraft Pulping1

    Science.gov (United States)

    Lapierre, Catherine; Pollet, Brigitte; Petit-Conil, Michel; Toval, Gabriel; Romero, Javier; Pilate, Gilles; Leplé, Jean-Charles; Boerjan, Wout; Ferret, Valérie; De Nadai, Véronique; Jouanin, Lise

    1999-01-01

    We evaluated lignin profiles and pulping performances of 2-year-old transgenic poplar (Populus tremula × Populus alba) lines severely altered in the expression of caffeic acid/5-hydroxyferulic acid O-methyltransferase (COMT) or cinnamyl alcohol dehydrogenase (CAD). Transgenic poplars with CAD or COMT antisense constructs showed growth similar to control trees. CAD down-regulated poplars displayed a red coloration mainly in the outer xylem. A 90% lower COMT activity did not change lignin content but dramatically increased the frequency of guaiacyl units and resistant biphenyl linkages in lignin. This alteration severely lowered the efficiency of kraft pulping. The Klason lignin level of CAD-transformed poplars was slightly lower than that of the control. Whereas CAD down-regulation did not change the frequency of labile ether bonds or guaiacyl units in lignin, it increased the proportion of syringaldehyde and diarylpropane structures and, more importantly with regard to kraft pulping, of free phenolic groups in lignin. In the most depressed line, ASCAD21, a substantially higher content in free phenolic units facilitated lignin solubilization and fragmentation during kraft pulping. These results point the way to genetic modification of lignin structure to improve wood quality for the pulp industry. PMID:9880356

  3. 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

  4. 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.

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

    Science.gov (United States)

    Zhao, Shou; Abu-Omar, Mahdi M

    2015-07-13

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

  6. 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...

  7. Reactivity of lignin with different composition of aromatic syringyl/guaiacyl structures and erythro/threo side chain structures in β-O-4 type during alkaline delignification: as a basis for the different degradability of hardwood and softwood lignin.

    Science.gov (United States)

    Shimizu, Satoko; Yokoyama, Tomoya; Akiyama, Takuya; Matsumoto, Yuji

    2012-07-04

    The reactivity of lignin during alkaline delignification was quantitatively investigated focusing on the effect of the structural differences between syringyl and guaiacyl aromatic nuclei and between erythro and threo in the side chain of β-O-4 type lignin substructure on the β-O-4 bond cleavage rate. It was known that the ratio of this reaction rate of the erythro to threo isomers of the dimeric β-O-4 type lignin model compound with two guaiacyl aromatic nuclei was ca. 4. However, the presence of a syringyl nucleus strongly influenced the rate, and the ratio of the syringyl type analogue was in the range between 2.7 and 8.0 depending on the reaction temperature. The effect of syringyl nucleus on the enhancement of the reaction rate appeared to be greater when the syringyl nucleus consists of the cleaving ether bond rather than being a member of the carbon framework.

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

    Science.gov (United States)

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

    2013-03-01

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

  9. Pd/TOMPP-catalysed telomerisation of 1,3-butadiene with lignin-type phenols and thermal Claisen rearrangement of linear telomers

    NARCIS (Netherlands)

    Hausoul, P.J.C.; Tefera, S.D.; Blekxtoon, J.; Bruijnincx, P.C.A.; Klein Gebbink, R.J.M.; Weckhuysen, B.M.

    2013-01-01

    The Pd/TOMPP-catalysed (TOMPP = tris(2-methoxyphenyl)phosphine) telomerisation of 1,3-butadiene was studied under solvent- and base-free conditions with phenolic substrates that can be potentially derived from lignin. Large differences in catalytic activity were observed, with reactivity increasing

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

    Science.gov (United States)

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

    2018-01-01

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

  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. Catalytic hydroprocessing of lignin β-O-4 ether bond model compound phenethyl phenyl ether over ruthenium catalysts

    NARCIS (Netherlands)

    Gomez-Monedero, B.; Faria, J.; Bimbela, F.; Ruiz, M.P.

    2017-01-01

    The catalytic hydroprocessing of phenethyl phenyl ether (PPE), a model compound of one of the most significant ether linkages within lignin structure, β-O-4, has been studied. Reactions were carried out using two ruthenium-based catalysts, supported on different materials: 3.8 wt.% Ru/C and 3.9 wt.%

  13. 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.

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

    Science.gov (United States)

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

    2015-12-07

    Lignin derivatives, which arise as waste products from the pulp and paper industry and are mainly used for heating, can be used as charge storage materials. The charge storage function is a result of the quinone groups formed in the lignin derivative. Herein, we modified lignins to enhance the density of such quinone groups by covalently linking monolignols and quinones through phenolation. The extra guaiacyl, syringyl, and hydroquinone groups introduced by phenolation of kraft lignin derivatives were monitored by (31) P nuclear magnetic resonance and size exclusion chromatography. Electropolymerization in ethylene glycol/tetraethylammonium tosylate electrolyte was used to synthesize the kraft lignin/polypyrrole hybrid films. These modifications changed the phenolic content of the kraft lignin with attachment of hydroquinone units yielding the highest specific capacity (around 70 mA h g(-1) ). The modification of softwood and hardwood lignin derivatives yielded 50 % and 23 % higher charge capacity than the original lignin, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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.

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

    Directory of Open Access Journals (Sweden)

    Shengming Zhang

    2017-07-01

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

  17. 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.

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

    Science.gov (United States)

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

    2018-01-23

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

  19. Electrochemical Study of Iodide in the Presence of Phenol and o-Cresol: Application to the Catalytic Determination of Phenol and o-Cresol

    Directory of Open Access Journals (Sweden)

    Davood Nematollahi

    2004-11-01

    Full Text Available Abstract: The electrochemical oxidation of iodide in the presence of phenol and o-cresol was investigated at a glassy carbon electrode in buffered media by cyclic voltammetry, linear sweep voltammetry and controlled–potential coulometry. The experimental results indicate that the phenol and o-cresol convert to their derivatives after participating in a halogenation coupled reaction (quasi-catalytic reaction following the oxidation of iodide to iodine. The concentrations of phenol and o-cresol have been determined in aqueous solutions according to the linear dependence of quasi-catalytic peak currents with the concentration. The calibration graphs show two linear sections of 0.0 to 1.0×10-4 M and 2.0×10-4 to 1.0 ×10-3 M for phenol and 4.2×10-5 to 1.0×10-4 M and 2.0×10-4 to 1.0×10-3 M for o-cresol. The theoretical detection limits and the relative standard deviations for ten measurements of phenol and o-cresol are 1.125×10-5 M, 1.06% and 4.201×10-5 M, 1.44%, respectively.

  20. 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.

  1. 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....

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

  3. Application of mesoporous Al-MCM-48 material to the conversion of lignin.

    Science.gov (United States)

    Lee, Hyung Won; Lee, In-Gu; Park, Sung Hoon; Jeon, Jong-Ki; Suh, Dong Jin; Jung, Jinho; Park, Young-Kwon

    2014-04-01

    Al-MCM-48 was applied to the catalytic pyrolysis of lignin for the first time. The pyrolysis reaction and in-situ product were analyzed by pyrolysis gas chromatography/mass spectrometry. The main products of the non-catalytic pyrolysis of lignin were phenols. The use of Al-MCM-48 increased the production of light phenols considerably. The yields of high-value-added compounds, such as hydrocarbons and aromatics, were also increased by catalytic upgrading. Al-MCM-48 is believed to promote cracking, aromatization and deoxygenation, such as decarbonylation. On the other hand, Si-MCM-48, which has no acid sites, showed lower deoxygenation efficiency than Al-MCM-48. Al-MCM-48 could be regenerated by calcining in air.

  4. 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.

  5. Sesquiterpenoids and phenolics from Taraxacum hondoense.

    Science.gov (United States)

    Kisiel, Wanda; Michalska, Klaudia

    2005-09-01

    Eleven sesquiterpene lactones, including the new guaianolide 11beta-hydroxydeacetylmatricarin-8-O-beta-glucopyranoside, along with four known phenolic glucosides were isolated from Taraxacum hondoense. The compounds were characterized by spectral methods.

  6. 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...

  7. Degradation of p-Nitrophenol by Lignin and Cellulose Chars: H2O2-Mediated Reaction and Direct Reaction with the Char.

    Science.gov (United States)

    Yang, Jing; Pignatello, Joseph J; Pan, Bo; Xing, Baoshan

    2017-08-15

    Chars and other black carbons are reactive toward certain compounds. Such reactivity has been attributed to reduction of O 2 by persistent free radicals in the solid to H 2 O 2 , which then back-reacts with the solid to generate reactive oxygen species (ROS; especially HO • ). We studied the decomposition of p-nitrophenol (PNP) by pure lignin and cellulose chars aged in moist air or a vacuum at room temperature for up to a month. In air, the chars chemisorbed oxygen, a portion of which was liberated as H 2 O 2 when the char was submerged in water. The evolved H 2 O 2 was simultaneously decomposed by the char. PNP reacted predominantly in the sorbed state and only reduction products (phenol, catechol) were identified. Aging the char in air sharply (within hours) reduced H 2 O 2 -producing capacity and free radical concentration, but more gradually reduced PNP decay rate over the month-long period. PNP decay was only modestly suppressed (12-30%) by H 2 O 2 removal (catalase), and had little effect on the free radical signal (reactive sites. Lignin char was generally more reactive than cellulose char. The Fe impurity in lignin played no role. The results are relevant to the fate of pollutants in black carbon-rich environments and the use of carbons in remediation.

  8. [Phenolic acid derivatives from Bauhinia glauca subsp. pernervosa].

    Science.gov (United States)

    Zhao, Qiao-Li; Wu, Zeng-Bao; Zheng, Zhi-Hui; Lu, Xin-Hua; Liang, Hong; Cheng, Wei; Zhang, Qing-Ying; Zhao, Yu-Ying

    2011-08-01

    To study the chemical constituents of Bauhinia glauca subsp. pernervosa, eleven phenolic acids were isolated from a 95% ethanol extract by using a combination of various chromatographic techniques including column chromatography over silica gel, ODS, MCI, Sephadex LH-20, and semi-preparative HPLC. By spectroscopic techniques including 1H NMR, 13C NMR, 2D NMR, and HR-ESI-MS, these compounds were identified as isopropyl O-beta-(6'-O-galloyl)-glucopyranoside (1), ethyl O-beta-(6'-O-galloyl)-glucopyranoside (2), 3, 4, 5-trimethoxyphenyl-(6'-O-galloyl)-O-beta-D-glucopyranoside (3), 3, 4, 5-trimethoxyphenyl-beta-D-glucopyranoside (4), gallic acid (5), methyl gallate (6), ethyl gallate (7), protocatechuic acid (8), 3, 5-dimethoxy-4-hydroxybenzoic acid (9), erigeside C (10) and glucosyringic acid (11). Among them, compound 1 is a new polyhydroxyl compound; compounds 2, 10, and 11 were isolated from the genus Bauhinia for the first time, and the other compounds were isolated from the plant for the first time. Compounds 6 and 8 showed significant protein tyrosine phosphatase1B (PTP1B) inhibitory activity in vitro with the IC50 values of 72.3 and 54.1 micromol x L(-1), respectively.

  9. Selective degradation of lignin and elimination of HO radicals in pulps by O3 and UV laser flash irradiation

    Institute of Scientific and Technical Information of China (English)

    林鹿; 周贤涛; 邱玉桂

    2002-01-01

    HO radical is an aggressive reagent to abstract hydrogen from diverse substitutes and lead them to degradation, however, in reaction of active oxygen species with lignins, complex phenolic polymers, in dispersed lignocellulose such as pulp for environment-benign delignification, HO radicals should be eliminated as more as possible to prevent cellulose from unfavorably concomitant degradation. A reaction system of O3 is constructed under UV laser flash irradiation, and HO radicals are controlled efficiently by it. A new mechanism is proposed, for the first time, that O radicals generated from reaction of O3 with UV laser flash irradiation might be the contributor to scavenge HO radicals.

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

    Science.gov (United States)

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

    2017-06-01

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

  11. A new phenolic glycoside from the aerial parts of Solidago canadensis.

    Science.gov (United States)

    Zhang, JinSong; Zhang, XinQin; Lei, GuangQing; Li, Bo; Chen, JiaKuan; Zhou, TongShui

    2007-01-01

    A new phenolic glycoside, 2'-hydroxy-4',6'-di-O-beta-D-glucopyranosyl-butyrrophenone (1), was isolated from the aerial parts of Solidago canadensis. The structure was elucidated on the basis of spectroscopic methods.

  12. 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.

  13. A facile one-pot preparation of Co3O4/g-C3N4 heterojunctions with excellent electrocatalytic activity for the detection of environmental phenolic hormones

    Science.gov (United States)

    Sun, Yanjuan; Jiang, Jizhou; Liu, Yi; Wu, Shengli; Zou, Jing

    2018-02-01

    The Co3O4/g-C3N4 heterojunctions were prepared by a facile one-pot thermal decomposition technique. Compared with g-C3N4, it was found that Co3O4/g-C3N4 heterojunctions possessed a higher Brunner-Emmet-Teller (BET) surface area, which was beneficial to the diffusion of aim molecules on the electrode surfaces. And the optimal Co3O4/g-C3N4 heterojunctions exhibited a narrower band gap and a higher donor density, resulting in an excellent electrocatalytic activity for environmental phenolic hormones. Moreover, the Co3O4/g-C3N4 heterojunctions were used for the electrochemical sensing of environmental phenolic hormones such as bisphenol A, pentachlorophenol, p-nitrophenol and octylphenol. All detection ranges reached three orders of magnitude, showing a lower limit of detection of 10-9 mol L-1. So, sensitivity and accurate determination of environmental phenolic hormones in real water samples may use this Co3O4/g-C3N4 heterojunctions modified electrode.

  14. 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

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

    Directory of Open Access Journals (Sweden)

    Xiaona Lin

    2015-06-01

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

  16. High Selectively Catalytic Conversion of Lignin-Based Phenols into para-/m-Xylene over Pt/HZSM-5

    Directory of Open Access Journals (Sweden)

    Guozhu Liu

    2016-01-01

    Full Text Available High selectively catalytic conversion of lignin-based phenols (m-cresol, p-cresol, and guaiacol into para-/m-xylene was performed over Pt/HZSM-5 through hydrodeoxygenation and in situ methylation with methanol. It is found that the p-/m-xylene selectivity is uniformly higher than 21%, and even increase up to 33.5% for m-cresol (with phenols/methanol molar ratio of 1/8. The improved p-/m-xylene selectivity in presence of methanol is attributed to the combined reaction pathways: methylation of m-cresol into xylenols followed by HDO into p-/m-xylene, and HDO of m-cresol into toluene followed by methylation into p-/m-xylene. Comparison of the product distribution over a series of catalysts indicates that both metals and supporters have distinct effect on the p-/m-xylene selectivity.

  17. ZnAl2O4@SiO2 nanocomposite catalyst for the acetylation of alcohols, phenols and amines with acetic anhydride under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Saeed Farhadi; Kosar Jahanara

    2014-01-01

    A ZnAl2O4@SiO2 nanocomposite was prepared from metal nitrates and tetraethyl orthosilicate by the sol-gel process, and characterized by X-ray diffraction, Fourier transform infrared, transmission electron microscopy, and N2 adsorption-desorption measurements. The nanocomposite was tested as a heterogeneous catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions. Under optimized conditions, efficient acetylation of these substrates with acetic anhy-dride over the ZnAl2O4@SiO2 nanocomposite was obtained. Acetylation of anilines and primary aliphatic amines proceeded rapidly at room temperature, while the reaction time was longer for the acetylation of alcohols and phenols, showing that an amine NH2 group can be selectively acetylated in the presence of alcoholic or phenolic OH groups. The catalyst can be reused without obvious loss of catalytic activity. The catalytic activity of the ZnAl2O4@SiO2 nanocomposite was higher than that of pure ZnAl2O4. The method gives high yields, and is clean, cost effective, compatible with sub-strates having other functional groups and it is suitable for practical organic synthesis.

  18. 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-...

  19. 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.

  20. Characterization of changes of lignin structure in the processes of cooking with solid alkali and different active oxygen.

    Science.gov (United States)

    Yang, Qiulin; Shi, Jianbin; Lin, Lu; Peng, Lincai; Zhuang, Junping

    2012-11-01

    The cooking with solid alkali and active oxygen has a high selectivity for delignification. In the present work, the O(2) and H(2)O(2) were separately combined with MgO used in cornstalk cooking for investigating their effects on delignification. After cooking, the lignins in raw material, pulp, and yellow liquor were all characterized by HSQC NMR. The results showed that the syringyl (S/S'/S″) units and β-O-4' (A/A'/A″) structures had different reactivity in the cooking with MgO and H(2)O(2) due to their different structures on side-chains. Whereas the syringyl (S/S'/S″) units could be completely decomposed when the MgO and O(2) were used, and the β-O-4' (A/A'/A″) structures could be partly degraded. A novel structure G' unit with a carbonyl group was only generated in the cooking with MgO and O(2). In addition, the H unit, non-phenolic β-β' (B) and β-5' (C) structures were all stable in both of the two cooking processes. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

  1. 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

  2. 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

  3. Lignin Valorisation for Chemicals and (Transportation) Fuels via (Catalytic) Pyrolysis and Hydrodeoxygenation

    NARCIS (Netherlands)

    de Wild, Paul; Van der Laan, Ron; Kloekhorst, Arjan; Heeres, Hero

    2009-01-01

    New technology is needed to exploit the potential of lignin as a renewable feedstock for fuels, chemicals and performance products. Fast fluidized bed pyrolysis of different lignins at 400 degrees C yields up to 2.1 wt% (d.b.) of a phenolic fraction containing 10 wt%, (d.b.) of several phenols.

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

    Directory of Open Access Journals (Sweden)

    Heber dos Santos Abreu

    1997-12-01

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

  5. 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.

  6. 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.

  7. 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.

  8. [Determination methods for the content of methyl salicylate-2-O-beta-D-galactopyranoside (1-4)-beta-D-glucopyranoside].

    Science.gov (United States)

    He, Xiu-Feng; Xia, Peng-Fei; Wang, Ai-Guo; Liu, Dong; Zhao, Li-Min

    2012-07-01

    The paper is to report the establishment of three methods for determination of methyl salicylate-2-O-beta-D-galactopyranoside (1-4)-beta-D-glucopyranoside (MSG) by HPLC, UV or potentiometric titration. The results determined by the three methods turned out to be of no significant difference (P>0.05). The method was chosen according to MSG difference test demands.

  9. 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

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

    Science.gov (United States)

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

    2003-01-21

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

  11. 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...

  12. [Effect of phenolic ketones on ethanol fermentation and cellular lipid composition of Pichia stipitis].

    Science.gov (United States)

    Yang, Jinlong; Cheng, Yichao; Zhu, Yuanyuan; Zhu, Junjun; Chen, Tingting; Xu, Yong; Yong, Qiang; Yu, Shiyuan

    2016-02-01

    Lignin degradation products are toxic to microorganisms, which is one of the bottlenecks for fuel ethanol production. We studied the effects of phenolic ketones (4-hydroxyacetophenone, 4-hydroxy-3-methoxy-acetophenone and 4-hydroxy-3,5-dimethoxy-acetophenone) derived from lignin degradation on ethanol fermentation of xylose and cellular lipid composition of Pichia stipitis NLP31. Ethanol and the cellular fatty acid of yeast were analyzed by high performance liquid chromatography (HPLC) and gas chromatography/mass spectrometry (GC/MS). Results indicate that phenolic ketones negatively affected ethanol fermentation of yeast and the lower molecular weight phenolic ketone compound was more toxic. When the concentration of 4-hydroxyacetophenone was 1.5 g/L, at fermentation of 24 h, the xylose utilization ratio, ethanol yield and ethanol concentration decreased by 42.47%, 5.30% and 9.76 g/L, respectively, compared to the control. When phenolic ketones were in the medium, the ratio of unsaturated fatty acids to saturated fatty acids (UFA/SFA) of yeast cells was improved. When 1.5 g/L of three aforementioned phenolic ketones was added to the fermentation medium, the UFA/SFA ratio of yeast cells increased to 3.03, 3.06 and 3.61, respectively, compared to 2.58 of the control, which increased cell membrane fluidity and instability. Therefore, phenolic ketones can reduce the yeast growth, increase the UFA/SFA ratio of yeast and lower ethanol productivity. Effectively reduce or remove the content of lignin degradation products is the key to improve lignocellulose biorefinery.

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

    DEFF Research Database (Denmark)

    Mussatto, Solange I.

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

  14. The lignin pyrolysis composition and pyrolysis products of palm kernel shell, wheat straw, and pine sawdust

    International Nuclear Information System (INIS)

    Chang, Guozhang; Huang, Yanqin; Xie, Jianjun; Yang, Huikai; Liu, Huacai; Yin, Xiuli; Wu, Chuangzhi

    2016-01-01

    Highlights: • The primarily pyrolysis composition of PKS lignin was p-hydroxyphenyl unit. • Higher phenol yield and lower gas energy yield were obtained from PKS pyrolysis. • PKS produced more bio-oil and biochar than WS and PS from pyrolysis at 650–850 °C. • PKS-char had poorer gasification reactivity due to higher ordering carbon degree. - Abstract: The lignin monomer composition of palm kernel shell (PKS) was characterized using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and the characteristics and distributions of products obtained from PKS pyrolysis were investigated using Py-GC/MS, GC, and a specially designed pyrolysis apparatus. The gasification reactivity of PKS biochar was also characterized using thermogravimetry (TG) and Raman spectroscopy. All the results were compared with those obtained from wheat straw (WS) and pine sawdust (PS). The results showed that PKS lignin is primarily composed of p-hydroxyphenyl structural units, while WS and PS lignins are mainly made up of guaiacyl units. Both the mass and energy yields of non-condensable gases from PKS pyrolysis were lower than those obtained from WS and PS pyrolysis at 650–850 °C, owing to the lower volatile content (75.21%) and lack of methoxy groups in PKS. Compared with WS and PS, higher bio-oil productivity was observed during PKS pyrolysis. Phenols were the main component of PKS bio-oil from pyrolysis at 500 °C, and the phenol content of PKS bio-oil (13.49%) was higher than in WS bio-oil (1.62%) and PS bio-oil (0.55%). A higher yield of biochar (on an ash-free basis) was also obtained from PKS pyrolysis. Because of its greater relative degree of ordered carbon, PKS biochar exhibited lower in situ reactivity during CO_2 or H_2O gasification than WS and PS biochars. A longer residence time and addition of steam were found to be beneficial during PKS biochar gasification.

  15. Structural Characterization of Lignin in Wild-Type versus COMT Down-Regulated Switchgrass

    Energy Technology Data Exchange (ETDEWEB)

    Samuel, Reichel [School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA (United States); BioEnergy Science Center, Oak Ridge, TN (United States); Pu, Yunqiao, E-mail: yunqiao.pu@ipst.gatech.edu [BioEnergy Science Center, Oak Ridge, TN (United States); Institute of Paper Science and Technology, Georgia Institute of Technology, Atlanta, GA (United States); Jiang, Nan [School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA (United States); BioEnergy Science Center, Oak Ridge, TN (United States); Fu, Chunxiang [Forage Improvement Division, The Samuel Roberts Noble Foundation, Ardmore, OK (United States); Wang, Zeng-Yu [BioEnergy Science Center, Oak Ridge, TN (United States); Forage Improvement Division, The Samuel Roberts Noble Foundation, Ardmore, OK (United States); Ragauskas, Arthur, E-mail: yunqiao.pu@ipst.gatech.edu [School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA (United States); BioEnergy Science Center, Oak Ridge, TN (United States)

    2014-01-20

    This study examined the chemical structural characteristics of cellulolytic enzyme lignin isolated from switchgrass focusing on comparisons between wild-type control and caffeic acid 3-O-methyltransferase (COMT) down-regulated transgenic line. Nuclear magnetic resonance techniques including {sup 13}C, {sup 31}P, and two-dimensional {sup 13}C-{sup 1}H heteronuclear single quantum coherence as well as gel permeation chromatography were employed. Compared to the wild-type, the COMT down-regulated transgenic switchgrass lignin demonstrated a decrease in syringyl (S):guaiacyl (G) ratio and p-coumarate:ferulate ratio, an increase in relative abundance of phenylcoumaran unit, and a comparable content of total free phenolic OH groups along with formation of benzodioxane unit. In addition, COMT down-regulation had no significant effects on the lignin molecular weights during its biosynthesis process.

  16. 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.

  17. 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.

  18. Lignin Valorisation for Chemicals and (Transportation) Fuels via (Catalytic) Pyrolysis and Hydrodeoxygenation

    Energy Technology Data Exchange (ETDEWEB)

    De Wild, P.J.; Van der Laan, R.R. [ECN Biomass, Coal and Environmental Research, Petten (Netherlands); Kloekhorst, A.; Heeres, E. [University of Groningen RUG, Groningen (Netherlands)

    2009-10-15

    New technology is needed to exploit the potential of lignin as a renewable feedstock for fuels, chemicals and performance products. Fast fluidized bed pyrolysis of different lignins at 400C yields up to 21 wt% (d.b.) of a phenolic fraction containing 10 wt% (d.b.) of several phenols. Subsequent catalytic hydrotreating of this phenolic fraction with 100 bar of hydrogen in dodecane at 350C yields mainly cycloalkanes, cyclohexanols and alkanes. For the production of monomeric phenols, it appears that the used ruthenium on carbon is a too active catalyst. However, cyclohexanols may be interesting products, e.g., for use as oxygenates in engine fuel.

  19. 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.

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

    International Nuclear Information System (INIS)

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

    1990-01-01

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

  1. 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...

  2. Phenolics of Arbutus unedo L. (Ericaceae) fruits: identification of anthocyanins and gallic acid derivatives.

    Science.gov (United States)

    Pawlowska, Agata Maria; De Leo, Marinella; Braca, Alessandra

    2006-12-27

    Arbutus unedo L., the strawberry tree (Ericaceae family), is an evergreen shrub or small tree, typical of the Mediterranean fringe and climate. The aim of the present study was to evaluate the profile of the phenolic constituents of A. unedo fruits. Seven compounds were purified by Sephadex LH-20 column chromatography of the MeOH extract followed by HPLC and were characterized as arbutin, beta-D-glucogalline, gallic acid 4-O-beta-D-glucopyranoside, 3-O-galloylquinic acid, 5-O-galloylquinic acid, 3-O-galloylshikimic acid, and 5-O-galloylshikimic acid, by means of NMR and ESI-MS analyses. Moreover, LC-PDA-MS analysis of the red pigment of A. unedo fruits revealed the presence of three anthocyanins recognized as cyanidin 3-O-beta-D-galactopyranoside, delphinidin 3-O-beta-D-glucopyranoside, and cyanidin 3-O-beta-D-arabinopyranoside. These pigments were also quantified.

  3. 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.

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

    Directory of Open Access Journals (Sweden)

    Mendu Venugopal

    2011-10-01

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

  5. 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

  6. 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...

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

    NARCIS (Netherlands)

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

    2016-01-01

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

  8. Enhanced degradation and mineralization of 4-chloro-3-methyl phenol by Zn-CNTs/O3 system.

    Science.gov (United States)

    Liu, Yong; Zhou, Anlan; Liu, Yanlan; Wang, Jianlong

    2018-01-01

    A novel zinc-carbon nanotubes (Zn-CNTs) composite was prepared, characterized and used in O 3 system for the enhanced degradation and mineralization of chlorinated phenol. The Zn-CNTs was characterized by SEM, BET and XRD, and the degradation of 4-chloro-3-methyl phenol (CMP) in aqueous solution was investigated using Zn-CNTs/O 3 system. The experimental results showed that the rate constant of total organic carbon (TOC) removal was 0.29 min -1 , much higher than that of only O 3 system (0.059 min -1 ) because Zn-CNTs/O 2 system could generate H 2 O 2 in situ, the concentration of H 2 O 2 could reach 156.14 mg/L within 60 min at pH 6.0. The high mineralization ratio of CMP by Zn-CNTs/O 3 occurred at wide pH range (3.0-9.0). The increase of Zn-CNTs dosage or gas flow rate contributed to the enhancement of CMP mineralization. The intermediates of CMP degradation were identified and the possible degradation pathway was tentatively proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. 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...

  10. DETERMINACIÓN DE FENOLES TOTALES EN DERIVADOS LÍGNICOS OBTENIDOS DEL “LICOR NEGRO” COMO ALTERNATIVA DE PRODUCCIÓN // DETERMINATION OF TOTAL PHENOL DERIVATIVES OBTAINED FROM LIGNIN "BLACK LIQUOR" AS ALTERNATIVE TO PRODUCTION

    Directory of Open Access Journals (Sweden)

    María José López Villalobos

    2015-06-01

    Full Text Available Lignin is an industrial waste being worthless in papermaking byproduct of black liquor obtained from the pulping process in some Venezuelan plants. The black liquor is obtained from the Kraft pulping process to extract lignin sulphite by acid precipitation and quantify the amount of total phenols in such lignin products used in this study. Spectrophotometry Molecular absorption in the UV-Visible and Infrared Spectroscopy (FTIR region were used to carry out these study techniques. The products obtained in the study had the same signs than commercial lignin (LA, along with the extracted lignin present little degradation HCl, confirmed by infrared spectra. Also, the amount of total phenols was quantified in derivative lignin obtained using the Folin-Ciocalteu. In the sulphite process extracted lignin with acetic acid derivative contains more phenols, and in the Kraft process, the derivative lignin extracted with fewer nitric acid present. The amount of total phenolics present in these derivatives are good for making antiseptics, detergents, nylon, resin and many industrial products. // RESUMEN La lignina es un subproducto del licor negro obtenido del proceso de despulpado en algunas plantas de Venezuela, siendo un desecho industrial que carece de valor en la fabricación de papel. En este estudio se utilizó el licor negro obtenido de los procesos de pulpado Kraft y Sulfito para extraer la lignina mediante precipitaciones ácidas y cuantificar la cantidad de fenoles totales en dichos productos lígnicos. Para llevar a cabo este estudio, se utilizaron las técnicas de Espectrofotometría de Absorción Molecular en la región UV-Visible y la Espectroscopia de Infrarrojo (FTIR. Los productos obtenidos en el estudio presentaron señales similares que la lignina comercial (LA, además la lignina extraída con HCl presentó poca degradación, corroborado por los espectros infrarrojos. Asimismo, se cuantificó la cantidad de fenoles totales en los

  11. Selective hydrogenolysis of Α–O–4, Β–O–4, 4–O–5 C–O bonds of lignin-model compounds and lignin-containing stillage derived from cellulosic bioethanol processing

    NARCIS (Netherlands)

    Gómez-Monedero, B.; Ruiz, M. P.; Bimbela, F.; Faria, J.

    2017-01-01

    Benzyl phenyl ether (BPE), phenethyl phenyl ether (PPE) and diphenyl ether (DPE) have been selected as model compounds of the most abundant and significant ether linkages found within the complex structure of lignin (e.g. α–O–4, β–O–4, and 4–O–5, respectively). The catalytic hydrogenolysis of these

  12. Spectroscopic investigations using density functional theory on 2-methoxy- 4(phenyliminomethyl)phenol: A non linear optical material

    Science.gov (United States)

    Hijas, K. M.; Madan Kumar, S.; Byrappa, K.; Geethakrishnan, T.; Jeyaram, S.; Nagalakshmi, R.

    2018-03-01

    Single crystals of 2-methoxy-4(phenyliminomethyl)phenol were grown from ethanol by slow evaporation solution growth technique. Single crystal X-ray diffraction experiment reveals the crystallization in orthorhombic system having non-centrosymmetric space group C2221. Geometrical optimization by density functional theory method was carried out using Gaussian program and compared with experimental results. Detailed experimental and theoretical vibrational analyses were carried out and the results were correlated to find close agreement. Thermal analyses show the material is thermally stable with a melting point of 159 °C. Natural bond orbital analysis was carried out to explain charge transfer interactions through hydrogen bonding. Relatively smaller HOMO-LUMO band gap favors the non linear optical activity of the molecule. Natural population analysis and molecular electrostatic potential calculations visualize the charge distribution in an isolated molecule. Calculated first-order molecular hyperpolarizability and preliminary second harmonic generation test carried out using Kurtz-Perry technique establish 2-methoxy-4(phenyliminomethyl)phenol crystal as a good non linear optical material. Z-scan proposes the material for reverse saturable absorption.

  13. Enzymes in Commercial Cellulase Preparations Bind Differently to Dioxane Extracted Lignins

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-04-24

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

  14. Comparison of the degradation of 14C-labeled DHP and corn stalk lignins by micro- and macrofungi and bacteria

    International Nuclear Information System (INIS)

    Haider, K.; Trojanowski, J.

    1980-01-01

    To what extent and by which mode microfungi and bacteria from soil are able to degrade lignin have been investigated and their activity compared with those of white and brown rot Basidiomycetes. The experiments were made by means of specifically 14C-labeled DHPs prepared by polymerization of correspondingly labeled coniferyl alcohol. Also, a corn stalk material was used which was specifically labeled in the lignin part. This material was prepared by infusion of specifically labeled cinnamic acid compounds into growing maize plants. The potential of the organisms to degrade several specifically labeled phenols was determined and compared. White and brown rot fungi, as well as several microscopic fungi, were able to degrade phenolcarboxylic and cinnamic acids and even some phenolic compounds with completely alkylated phenolic hydroxl groups. They could also introduce hydroxl groups into benzoic and pi-hydroxybenzoic acids before ring cleavage. As compared to brown rot, the white rot fungi released higher amounts of CO2 from the aromatic and side chain carbons of DHP and plant lignins. Some brown rot fungi, however, had similar capacities in degrading DHP lignin as white rot fungi. They especially released more CO2 from methoxyl groups. This release was dependent upon the added carbohydrate source and could be either repressed or enhanced. Several bacteria, especially Nocardia spp. and Pseudomonas spp., were tested for their potential to degrade the labeled lignins or phenols. Most of these bacteria did not appreciably degrade lignins, although they were highly active in the metabolization of phenols. Some Nocardia spp., however, were found to have a noteworthy capacity in the degradation of lignins and phenols. Preliminary studies of the potentials of the organisms to attack labeled lignin sulfonates either in liquid or soil cultures are presented. (Refs. 100)

  15. METHODS TO IMPROVE LIGNIN’S REACTIVITY AS A PHENOL SUBSTITUTE AND AS REPLACEMENT FOR OTHER PHENOLIC COMPOUNDS: A BRIEF REVIEW

    OpenAIRE

    Yonghong Zhou; Meng Zhang; Hui Pan; Lihong Hu

    2011-01-01

    Lignin is readily available as a by-product from the pulp and paper industry. It is considered to be a promising substitute for phenol in phenol-formaldehyde (PF) resin synthesis, given the increasing concerns of the shortage of fossil resources and the environmental impact from petroleum-based products. One hurdle that prevents the commercial utilization of lignin is its low reactivity due to its chemical structure. Many efforts have been made to improve its reactivity by modification and/or...

  16. ASETILASI PADA FENOL DAN ANISOL MENGGUNAKAN ANHIDRIDA ASAM ASETAT BERKATALIS Zr4+-ZEOLIT BETA

    Directory of Open Access Journals (Sweden)

    DA Retnoningrum

    2015-07-01

    was studied in the acetylation reaction of phenol and anisole. Reaction was carried out at various temperatures, i.e. 100 and 130C with the reaction time at 4th, 8th and 12th hours. Acetylation results were then analyzed using GC, FTIR and product analysis using GC-MS. Acetylation of phenol with catalyst Zr4+- beta zeolite produced phenyl ethanoate at level of 95.87% and selectivity 100%. These results were obtained at a reaction temperature of 130C and the reaction time of 8 hours. Acetylation at both the benzene ring of phenol and anisole did not occur, it is because acetylation at the benzene ring was more difficult than acetylation at the OH group of phenol. It needs to apply other conditions to do acetylation of benzene ring. Acetylation of anisole at 24-h reaction time and temperature of 130C resulted in product with level of 74%. 

  17. Reactivity of long chain alkylamines to lignin moieties: implications on hydrophobicity of lignocellulose materials.

    Science.gov (United States)

    Kudanga, Tukayi; Prasetyo, Endry Nugroho; Sipilä, Jussi; Guebitz, Georg M; Nyanhongo, Gibson S

    2010-08-20

    Enzymatic processes provide new perspectives for modification of lignocellulose materials. In the current study, laccase catalyzed coupling of long chain alkylamines to lignin model molecules and lignocellulose was investigated. Up to two molecules of dodecylamine (DA) and dihexylamine (DHA) were successfully coupled with lignin monomers (guaiacol, catechol and ferulic acid) while coupling onto complex lignin model compounds (syringylglycerol beta-guaiacyl ether, guaiacylglycerol beta-guaiacyl ether and dibenzodioxocin) yielded 1:1 coupling products. Surface analysis of beech veneers enzymatically grafted with DA showed an increase in nitrogen content of 3.18% compared to 0.71% in laccase only treated controls while the O/C ratio decreased from 0.52 to 0.46. Concomitantly the grafting of DHA or DA onto beech veneers resulted in a 53.8% and 84.2% increase in hydrophobicity, respectively when compared to simple adsorption. Therefore, laccase-mediated grafting of long chain alkylamines onto lignocellulose materials can be potentially exploited for improving their hydrophobicity. Copyright 2010 Elsevier B.V. All rights reserved.

  18. 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.

  19. Iron Oxide-Cobalt Nanocatalyst for O-tert-Boc Protection and O-Arylation of Phenols

    Directory of Open Access Journals (Sweden)

    Vilas B. Gade

    2018-04-01

    Full Text Available Efficient and general protocols for the O-tert-boc protection and O-arylation of phenols were developed in this paper using a recyclable magnetic Fe3O4-Co3O4 nanocatalyst (Nano-Fe-Co, which is easily accessible via simple wet impregnation techniques in aqueous mediums from inexpensive precursors. The results showed the catalysts were well characterized by XRD (X-ray Diffraction, ICP-AES (Inductive Coupled Plasma Atomic Emission Spectroscopy, TEM (Transmission Electron Microscopy, TOF-SIMS (Time-Of-Flight Secondary Ion Mass Spectrometry and XPS (X-ray Photoelectron Spectroscopy. The O-tert-boc protection and O-arylation of phenols was accomplished in good to excellent yields (85–95% and the catalyst was reusable and recyclable with no loss of catalytic activity for at least six repetitions.

  20. 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...

  1. 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)

  2. 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

  3. [Phenolic compounds in branches of Tamarix rasissima].

    Science.gov (United States)

    Li, Juan; Li, Wei-Qi; Zheng, Ping; Wang, Rui; Yu, Jian-Qiang; Yang, Jian-Hong; Yao, Yao

    2014-06-01

    To study the chemical constituents of the branches of Tamarix rasissima, repeated silica gel column chromatography, Sephadex LH-20 chromatography and recrystallization were applied for chemical constituents isolation and purification. Ten phenolic compounds were isolated from the n-BuOH fraction and their structures were elucidated by physical properties and spectra analysis such as UV, ESI-MS and NMR as monodecarboxyellagic acid (1), ellagic acid (2), 3, 3'-di-O-methylellagic acid (3), 3, 3'-di-O-methylellagic acid-4-O-beta-D-glucopyranoside (4), 3, 3'-di-O-methylellagic acid-4'-O-alpha-D-arabinfuranoside (5), ferulic acid (6), isoferulic acid (7), caffeic acid (8), 4-O-acetyl-caffeic acid (9), and 4-methyl-1, 2-benzenediol (10). All compounds except for isoferulic acid were isolated firstly from this plant except for isoferulic acid, and compounds 5, 9 and 10 were obtained from Tamarix genus for the first time.

  4. Elimination of Phenol and Color from Pulping Black Liquor Using Electrocoagulation Process

    OpenAIRE

    Nahid Rastegarfar; Rabi Behrouz; Nader Bahramifar

    2013-01-01

    There are many non-wood lignocelluloses resources such as wheat, rice straw and other agriculture by- products with appropriate feature for pulp production in Iran. The most major deterrent to their use is presence of pulping black liquor that due to lignin of lignocelluloses solution contains significant amounts of color and phenol compounds. The aim of this paper was investigation of the ability to remove phenol and color as the most important organic pollutants from back liquor of agri-bas...

  5. Formation of aromatic products at radiation-thermal destruction of lignin

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  6. Cupric Oxide (CuO) Oxidation Detects Pyrogenic Carbon in Burnt Organic Matter and Soils

    Science.gov (United States)

    Hatten, Jeff; Goñi, Miguel

    2016-01-01

    Wildfire greatly impacts the composition and quantity of organic carbon stocks within watersheds. Most methods used to measure the contributions of fire altered organic carbon–i.e. pyrogenic organic carbon (Py-OC) in natural samples are designed to quantify specific fractions such as black carbon or polyaromatic hydrocarbons. In contrast, the CuO oxidation procedure yields a variety of products derived from a variety of precursors, including both unaltered and thermally altered sources. Here, we test whether or not the benzene carboxylic acid and hydroxy benzoic acid (BCA) products obtained by CuO oxidation provide a robust indicator of Py-OC and compare them to non-Py-OC biomarkers of lignin. O and A horizons from microcosms were burned in the laboratory at varying levels of fire severity and subsequently incubated for 6 months. All soils were analyzed for total OC and N and were analyzed by CuO oxidation. All BCAs appeared to be preserved or created to some degree during burning while lignin phenols appeared to be altered or destroyed to varying extents dependent on fire severity. We found two specific CuO oxidation products, o-hydroxybenzoic acid (oBd) and 1,2,4-benzenetricarboxylic acid (BTC2) that responded strongly to burn severity and withstood degradation during post-burning microbial incubations. Interestingly, we found that benzene di- and tricarboxylic acids (BDC and BTC, respectively) were much more reactive than vanillyl phenols during the incubation as a possible result of physical protection of vanillyl phenols in the interior of char particles or CuO oxidation derived BCAs originating from biologically available classes of Py-OC. We found that the ability of these compounds to predict relative Py-OC content in burned samples improved when normalized by their respective BCA class (i.e. benzene monocarboxylic acids (BA) and BTC, respectively) and when BTC was normalized to total lignin yields (BTC:Lig). The major trends in BCAs imparted by burning

  7. Simultaneous bond degradation and bond formation during phenol-formaldehyde curing with wood

    Science.gov (United States)

    Daniel J. Yelle; John Ralph

    2016-01-01

    Bonding of wood using phenol–formaldehyde adhesive develops highly durable bonds. Phenol– formaldehyde is believed to form primary bonds with wood cell wall polymers (e.g., lignin). However, it is unclear how this adhesive interacts and bonds to lignin. Through wood solubilisation methodologies, earlywood and latewood bonded assemblies were characterized using two-...

  8. Purification and characterization of lignin peroxidases from Penicillium decumbens P6

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-06-01

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

  9. 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.

  10. Substituent Effects on the Hydrogen Bonding between 4-Substituted Phenols and HF, H2O, NH3

    Institute of Scientific and Technical Information of China (English)

    程宇辉; 傅尧; 刘磊; 郭庆祥

    2003-01-01

    Density function theory UB3LYP/6-31+g(d) calculations were performed to study the hydrogen bonds between para-substituted phenols and HF, H2O, or NH3. It revealed that many properties of the non-covalent complexes, such as the interaction energies, donor-acceptor distances, bond lengths and vibration frequencies, showed well-defined substituent effects. Therefore, from the substituent effects not only the mechanism of a certain non-covalent interaction can be better understood, but also the interaction energies and structures of a certain non-covalent complex, which otherwise might be very hard or resource-consuming to estimate, can be easily predicted.

  11. High-pressure behavior of beta-Ga2O3 nanocrystals

    DEFF Research Database (Denmark)

    Wang, H.; He, Y.; Chen, W.

    2010-01-01

    that nanocrystalline monoclinic beta-Ga2O3 underwent a phase transition to rhombohedral alpha-Ga2O3. It was found that beta- to alpha-Ga2O3 transition began at about 13.6-16.4 GPa, and extended up to 39.2 GPa. At the highest pressure used, only alpha-Ga2O3 was present, which remained after pressure release. A Birch......-Murnaghan fit to the P-V data yielded a zero-pressure bulk modulus at fixed B-0(')=4: B-0=228(9) GPa and B-0=333(19) GPa for beta-Ga2O3 and alpha-Ga2O3 phases, respectively. We compared our results with bulk beta-Ga2O3, and concluded that the phase-transition pressure and bulk modulus of nanocrystalline beta...

  12. A supramolecular proposal of lignin structure and its relation with the wood properties

    Directory of Open Access Journals (Sweden)

    Heber S. Abreu

    2009-03-01

    Full Text Available In spite of the great importance of cellulose the lignin is considered the second most abundant substance of the wood. However, little attention has been given it, mainly to wood properties. The lignin as well as other structural compounds (cellulose and hemicelluloses, has obviously an important role on the wood properties, probably due its composition and existent bonds. In general lignins have β-O-4 (Alkyl Aril Ether as majoritary bond. This bond in a continued structure form big molecules with spiral conformation as virtual model. Based on this idea, lignins that have high/low β-O-4 content may have differentiated spiraled structures,suggesting different behaviors on the wood properties,which shows that the lignins (Guaicyl:Syringyl (GS of angiosperms, for example, which have higher β-O-4 content would present higher spiral conformation than gymnosperms lignins(HG. On the other hand HG lignins have chance of being more anchored on the matrix compound than GS lignins. In this context, the β-O-4 bonds of lignins possibly affect the wood properties, therefore, it is considered relevant for wood technology science discussion.Apesar da grande importância da celulose a lignina é considerada a segunda substância mais abundante da madeira. Entretanto, pouca atenção tem sido dada a ela, principalmente com relação às propriedades da madeira. A lignina assim como outras substâncias (celulose e hemicelulose, tem obviamente um papel importante sobre as propriedades da madeira, provavelmente devido a sua composição e a existências de ligações. Geralmente as ligninas possuem majoritariamente ligaçõesβ-O-4 (Éter Alquil-Arílico, esta ligação em uma estrutura contínua forma grandes moléculas com conformação em espiral, como visto em modelo virtual. Com base nesta idéia, ligninas que possuem alto/baixo teor de β-O-4, podem ter estruturas espiraladas diferenciadas, sugerindo comportamentos diferentes sobre as propriedades da

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

    OpenAIRE

    Hemmilä, Venla; Trischler, Johann; Sandberg, Dick

    2013-01-01

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

  14. 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.

  15. Characterization of Trapped Lignin-Degrading Microbes in Tropical Forest Soil

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-14

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

  16. Characterization of trapped lignin-degrading microbes in tropical forest soil

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-03-01

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

  17. Ammonia-modified graphene sheets decorated with magnetic Fe{sub 3}O{sub 4} nanoparticles for the photocatalytic and photo-Fenton degradation of phenolic compounds under sunlight irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Boruah, Purna K. [Advanced Materials Group, Materials Sciences and Technology Division, CSIR-North East Institute of Science & Technology, Jorhat 785006 (India); Academy of Scientific and Innovative Research (AcSIR) (India); Sharma, Bhagyasmeeta [Advanced Materials Group, Materials Sciences and Technology Division, CSIR-North East Institute of Science & Technology, Jorhat 785006 (India); Karbhal, Indrapal; Shelke, Manjusha V. [Academy of Scientific and Innovative Research (AcSIR) (India); Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Pune-11008, Maharashtra (India); Das, Manash R., E-mail: mnshrdas@yahoo.com [Advanced Materials Group, Materials Sciences and Technology Division, CSIR-North East Institute of Science & Technology, Jorhat 785006 (India); Academy of Scientific and Innovative Research (AcSIR) (India)

    2017-03-05

    Highlights: • Ammonia-modified graphene sheets decorated with magnetic Fe{sub 3}O{sub 4} nanoparticles. • Photocatalytic and photo-Fenton degradation of phenolic compounds. • An excellent reusability of the nanocomposite was observed up to ten cycles. - Abstract: Synthesis of easily separable and eco-friendly efficient catalyst with both photocatalytic and photo-Fenton degradation properties is of great importance for environment remediation application. Herein, ammonia-modified graphene (AG) sheets decorated with Fe{sub 3}O{sub 4} nanoparticles (AG/Fe{sub 3}O{sub 4}) as a magnetically recoverable photocatalyst by a simple in situ solution chemistry approach. First, we have functionalized graphene oxide (GO) sheets by amide functional group and then Fe{sub 3}O{sub 4} nanoparticles (NPs) are doped onto the functionalized GO surface. The AG/Fe{sub 3}O{sub 4} nanocomposite showed efficient photocatalytic activity towards degradation of phenol (92.43%), 2-nitrophenol (2-NP) (98%) and 2-chlorophenol (2-CP) (97.15%) within 70–120 min. Consequently, in case of photo-Fenton degradation phenomenon, 93.56% phenol, 98.76% 2-NP and 98.06% of 2-CP degradation were achieved within 50–80 min using AG/Fe{sub 3}O{sub 4} nanocomposite under sunlight irradiation. The synergistic effect between amide functionalized graphene and Fe{sub 3}O{sub 4} nanoparticles (NPs) enhances the photocatalytic activity by preventing the recombination rate of electron-hole-pair in Fe{sub 3}O{sub 4} NPs. Furthermore, the remarkable reusability of the AG/Fe{sub 3}O{sub 4} nanocomposite was observed up to ten cycles during the photocatalytic degradation of these phenolic compounds.

  18. Phenolic constituents and antioxidant activity of geopropolis from two species of amazonian stingless bees

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Ellen Cristina Costa da; Muniz, Magno Perea; Nunomura, Rita de Cassia Saraiva, E-mail: ellensilva@yahoo.com.br [Departamento de Quimica, Instituto de Ciencias Exatas, Universidade Federal do Amazonas, Manaus, AM (Brazil); Nunomura, Sergio Massayoshi [Departamento de Produtos Naturais, Instituto Nacional de Pesquisas da Amazonia, Manaus, AM (Brazil); Zilse, Gislene Almeida Carvalho [Departamento de Biodiversidade, Instituto Nacional de Pesquisas da Amazonia, Manaus, AM (Brazil)

    2013-09-01

    We investigated the phenolic constituents and antioxidant activity of geopropolis from two species of stingless Amazonian bees, Melipona interrupta and Melipona seminigra. The chemical investigation of geopropolis from Melipona interrupta led to the isolation of 5,7,4'-trihydroxyflavonone, 3,5,6,7,4'-pentahydroxyflavonol, naringenine-4'-O-{beta}-D-glucopyranoside and myricetin-3-O-{beta}-D-glucopyranoside. Their structures were assigned based on spectroscopic analyses, including two-dimensional NMR techniques. Antioxidant activity of methanol and ethanol extracts of M. interrupta and M. seminigra were measured using the 1,2-diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging assay. This is also the first work reporting the chemical investigation of stingless bee species from the Amazonian region. (author)

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

    Directory of Open Access Journals (Sweden)

    Daniel Forchheim

    2012-01-01

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

  20. Study of formation of deep trapping mechanism by UV, beta and gamma irradiated Eu(3+) activated SrY2O4 and Y4Al2O9 phosphors.

    Science.gov (United States)

    Dubey, Vikas; Kaur, Jagjeet; Parganiha, Yogita; Suryanarayana, N S; Murthy, K V R

    2016-04-01

    This paper reports the thermoluminescence properties of Eu(3+) doped different host matrix phosphors (SrY2O4 and Y4Al2O9). The phosphor is prepared by high temperature solid state reaction method. The method is suitable for large scale production and fixed concentration of boric acid using as a flux. The prepared samples were characterized by X-ray diffraction technique and the crystallite size calculated by Scherer's formula. The prepared phosphor characterized by Scanning Electron Microscopic (SEM), Fourier Transform Infrared (FTIR), Energy Dispersive X-ray analysis (EDX), thermoluminescence (TL) and Transmission Electron Microscopic (TEM) techniques. The prepared phosphors for different concentration of Eu(3+) ions were examined by TL glow curve for UV, beta and gamma irradiation. The UV 254nm source used for UV irradiation, Sr(90) source was used for beta irradiation and Co(60) source used for gamma irradiation. SrY2O4:Eu(3+)and Y4Al2O9:Eu(3+) phosphors which shows both higher temperature peaks and lower temperature peaks for UV, beta and gamma irradiation. Here UV irradiated sample shows the formation of shallow trap (surface trapping) and the gamma irradiated sample shows the formation of deep trapping. The estimation of trap formation was evaluated by knowledge of trapping parameters. The trapping parameters such as activation energy, order of kinetics and frequency factor were calculated by peak shape method. Here most of the peak shows second order of kinetics. The effect of gamma, beta and UV exposure on TL studies was also examined and it shows linear response with dose which indicate that the samples may be useful for TL dosimetry. Formation of deep trapping mechanism by UV, beta and gamma irradiated Eu(3+) activated SrY2O4 and Y4Al2O9 phosphors is discussed in this paper. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. The impact of lignin downregulation on alfalfa yield, chemical composition, and in vitro gas production.

    Science.gov (United States)

    Getachew, Girma; Laca, Emilio A; Putnam, Daniel H; Witte, Dave; McCaslin, Mark; Ortega, Kara P; DePeters, Edward J

    2018-02-06

    Lignin is a complex, phenolic polymer found in plant cell walls that is essential for mechanical support, water and mineral transport, and defense in vascular plants. Over ten different enzymes play a role in the synthesis of lignin in plants. Suppression of any one enzyme or combinations of these enzymes may change the concentration and composition of lignin in the genetically transformed plants. Two lines of alfalfa that were downregulated for caffeoyl coenzyme A O-methyltransferase were used to assess the impact of lignin downregulation on chemical composition and fermentation rate and extent using an in vitro gas production technique. A total of 64 samples consisting of two reduced lignin (RL) and two controls (CL), four field replicates, two cutting intervals (CIs; 28 and 35 days), and two cuts (Cut-1 and Cut-3) were used. No differences were detected in yield, crude protein, neutral detergent fiber (aNDF), and acid detergent fiber between the lines when harvested at the 28-day CI. The acid detergent lignin (ADL) concentration in RL alfalfa lines was significantly (P gas production and metabolizable energy content were greater in RL than in CL alfalfa. RL lines had 3.8% indigestible aNDF per unit ADL, whereas CL had 3.4% (P < 0.01). The positive effect of lignin downregulation was more pronounced when intervals between harvests were longer (35-day CI compared with the 28-day CI). Lignin downregulation in alfalfa offers an opportunity to extend harvesting time (CI) for higher yield without compromising the nutritional quality of the alfalfa forage for dairy and livestock feeding. However, the in vitro results reported here warrant further study using in vivo methods. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

  2. 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

  3. 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.

  4. C[sub 10]-O[sub eq]-N-(4-azido-5-[sup 125]iodo salicyloyl)-[beta]-alanyl-[beta] alanyl ryanodine (Az-[beta]AR), a novel photo-affinity ligand for the ryanodine binding site

    Energy Technology Data Exchange (ETDEWEB)

    Bidasee, K.R.; Besch, H.R. Jr.; Kwon, Sangyeol; Emmick, J.T.; Besch, K.T.; Gerzon, Koert; Humerickhouse, R.A. (Indiana Univ., Indianapolis, IN (United States). School of Medicine)

    1994-01-01

    A high affinity, photoactivatable, radio-iodinated ligand for the ryanodine binding site(s) of the sarcoplasmic reticulum calcium-release channel, C[sub 10]-O[sub e]-N-(4-azido-5-[sup 125]iodo salicyloyl)-[beta]-alanyl-[beta]-alanyl ryanodine (Az-[beta]AR), was synthesized at a specific activity of 1400mCi/mmol. (Author).

  5. Reaction of formaldehyde with phenols: a computational chemistry study.

    Science.gov (United States)

    Tohru Mitsunaga; Anthony H. Conner; Charles G. Hill

    2001-01-01

    Phenolic resins are important adhesives used by the forest products industry. The phenolic compounds in these resins are derived primarily from petrochemical sources. Alternate sources of phenolic compounds include tannins, lignins, biomass pyrolysis products, and coal gasification products. Because of variations in their chemical structures, the reactivities of these...

  6. Principal components of phenolics to characterize red Vinho Verde grapes: anthocyanins or non-coloured compounds?

    Science.gov (United States)

    Dopico-García, M S; Fique, A; Guerra, L; Afonso, J M; Pereira, O; Valentão, P; Andrade, P B; Seabra, R M

    2008-06-15

    Phenolic profile of 10 different varieties of red "Vinho Verde" grapes (Azal Tinto, Borraçal, Brancelho, Doçal, Espadeiro, Padeiro de Basto, Pedral, Rabo de ovelha, Verdelho and Vinhão), from Minho (Portugal) were studied. Nine Flavonols, four phenolic acids, three flavan-3-ols, one stilben and eight anthocyanins were determined. Malvidin-3-O-glucoside was the most abundant anthocyanin while the main non-coloured compound was much more heterogeneous: catechin, epicatechin, myricetin-3-O-glucoside, quercetin-3-O-glucoside or syringetin-3-O-glucoside. Anthocyanin contents ranged from 42 to 97%. Principal component analysis (PCA) was applied to analyse the date and study the relations between the samples and their phenolic profiles. Anthocyanin profile proved to be a good marker to characterize the varieties even considering different origin and harvest. "Vinhão" grapes showed anthocyanins levels until twenty four times higher than the rest of the samples, with 97% of these compounds.

  7. 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.

  8. Carbohydrates and phenols as quantitative molecular vegetation proxies in peats

    Science.gov (United States)

    Kaiser, K.; Benner, R. H.

    2012-12-01

    Vegetation in peatlands is intricately linked to local environmental conditions and climate. Here we use chemical analyses of carbohydrates and phenols to reconstruct paleovegetation in peat cores collected from 56.8°N (SIB04), 58.4°N (SIB06), 63.8°N (G137) and 66.5°N (E113) in the Western Siberian Lowland. Lignin phenols (vanillyl and syringyl phenols) were sensitive biomarkers for vascular plant contributions and provided additional information on the relative contributions of angiosperm and gymnosperm plants. Specific neutral sugar compositions allowed identification of sphagnum mosses, sedges (Cyperaceae) and lichens. Hydroxyphenols released by CuO oxidation were useful tracers of sphagnum moss contributions. The three independent molecular proxies were calibrated with a diverse group of peat-forming plants to yield quantitative estimates (%C) of vascular plant, sphagnum moss and lichen contributions in peat core samples. Correlation analysis indicated the three molecular proxies produced fairly similar results for paleovegetation compositions, generally within the error interval of each approach (≤26%). The lignin-based method generally lead to higher estimates of vascular plant vegetation. Several significant deviations were also observed due to different reactivities of carbohydrate and phenolic polymers during peat decomposition. Rapid vegetation changes on timescales of 50-200 years were observed in the southern cores SIB04 and SIB06 over the last 2000 years. Vanillyl and syringyl phenol ratios indicated these vegetation changes were largely due to varying inputs of angiosperm and gymnosperm plants. The northern permafrost cores G137 and E113 showed a more stable development. Lichens briefly replaced sphagnum mosses and vascular plants in both of these cores. Shifts in vegetation did not correlate well with Northern hemisphere climate variability over the last 2000 years. This suggested that direct climate forcing of peatland dynamics was overridden

  9. 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

  10. Beta radiation induced luminescence of polycrystalline Cu-doped Li{sub 2}B{sub 4}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Cruz-Zaragoza, E., E-mail: ecruz@nucleares.unam.mx [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, A.P. 70543, México D.F. 04510, México (Mexico); Furetta, C. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, A.P. 70543, México D.F. 04510, México (Mexico); Marcazzó, J.; Santiago, M. [Instituto de Física Arroyo Seco (UNCPBA) and CIFICEN (UNCPBA – CICPBA – CONICET), Pinto 399, 7000 Tandil (Argentina); Guarneros, C. [Centro de Investigación en Ciencia y Tecnología Avanzada- IPN, Carretera Puerto Industrial Altamira Km 14.5, 896000 Altamira, Tamaulipas, México (Mexico); Consejo Nacional de Ciencia y Tecnología, Av. Insurgentes Sur 1582, 03940 México D.F., México (Mexico); Pacio, M. [Centro de Investigación en Dispositivos Semiconductores, Instituto de Ciencias Universidad Autónoma de Puebla, Av. 14 Sur, 72570 Puebla, México (Mexico); Palomino, R. [Facultad de Ciencias Físico-Matemáticas, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, México (Mexico)

    2016-11-15

    Thermoluminescence (TL) and radioluminescence (RL) properties of polycrystalline lithium tetraborate (Li{sub 2}B{sub 4}O{sub 7}) doped with different concentrations of copper (0.25, 0.5, 1 wt %) under beta irradiation have been investigated. The feasibility of using this borate in radiation dosimetry at low doses has been evaluated. Tissue equivalent Li{sub 2}B{sub 4}O{sub 7} was prepared by solid state reaction using mixing stoichiometric compositions of lithium carbonate (Li{sub 2}CO{sub 3}) and boric acid (H{sub 3}BO{sub 3}) and a solution of CuCl{sub 2} as dopant. The glow curve of the most efficient copper doped borate (Li{sub 2}B{sub 4}O{sub 7}:Cu 0.5 wt %) shows a main stable peak centered at 225 °C and a second low temperature peak centered at 80 °C. The low temperature peak fades completely after 24 h of storage in darkness and at room temperature or after an annealing at 120 °C for 10 s. The main peak of the Li{sub 2}B{sub 4}O{sub 7}:Cu remains constant. The TL response of Li{sub 2}B{sub 4}O{sub 7}:Cu shows good linearity in the analyzed dose range. The stability and repeatability of RL signals of the borate have been studied and the Li{sub 2}B{sub 4}O{sub 7}:Cu (0.5 wt %) shows the higher RL emission and a stable and repetitive response. Results show that polycrystalline Li{sub 2}B{sub 4}O{sub 7}:Cu has prospects to be used in beta radiation dosimetry. - Highlights: • Polycrystalline Cu-doped lithium tetraborate (LTB) was obtained by high temperature solid state reaction. • Beta-irradiated LTB:Cu (0.5 wt %) showed to have the highest TL and RL response. • A very good TL linearity in the dose range from 0.01 up to 100 Gy was obtained. • No fading is observed when an annealing at 120 °C for 10 s is carried out. • Results show that LTB:Cu has good prospects to be used in beta radiation dosimetry.

  11. Phenolic constituents and antioxidant activity of geopropolis from two species of amazonian stingless bees

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Ellen Cristina Costa da; Muniz, Magno Perea; Nunomura, Rita de Cassia Saraiva, E-mail: ellensilva@yahoo.com.br [Departamento de Quimica, Instituto de Ciencias Exatas, Universidade Federal do Amazonas, Manaus, AM (Brazil); Nunomura, Sergio Massayoshi [Departamento de Produtos Naturais, Instituto Nacional de Pesquisas da Amazonia, Manaus, AM (Brazil); Zilse, Gislene Almeida Carvalho [Departamento de Biodiversidade, Instituto Nacional de Pesquisas da Amazonia, Manaus, AM (Brazil)

    2013-09-01

    We investigated the phenolic constituents and antioxidant activity of geopropolis from two species of stingless Amazonian bees, Melipona interrupta and Melipona seminigra. The chemical investigation of geopropolis from Melipona interrupta led to the isolation of 5,7,4'-trihydroxyflavonone, 3,5,6,7,4'-pentahydroxyflavonol, naringenine-4'-O-{beta}-D-glucopyranoside and myricetin-3-O-{beta}-D-glucopyranoside. Their structures were assigned based on spectroscopic analyses, including two-dimensional NMR techniques. Antioxidant activity of methanol and ethanol extracts of M. interrupta and M. seminigra were measured using the 1,2-diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging assay. This is also the first work reporting the chemical investigation of stingless bee species from the Amazonian region. (author)

  12. Selective Conversion of Lignin-Derivable 4-Alkylguaiacols to 4-Alkylcyclohexanols over Noble and Non-Noble-Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Schutyser, Wouter; Van den Bossche, Gil; Raaffels, Anton; Van den Bosch, Sander; Koelewijn, Steven-Friso; Renders, Tom; Sels, Bert F.

    2016-10-03

    Recent lignin-first catalytic lignocellulosic biorefineries produce large quantities of two potential platform chemicals, 4-n-propylguaiacol (PG) and 4-n-propylsyringol. Because conversion into 4-n-propylcyclohexanol (PCol), a precursor for novel polymer building blocks, presents a promising valorization route, reductive demethoxylation of PG was examined here in the liquid-phase over three commercial hydrogenation catalysts, viz. 5 wt % Ru/C, 5 wt % Pd/C and 65 wt % Ni/SiO2-Al2O3, at elevated temperatures ranging from 200 to 300 degrees C under hydrogen atmosphere. Kinetic profiles suggest two parallel conversion pathways: Pathway I involves PG hydrogenation to 4-n-propyl-2-methoxycyclohexanol (PMCol), followed by its demethoxylation to PCol, whereas Pathway II constitutes PG hydrodemethoxylation to 4-n-propylphenol (PPh), followed by its hydrogenation into PCol. The slowest step in the catalytic formation of PCol is the reductive methoxy removal from PMCol. Moreover, under the applied reaction conditions, PCol may react further into hydrocarbons. The following criteria are therefore essential to reach a high PCol yield: (i) catalytic pathway II is preferred as this route does not involve stable intermediates; (ii) reactivity of PMCol should be higher than that of PCol, and (iii) the overall carbon balance should be high. Both the catalyst type and the reaction conditions have a substantial impact on the PCol yield. Only the commercial Ni catalyst meets the three criteria, provided the reaction is performed at 250 degrees C in hexadecane. Additional advantages of this solvent choice are a high boiling point (low operational pressure in closed reactor systems), high solubility of PG and derived products, high thermal, reductive stability, and easy derivability from fatty biomass feedstock. This Ni catalyst also showed an excellent stability in recycling runs and is capable of converting highly concentrated (up to 20 wt %) PG in hexadecane. Ru and Pd on carbon

  13. [Studies on phenolic constituents from leaves of pineapple (Ananas comosus)].

    Science.gov (United States)

    Wang, Wei; Ding, Yi; Xing, Dong-ming; Wang, Jin-ping; Du, Li-jun

    2006-08-01

    To study the phenolic constituents of the leaves of pineapple. Chromatographic methods were used to isolate compounds from the leaves of pineapple and spectroscopic methods were used to identify the structures of the isolated compounds. 7 compounds, ananasate (1), 1-O-caffeoylglycerol (2), 1-O-p-coumaroylglycerol (3), caffeic acid (4), p-coumaric acid (5), beta-sitosterol (6) and daucosterol (7), were isolated from the leaves of pineapple. 1 was a new compound, and others were obtained from this plant for the first time.

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

    Science.gov (United States)

    Ferrini, Paola; Rinaldi, Roberto

    2014-08-11

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

  15. 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

  16. Techniques for Analysis of Plant Phenolic Compounds

    Directory of Open Access Journals (Sweden)

    Thomas H. Roberts

    2013-02-01

    Full Text Available Phenolic compounds are well-known phytochemicals found in all plants. They consist of simple phenols, benzoic and cinnamic acid, coumarins, tannins, lignins, lignans and flavonoids. Substantial developments in research focused on the extraction, identification and quantification of phenolic compounds as medicinal and/or dietary molecules have occurred over the last 25 years. Organic solvent extraction is the main method used to extract phenolics. Chemical procedures are used to detect the presence of total phenolics, while spectrophotometric and chromatographic techniques are utilized to identify and quantify individual phenolic compounds. This review addresses the application of different methodologies utilized in the analysis of phenolic compounds in plant-based products, including recent technical developments in the quantification of phenolics.

  17. 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.

  18. Facile preparation of well-combined lignin-based carbon/ZnO hybrid composite with excellent photocatalytic activity

    Science.gov (United States)

    Wang, Huan; Qiu, Xueqing; Liu, Weifeng; Yang, Dongjie

    2017-12-01

    In this work, a novel lignin-based carbon/ZnO (LC/ZnO) hybrid composite with excellent photocatalytic performance was prepared through a convenient and environment friendly method using alkali lignin (AL) as carbon source. The morphological, microstructure and optical properties of the as-prepared LC/ZnO hybrid composite was characterized with scanning electron microscope (SEM), X-ray diffraction (XRD), Raman and UV-vis. The resulting LC/ZnO hybrid is composed of highly dispersed ZnO nanoparticles embedded on a lignin-based carbon nanosheet, showing excellent photogenerated electrons and holes separation and migration efficiency. The photocatalytic activity of LC/ZnO was much higher than the pure ZnO. The LC/ZnO hybrid composite showed different photocatalytic mechanism for degradation of negative methyl orange (MO) and positive Rhodamine B (RhB). It showed that h+ was the main photocatalytic active group during the degradation of MO, ·O2- and ·OH were the photocatalytic active groups during degradation of RhB. This reported photocatalyst with selective degradation of positive and negative organic dyes may have a great application prospect for photoelectric conversion and catalytic materials. Results of this work were of practical importance for high-valued utilization of lignin for carbon materials.

  19. Kinetic model describing the UV/H2O2 photodegradation of phenol from water

    Directory of Open Access Journals (Sweden)

    Rubio-Clemente Ainhoa

    2017-01-01

    Full Text Available A kinetic model for phenol transformation through the UV/H2O2 system was developed and validated. The model includes the pollutant decomposition by direct photolysis and HO•, HO2• and O2 •- oxidation. HO• scavenging effects of CO3 2-, HCO3 -, SO4 2- and Cl- were also considered, as well as the pH changes as the process proceeds. Additionally, the detrimental action of the organic matter and reaction intermediates in shielding UV and quenching HO• was incorporated. It was observed that the model can accurately predict phenol abatement using different H2O2/phenol mass ratios (495, 228 and 125, obtaining an optimal H2O2/phenol ratio of 125, leading to a phenol removal higher than 95% after 40 min of treatment, where the main oxidation species was HO•. The developed model could be relevant for calculating the optimal level of H2O2 efficiently degrading the pollutant of interest, allowing saving in costs and time.

  20. 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.

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Science.gov (United States)

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

    2016-05-01

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

  3. 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.

  4. TiO2–AgCl Based Nanoparticles for Photocatalytic Production of Phenolic Compounds from Lignocellulosic Residues

    DEFF Research Database (Denmark)

    Tsapekos, Panagiotis; Alvarado-Morales, Merlin; Boscaro, Davide

    2018-01-01

    Lignocellulosic biomass residues can be used as an interesting resource for the production of biochemicals or sustainable fuels. In this optic, lignin represents an interesting raw material for the production of chemicals, such as aromatic compounds, or fuels. This can contribute in moving away...... for optimal phenolic compounds production. It was found that the photocatalytic treatment boosted the phenolic production from wheat straw. The efficiency of the process depended on the initial pH and catalyst concentration. Process optimization towards increased phenolic compounds production was performed...... of toxic compounds presented in the catalyst-straw solution and specifically, HNO3 was toxic to methanogenic communities. Hence, to succeed in an efficient biorefinery framework where total phenols and biogas production are combined, the usage of HNO3 for catalyst synthesis should be avoided....

  5. Crystal structure and DFT study of (E-4-[({4-[(pyridin-2-ylmethylideneamino]phenyl}aminomethyl]phenol

    Directory of Open Access Journals (Sweden)

    Md. Serajul Haque Faizi

    2018-03-01

    Full Text Available In the title Schiff base compound, C19H17N3O, the configuration about the C=N bond is E. The molecule is non-planar, with the phenolic and pyridine rings being inclined to the central benzene ring by 56.59 (4 and 15.13 (14°, respectively. In the crystal, molecules are linked by pairs of O—H...N hydrogen bonds, forming inversion dimers. The dimers are connected to neighbouring dimers by N—H...O hydrogen bonds and C—H...π interactions, forming layers parallel to the bc plane. The layers are linked by offset π–π interactions [intercentroid distance = 3.779 (2 Å], forming a three-dimensional supramolecular structure. Quantum chemical calculations of the molecule are in good agreement with the solid-state structure.

  6. Kaempferol-3,4'-di-O-beta-glucopyranoside-7-O-alpha-rhamnopyranoside as a new flavonoid from Iberis amara L.

    Science.gov (United States)

    Kroll, U; Reif, K; Lederer, I; Förster, G; Zapp, J

    2009-02-01

    A new flavonol glycoside, kaempferol-3,4'-di-O-beta-glucopyranoside-7-O-alpha-rhamno-pyranoside, was isolated from the ethanolic extract of the whole fresh plant of Iberis amara L., an European plant used in gastrointestinal medicine. The structure was established by a combination of 1D and 2D NMR techniques (COSY, HSQC, HMBC, NOESY) as well as UV, IR and mass spectral data.

  7. A click chemistry approach to glycomimetics: Michael addition of 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose to 4-deoxy-1,2-O-isopropylidene-L-glycero-pent-4-enopyranos-3-ulose--a convenient route to novel 4-deoxy-(1-->5)-5-C-thiodisaccharides.

    Science.gov (United States)

    Witczak, Zbigniew J; Lorchak, David; Nguyen, Nguyen

    2007-09-03

    The base catalyzed conjugate Michael addition of the 1-thiosugar, 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranose, 1, to a new highly reactive enone 4-deoxy-1,2-O-isopropylidene-L-glycero-pent-4-enopyranos-3-ulose, 2, proceeds steroselectively with formation of adduct 3 in 94% yield. Convenient stereoselective reduction of the C-3 keto function of 3 with L-Selectride followed by in situ acetylation produces thiodisaccharide 4 in good 82% yield. Cleavage of the 1,2-O-isopropylidene protecting group with p-toluenesulfonic acid in methanol, followed by de-O-acetylation, produced an inseparable anomeric mixture of methyl 4-deoxy-5-C-(beta-D-glucopyranosyl)-thio-alpha/beta-L-ribo-pyranoside 5 in 72% overall yield. This approach constitutes a new general two-step click chemistry route to the previously unknown class of 4-deoxy-(1-->5)-5-C-thiodisaccharides as stable and biologically important glycomimetics.

  8. 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.

  9. Antioxidant Activity of the Lignins Derived from Fluidized-Bed Fast Pyrolysis

    Directory of Open Access Journals (Sweden)

    Sohail S. Qazi

    2017-03-01

    Full Text Available A challenge in recent years has been the rational use of forest and agriculture residues for the production of bio-fuel, biochemical, and other bioproducts. In this study, potentially useful compounds from pyrolytic lignins were identified by HPLC-MS/MS and untargeted metabolomics. The metabolites identified were 2-(4-allyl-2-methoxyphenoxy-1-(4-hydroxy-3-methoxyphenyl-1-propanol, benzyl benzoate, fisetinidol, phenyllactic acid, 2-phenylpropionic acid, 6,3′-dimethoxyflavone, and vanillin. The 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity (DPPH, trolox equivalent antioxidant capacity (TEAC, and total phenolics content (TPC per gram of pyrolytic lignin ranged from 14 to 503 mg ascorbic acid equivalents, 35 to 277 mg trolox equivalents, and 0.42 to 50 mg gallic acid equivalents, respectively. A very significant correlation was observed between the DPPH and TPC (r = 0.8663, p ≤ 0.0001, TEAC and TPC (r = 0.8044, p ≤ 0.0001, and DPPH and TEAC (r = 0.8851, p ≤ 0.0001. The polyphenolic compounds in the pyrolytic lignins which are responsible for radical scavenging activity and antioxidant properties can be readily profiled with HPLC-MS/MS combined with untargeted metabolomics. The results also suggest that DPPH, TEAC, and TPC assays are suitable methods for the measurement of antioxidant activity in a variety of pyrolytic lignins. These data show that the pyrolytic lignins can be considered as promising sources of natural antioxidants and value-added chemicals.

  10. 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

  11. Phase relationships in the area of the beta aluminate of the system K{sub 2}O-MgO-AL{sub 2}O{sub 3}; Phasenbeziehungen im Bereich der Beta-Aluminate des Systems K{sub 2}O-MgO-Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Kroon, P de

    1996-12-01

    The aim of this work was to be able to make statements about the thermodynamic stability of K-{beta}``-Al{sub 2}O{sub 3} in the pseudo-binary system K{sub 2}O-Al{sub 2}O{sub 3} and in the pseudo-ternary system K{sub 2}O-MgO-Al{sub 2}O{sub 3} relative to the adjacent phases of KAlO{sub 2} {alpha}-Al{sub 2}O{sub 3}, MgAl{sub 2}O{sub 4} and K-{beta}-Al{sub 2}O{sub 3}. (orig./MM) [Deutsch] Ziel dieser Arbeit war es, Aussagen ueber die thermodynamische Stabilitaet von K-{beta}``-Al{sub 2}O{sub 3} im pseudobinaeren System K{sub 2}O-Al{sub 2}O{sub 3} und im pseudoternaeren System K{sub 2}O-MgO-Al{sub 2}O{sub 3} relativ zu den benachbarten Phasen KAlO{sub 2}, {alpha}-Al{sub 2}O{sub 3}, MgAl{sub 2}O{sub 4} und K-{beta}-Al{sub 2}O{sub 3} machen zu koennen. (orig./MM)

  12. Consequences of plant phenolic compounds for productivity and health of ruminants.

    Science.gov (United States)

    Waghorn, Garry C; McNabb, Warren C

    2003-05-01

    Plant phenolic compounds are diverse in structure but are characterised by hydroxylated aromatic rings (e.g. flavan-3-ols). They are categorised as secondary metabolites, and their function in plants is often poorly understood. Many plant phenolic compounds are polymerised into larger molecules such as the proanthocyanidins (PA; condensed tannins) and lignins. Only the lignins, PA, oestrogenic compounds and hydrolysable tannins will be considered here. Lignins slow the physical and microbial degradation of ingested feed, because of resilient covalent bonding with hemicellulose and cellulose, rather than any direct effects on the rumen per se. The PA are prevalent in browse and are expressed in the foliage of some legumes (e.g. Lotus spp.), but rarely in grasses. They reduce the nutritive value of poor-quality diets, but can also have substantial benefits for ruminant productivity and health when improved temperate forages are fed. Beneficial effects are dependent on the chemical and physical structure, and concentration of the PA in the diet, but they have been shown to improve live-weight gain, milk yield and protein concentration, and ovulation rate. They prevent bloat in cattle, reduce gastrointestinal nematode numbers, flystrike and CH4 production. Some phenolic compounds (e.g. coumestans) cause temporary infertility, whilst those produced by Fusarium fungi found in pasture, silage or stored grains can cause permanent infertility. The HT may be toxic because products of their metabolism can cause liver damage and other metabolic disorders.

  13. BSA treatment to enhance enzymatic hydrolysis of cellulose in lignin containing substrates.

    Science.gov (United States)

    Yang, Bin; Wyman, Charles E

    2006-07-05

    Cellulase and bovine serum albumin (BSA) were added to Avicel cellulose and solids containing 56% cellulose and 28% lignin from dilute sulfuric acid pretreatment of corn stover. Little BSA was adsorbed on Avicel cellulose, while pretreated corn stover solids adsorbed considerable amounts of this protein. On the other hand, cellulase was highly adsorbed on both substrates. Adding a 1% concentration of BSA to dilute acid pretreated corn stover prior to enzyme addition at 15 FPU/g cellulose enhanced filter paper activity in solution by about a factor of 2 and beta-glucosidase activity in solution by about a factor of 14. Overall, these results suggested that BSA treatment reduced adsorption of cellulase and particularly beta-glucosidase on lignin. Of particular note, BSA treatment of pretreated corn stover solids prior to enzymatic hydrolysis increased 72 h glucose yields from about 82% to about 92% at a cellulase loading of 15 FPU/g cellulose or achieved about the same yield at a loading of 7.5 FPU/g cellulose. Similar improvements were also observed for enzymatic hydrolysis of ammonia fiber explosion (AFEX) pretreated corn stover and Douglas fir treated by SO(2) steam explosion and for simultaneous saccharification and fermentation (SSF) of BSA pretreated corn stover. In addition, BSA treatment prior to hydrolysis reduced the need for beta-glucosidase supplementation of SSF. The results are consistent with non-specific competitive, irreversible adsorption of BSA on lignin and identify promising strategies to reduce enzyme requirements for cellulose hydrolysis. (c) 2006 Wiley Periodicals, Inc.

  14. Capillary electrophoretic determination of selected phenolic compounds in humic substances of well waters and fertilizers.

    Science.gov (United States)

    Chen, Mei-Ying; Chang, Yan-Zin; Lu, Fung-Jou; Chen, Jian-Lian

    2010-01-01

    Humic substances (HS) from well waters, fertilizers, and synthetic phenolic polymers were characterized by elemental and UV-VIS spectroscopic analyses. Capillary zone electrophoresis (CZE) with UV absorption detection was used to analyze the lignin-derived phenolic distribution in the degradation residues after alkaline CuO oxidation of HS samples. Eleven phenols with p-acetyl, vanillyl and syringyl substituents were selected to optimize the CZE parameters. For well waters and fertilizers, the content of phenolic fragments was in agreement with the findings of the elemental and spectroscopic measurements. Additionally, parameters derived from the vanillic acid/vanilline, syringyl acid/syringaldehyde, p-hydroxyl/vanillyl and syringyl/vanillyl ratios matched analogous studies on dissolved organic matter from natural waters and on humic acids from terrestrial substances. The amount of phenolic monomer bonded within two synthetic HS polymers was found to be 25.9% protocatechuic acid and 71.3% gallic acid.

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

    Directory of Open Access Journals (Sweden)

    Lan Yao

    2018-02-01

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

  16. 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.

  17. Application of adsorption analysis to the investigation of phenols and bases in low-temperature tar

    Energy Technology Data Exchange (ETDEWEB)

    Kalechts, I V; Salimgareeva, F G; Tumbusova, Z P

    1955-01-01

    The use of chromatographic adsorption for the separation of mono- and bicyclic phenols and bases from coal tar and from its hydrogenation products were studied with o-cresol, ..beta..-naphthol, pyridine, and quinoline. Experimental data show that Al/sub 2/O/sub 3/ was preferable for separating phenols, but that silica gel was better for the bases. The best order of use of the developers was as follows: C/sub 6/H/sub 6/, Et/sub 2/O, EtOH. The data show that the destructive hydrogenation process degrades the higher series phenols to lower ones.

  18. Sesquiterpenoids and phenolics from roots of Taraxacum udum.

    Science.gov (United States)

    Michalska, Klaudia; Marciniuk, Jolanta; Kisiel, Wanda

    2010-07-01

    From roots of Taraxacum udum, two new and four known sesquiterpene lactones were isolated, together with five known phenolic compounds. The new compounds were characterized as 11beta, 13-dihydrotaraxinic acid and taraxinic acid 6-O-acetyl-beta-glucopyranosyl ester by spectroscopic methods, especially 1D and 2D NMR, and by comparison with structurally related compounds. The plant material was shown to be a good source of taraxinic acid derivatives. Copyright 2009 Elsevier B.V. All rights reserved.

  19. Monolignol 4-O-methyltransferases and uses thereof

    Science.gov (United States)

    Liu, Chang-Jun; Bhuiya, Mohammad-Wadud; Zhang, Kewei

    2014-11-18

    Modified (iso)eugenol 4-O-methyltransferase enzymes having novel capacity for methylation of monolignols and reduction of lignin polymerization in plant cell wall are disclosed. Sequences encoding the modified enzymes are disclosed.

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

    Directory of Open Access Journals (Sweden)

    Pere ePicart

    2015-09-01

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

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

    Science.gov (United States)

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

    2015-01-01

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

  2. 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.

  3. Assignment of the Raman lines in single crystal barium metaborate (beta-BaB sub 2 O sub 4)

    CERN Document Server

    Ney, P; Maillard, A; Polgar, K

    1998-01-01

    A Raman-scattering study performed on beta-BaB sub 2 O sub 4 (beta-BBO) at room temperature allows us to assign all the vibrational modes detected in the Raman spectra. The internal and external vibration modes are properly obtained by taking account of the light polarization, mode contamination and isotope effects. A correspondence between the lattice and the free-ring modes is also presented. (author)

  4. 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.

  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. Non-selective beta-adrenergic blockade prevents reduction of the cerebral metabolic ratio during exhaustive exercise in humans

    DEFF Research Database (Denmark)

    Larsen, T.S.; Rasmussen, P.; Overgaard, M.

    2008-01-01

    Intense exercise decreases the cerebral metabolic ratio of oxygen to carbohydrates [O(2)/(glucose + (1/2)lactate)], but whether this ratio is influenced by adrenergic stimulation is not known. In eight males, incremental cycle ergometry increased arterial lactate to 15.3 +/- 4.2 mm (mean +/- s.......d.) and the arterial-jugular venous (a-v) difference from -0.02 +/- 0.03 mm at rest to 1.0 +/- 0.5 mm (P cerebral metabolic ratio decreased from 5.5 +/- 1.4 to 3.0 +/- 0.3 (P ... of a non-selective beta-adrenergic (beta(1) + beta(2)) receptor antagonist (propranolol) reduced heart rate (69 +/- 8 to 58 +/- 6 beats min(-1)) and exercise capacity (239 +/- 42 to 209 +/- 31 W; P

  7. Catalytic Fast Pyrolysis of Alcell Lignin with Nano-NiO

    Directory of Open Access Journals (Sweden)

    Jiao Chen

    2015-11-01

    Full Text Available Catalytic fast pyrolysis of Alcell lignin with various additive ratios (5%, 10%, and 15%, mass ratio of nano-NiO was investigated using a horizontal pyrolyzer. Characterization methods, including Fourier transform infrared spectroscopy (FTIR, gas chromatography (GC, gas chromatography coupled with mass spectrometry (GC/MS, and elemental analysis, were utilized to identify the catalytic fast pyrolysis products. The results indicated that the nano-NiO catalyst had remarkable effects on the yield and quality of these products. The formation of gases, especially CO, CO2, and CH4, were greatly promoted when the additive ratio increased, while the formation of bio-char was clearly inhibited. However, when the additive ratio was 10%, the maximum yield of bio-oil (53.09 wt.% was obtained, and the corresponding maximum higher heating value (HHV was 25.33 MJ/kg. Furthermore, nano-NiO caused a large variation in the species of the compounds in bio-oil. Operating with the optimal nano-NiO additive ratio (10%, the carbon conversion rate was 65.50%, and the energy conversion rate was 74.53%.

  8. Efficient photocatalytic degradation of phenol in aqueous solution by SnO2:Sb nanoparticles

    International Nuclear Information System (INIS)

    Al-Hamdi, Abdullah M.; Sillanpää, Mika; Bora, Tanujjal; Dutta, Joydeep

    2016-01-01

    Highlights: • Sb doped SnO 2 nanoparticles were synthesized using sol–gel process. • Photocatalytic degradation of phenol were studies using SnO 2 :Sb nanoparticles. • Under solar light phenol was degraded within 2 h. • Phenol mineralization and intermediates were investigated by using HPLC. - Abstract: Photodegradation of phenol in the presence of tin dioxide (SnO 2 ) nanoparticles under UV light irradiation is known to be an effective photocatalytic process. However, phenol degradation under solar light is less effective due to the large band gap of SnO 2 . In this study antimony (Sb) doped tin dioxide (SnO 2 ) nanoparticles were prepared at a low temperature (80 °C) by a sol–gel method and studied for its photocatalytic activity with phenol as a test contaminant. The catalytic degradation of phenol in aqueous media was studied using high performance liquid chromatography and total organic carbon measurements. The change in the concentration of phenol affects the pH of the solution due to the by-products formed during the photo-oxidation of phenol. The photoactivity of SnO 2 :Sb was found to be a maximum for 0.6 wt.% Sb doped SnO 2 nanoparticles with 10 mg L −1 phenol in water. Within 2 h of photodegradation, more than 95% of phenol could be removed under solar light irradiation.

  9. Multicomponent kinetic analysis and theoretical studies on the phenolic intermediates in the oxidation of eugenol and isoeugenol catalyzed by laccase.

    Science.gov (United States)

    Qi, Yan-Bing; Wang, Xiao-Lei; Shi, Ting; Liu, Shuchang; Xu, Zhen-Hao; Li, Xiqing; Shi, Xuling; Xu, Ping; Zhao, Yi-Lei

    2015-11-28

    Laccase catalyzes the oxidation of natural phenols and thereby is believed to initialize reactions in lignification and delignification. Numerous phenolic mediators have also been applied in laccase-mediator systems. However, reaction details after the primary O-H rupture of phenols remain obscure. In this work two types of isomeric phenols, EUG (eugenol) and ISO (trans-/cis-isoeugenol), were used as chemical probes to explore the enzymatic reaction pathways, with the combined methods of time-resolved UV-Vis absorption spectra, MCR-ALS, HPLC-MS, and quantum mechanical (QM) calculations. It has been found that the EUG-consuming rate is linear to its concentration, while the ISO not. Besides, an o-methoxy quinone methide intermediate, (E/Z)-4-allylidene-2-methoxycyclohexa-2,5-dienone, was evidenced in the case of EUG with the UV-Vis measurement, mass spectra and TD-DFT calculations; in contrast, an ISO-generating phenoxyl radical, a (E/Z)-2-methoxy-4-(prop-1-en-1-yl) phenoxyl radical, was identified in the case of ISO. Furthermore, QM calculations indicated that the EUG-generating phenoxyl radical (an O-centered radical) can easily transform into an allylic radical (a C-centered radical) by hydrogen atom transfer (HAT) with a calculated activation enthalpy of 5.3 kcal mol(-1) and then be fast oxidized to the observed eugenol quinone methide, rather than an O-radical alkene addition with barriers above 12.8 kcal mol(-1). In contrast, the ISO-generating phenoxyl radical directly undergoes a radical coupling (RC) process, with a barrier of 4.8 kcal mol(-1), while the HAT isomerization between O- and C-centered radicals has a higher reaction barrier of 8.0 kcal mol(-1). The electronic conjugation of the benzyl-type radical and the aromatic allylic radical leads to differentiation of the two pathways. These results imply that competitive reaction pathways exist for the nascent reactive intermediates generated in the laccase-catalyzed oxidation of natural phenols, which is

  10. Study on The Application of Composed TiO2-diatomite in The Removal of Phenol in Water

    Science.gov (United States)

    Liu, S.; Li, J.

    2017-10-01

    As an environmentally friendly pollution control technology, TiO2 photocatalytic technology has a broad prospect in the field of environmental protection. In this paper, composed nano-TiO2-diatomite were prepared by depositing TiO2 nanoparticles on the surface of diatomite microparticles. The nano-TiO2/diatomite composed photocatalyst is used to remove phenol in water in a specific designed reaction box under 4 different operation factors such as different reaction time, different pollutant concentration, different UV light powers and different amount of catalytic powder. The experimental results indicate that the phenol removal percentages are influenced by the reaction time most significantly, the second is the phenol concentration, the next one is the photocatalyst amount and the UV light powers’ effect is quite limited. Tthe degradation of phenol typically slows down at the reaction time about 30 or 60 minutes. Besides that, the phenol removal kinetic removal rates were also investigated.

  11. The comparative geochemistries of lignins and carbohydrates in an anoxic fjord

    Science.gov (United States)

    Hamilton, Susan E.; Hedges, John I.

    1988-01-01

    A reducing, varved sediment core and monthly (May-September) plankton and sediment trap samples from Saanich Inlet, B.C., Canada, were analyzed for their elemental, lignin and neutral sugar compositions. Total yields of lignin-derived phenols from both the sediment trap and core samples indicated less than 15% and 30%, respectively, of chemically recognizable vascular plant remains, derived predominantly from gymnosperm wood and nonwoody angiosperm tissues. The elevated vanillyl and syringyl acid/aldehyde ratios of this material compared to fresh plant material indicated that it suffered mild aerobic decomposition prior to introduction to the Inlet. Most of the remaining particular organic material was nitrogen-rich, carbohydrate-poor and apparently plankton-derived. Organic carbon, total nitrogen, and total neutral sugars and lignin phenols all exhibited decreasing concentrations with depth in a region of uniform varving (upper 15 cm) in the sediment core. All profiles exhibited particularly steep concentration decreases within the top 2 cm of sediment. First-order decay constants for all four chemical categories within the upper 14 cm of the core ranged between 0.1-0.2 yr -1. Neutral sugars were consistently the most reactive chemical class, accounting for roughly 15% of the total organic carbon turnover. Although lignin appeared to be degraded within the sediment core, this degradation was nonselective for different lignin types and did not lead to increased acid/aldehyde ratios as occur during aerobic lignin decomposition. Comparisons of the yields of individual neutral sugars from the sediment and sediment trap samples to those expected from the vascular plant component alone indicated that the vascular plant debris in the upper portion of the sediment core had lost a portion of its initial glucose, lyxose, and mannose. In contrast, rhamnose and fucose were produced by all samples in large excess of total yields expected for chemically intact vascular plant

  12. Structure-function analyses of a caffeic acid O-methyltransferase from perennial ryegrass reveal the molecular basis for substrate preference.

    Science.gov (United States)

    Louie, Gordon V; Bowman, Marianne E; Tu, Yi; Mouradov, Aidyn; Spangenberg, German; Noel, Joseph P

    2010-12-01

    Lignin forms from the polymerization of phenylpropanoid-derived building blocks (the monolignols), whose modification through hydroxylation and O-methylation modulates the chemical and physical properties of the lignin polymer. The enzyme caffeic acid O-methyltransferase (COMT) is central to lignin biosynthesis. It is often targeted in attempts to engineer the lignin composition of transgenic plants for improved forage digestibility, pulping efficiency, or utility in biofuel production. Despite intensive investigation, the structural determinants of the regiospecificity and substrate selectivity of COMT remain poorly defined. Reported here are x-ray crystallographic structures of perennial ryegrass (Lolium perenne) COMT (Lp OMT1) in open conformational state, apo- and holoenzyme forms and, most significantly, in a closed conformational state complexed with the products S-adenosyl-L-homocysteine and sinapaldehyde. The product-bound complex reveals the post-methyl-transfer organization of COMT's catalytic groups with reactant molecules and the fully formed phenolic-ligand binding site. The core scaffold of the phenolic ligand forges a hydrogen-bonding network involving the 4-hydroxy group that anchors the aromatic ring and thereby permits only metahydroxyl groups to be positioned for transmethylation. While distal from the site of transmethylation, the propanoid tail substituent governs the kinetic preference of ryegrass COMT for aldehydes over alcohols and acids due to a single hydrogen bond donor for the C9 oxygenated moiety dictating the preference for an aldehyde.

  13. Structural and optical characterization of Eu3+ doped beta-Ga2O3 nanoparticles using a liquid-phase precursor method.

    Science.gov (United States)

    Kim, Moung-O; Kang, Bongkyun; Yoon, Daeho

    2013-08-01

    Eu3+ doped beta-Ga2O3 and non-doped beta-Ga2O3 nanoparticles were synthesized at 800 degrees C using a liquid-phase precursor (LPP) method, with different annealing times and Eu3+ ion concentrations. Eu3+ doped beta-Ga2O3 nanoparticles showed broad XRD peaks, revealing a second phase compared with the non-doped beta-Ga2O3 nanoparticles. The cathode luminescence (CL) spectra of beta-Ga2O3 and Eu3+ doped beta-Ga2O3 nanoparticles showed a broad band emission (300-500 nm) of imperfection and two component emissions. The luminescence quenching properties of Eu3+ dopant ion concentration appeared gradually beyond 5 mol% in our investigation.

  14. Total catalytic wet oxidation of phenol and its chlorinated derivates with MnO2/CeO2 catalyst in a slurry

    Directory of Open Access Journals (Sweden)

    A. J. Luna

    2009-09-01

    Full Text Available In the present work, a synthetic effluent of phenol was treated by means of a total oxidation process-Catalyzed Wet Oxidation (CWO. A mixed oxide of Mn-Ce (7:3, the catalyst, was synthesized by co-precipitation from an aqueous solution of MnCl2 and CeCl3 in a basic medium. The mixed oxide, MnO2/CeO2, was characterized and used in the oxidation of phenol in a slurry reactor in the temperature range of 80-130ºC and pressure of 2.04-4.76 MPa. A phenol solution containing 2.4-dichlorophenol and 2.4-dichlorophenoxyacetic acid was also degraded with good results. A lumped kinetic model, with two parallel reaction steps, fits precisely with the integrated equation and the experimental data. The kinetic parameters obtained are in agreement with the Arrhenius equation. The activation energies were determined to be 38.4 for the total oxidation and 53.4 kJ/mol for the organic acids formed.

  15. 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.

  16. Enhancement of Lignin Biopolymer Isolation from Hybrid Poplar by Organosolv Pretreatments

    Directory of Open Access Journals (Sweden)

    Miao Wu

    2014-01-01

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

  17. Experimental Studies on the Hydrotreatment of Kraft Lignin to Aromatics and Alkylphenolics Using Economically Viable Fe-Based Catalysts

    Science.gov (United States)

    2017-01-01

    Limonite, a low-cost iron ore, was investigated as a potential hydrotreatment catalyst for kraft lignin without the use of an external solvent (batch reactor, initial H2 pressure of 100 bar, 4 h). The best results were obtained at 450 °C resulting in 34 wt % of liquefied kraft lignin (lignin oil) on lignin intake. The composition of the lignin oil was determined in detail (elemental composition, GC-MS, GC×GC-FID, and GPC). The total GC-detectable monomeric species amounts up to 31 wt % on lignin intake, indicating that 92 wt % of the products in the lignin oil are volatile and thus of low molecular weight. The lignin oil was rich in low-molecular-weight alkylphenolics (17 wt % on lignin) and aromatics (8 wt % on lignin). Performance of the limonite catalyst was compared to other Fe-based catalysts (goethite and iron disulfide) and limonite was shown to give the highest yields of alkylphenolics and aromatics. The limonite catalyst before and after reaction was characterized using XRD, TEM, and nitrogen physisorption to determine changes in structure during reaction. Catalyst recycling tests were performed and show that the catalyst is active after reuse, despite the fact that the morphology changed and that the surface area of the catalyst particles was decreased. Our results clearly reveal that cheap limonite catalysts have the potential to be used for the depolymerization/hydrodeoxygenation of kraft lignin for the production of valuable biobased phenolics and aromatics. PMID:28413733

  18. Interaction of tertiary phosphines with lignin-type, alpha,beta-unsaturated aldehydes in water.

    Science.gov (United States)

    Moiseev, Dmitry V; Patrick, Brian O; James, Brian R; Hu, Thomas Q

    2007-10-29

    To learn more about the bleaching action of pulps by (hydroxymethyl)phosphines, lignin chromophores, such as the alpha,beta-unsaturated aromatic aldehydes, sinapaldehyde, coniferylaldehyde, and coumaraldehyde, were reacted with the tertiary phosphines R2R'P [R = R' = Me, Et, (CH2)3OH, iPr, cyclo-C6H11, (CH2)2CN; R = Me or Et, R' = Ph; R = Ph, R' = Me, m-NaSO3-C6H4] in water at room temperature under argon. In all cases, initial nucleophilic attack of the phosphine occurs at the activated C=C bond to form a zwitterionic monophosphonium species. With the phosphines PR3 [R = Me, Et, (CH2)3OH] and with R2R'P (R = Me or Et, R' = Ph), the zwitterion undergoes self-condensation to give a bisphosphonium zwitterion that can react with aqueous HCl to form the corresponding dichloride salts (as a mixture of R,R- and S,S-enantiomers); X-ray structures are presented for the bisphosphonium chlorides synthesized from the Et3P and Me3P reactions with sinapaldehyde. With the more bulky phosphines, iPr3P, MePPh2, (cyclo-C6H11)3P, and Na[Ph2P(m-SO3-C6H4)], only an equilibrium of the monophosphonium zwitterion with the reactant aldehyde is observed. The weakly nucleophilic [NC(CH2)2]3P does not react with sinapaldehyde. An analysis of some exceptional 1H NMR data within the prochiral phosphorus centers of the bisphosphonium chlorides is also presented.

  19. Thermoreflectance characterization of beta-Ga2O3 thin-film nanostrips.

    Science.gov (United States)

    Ho, Ching-Hwa; Tseng, Chiao-Yeh; Tien, Li-Chia

    2010-08-02

    Nanostructure of beta-Ga(2)O(3) is wide-band-gap material with white-light-emission function because of its abundance in gap states. In this study, the gap states and near-band-edge transitions in beta-Ga(2)O(3) nanostrips have been characterized using temperature-dependent thermoreflectance (TR) measurements in the temperature range between 30 and 320 K. Photoluminescence (PL) measurements were carried to identify the gap-state transitions in the beta-Ga(2)O(3) nanostrips. Experimental analysis of the TR spectra revealed that the direct gap (E(0)) of beta-Ga(2)O(3) is 4.656 eV at 300 K. There are a lot of gap-state and near-band-edge (GSNBE) transitions denoted as E(D3), E(W1), E(W2), E(W3), E(D2), EDBex, E(DB), E(D1), E(0), and E(0)' can be detected in the TR and PL spectra at 30 K. Transition origins for the GSNBE features in the beta-Ga(2)O(3) nanostrips are respectively evaluated. Temperature dependences of transition energies of the GSNBE transitions in the beta-Ga(2)O(3) nanostrips are analyzed. The probable band scheme for the GSNBE transitions in the beta-Ga(2)O(3) nanostrips is constructed.

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

    International Nuclear Information System (INIS)

    Gonzalez Arzola, K.; Arevalo, M.C.; Falcon, M.A.

    2009-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-03-30

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  3. 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

  4. Structure-Function Analyses of a Caffeic Acid O-Methyltransferase from Perennial Ryegrass Reveal the Molecular Basis for Substrate Preference[W][OA

    Science.gov (United States)

    Louie, Gordon V.; Bowman, Marianne E.; Tu, Yi; Mouradov, Aidyn; Spangenberg, German; Noel, Joseph P.

    2010-01-01

    Lignin forms from the polymerization of phenylpropanoid-derived building blocks (the monolignols), whose modification through hydroxylation and O-methylation modulates the chemical and physical properties of the lignin polymer. The enzyme caffeic acid O-methyltransferase (COMT) is central to lignin biosynthesis. It is often targeted in attempts to engineer the lignin composition of transgenic plants for improved forage digestibility, pulping efficiency, or utility in biofuel production. Despite intensive investigation, the structural determinants of the regiospecificity and substrate selectivity of COMT remain poorly defined. Reported here are x-ray crystallographic structures of perennial ryegrass (Lolium perenne) COMT (Lp OMT1) in open conformational state, apo- and holoenzyme forms and, most significantly, in a closed conformational state complexed with the products S-adenosyl-l-homocysteine and sinapaldehyde. The product-bound complex reveals the post-methyl-transfer organization of COMT’s catalytic groups with reactant molecules and the fully formed phenolic-ligand binding site. The core scaffold of the phenolic ligand forges a hydrogen-bonding network involving the 4-hydroxy group that anchors the aromatic ring and thereby permits only metahydroxyl groups to be positioned for transmethylation. While distal from the site of transmethylation, the propanoid tail substituent governs the kinetic preference of ryegrass COMT for aldehydes over alcohols and acids due to a single hydrogen bond donor for the C9 oxygenated moiety dictating the preference for an aldehyde. PMID:21177481

  5. A novel multifunctional O-methyltransferase implicated in a dual methylation pathway associated with lignin biosynthesis in loblolly pine

    OpenAIRE

    Li, Laigeng; Popko, Jacqueline L.; Zhang, Xing-Hai; Osakabe, Keishi; Tsai, Chung-Jui; Joshi, Chandrashekhar P.; Chiang, Vincent L.

    1997-01-01

    S-adenosyl-l-methionine (SAM)-dependent O-methyltransferases (OMTs) catalyze the methylation of hydroxycinnamic acid derivatives for the synthesis of methylated plant polyphenolics, including lignin. The distinction in the extent of methylation of lignins in angiosperms and gymnosperms, mediated by substrate-specific OMTs, represents one of the fundamental differences in lignin biosynthesis between these two classes of plants. In angiosperms, two types of structurally and functionally distinc...

  6. 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.

  7. Leaf phenolics and seaweed tannins : analysis, enzymatic oxidation and non-covalent protein binding

    NARCIS (Netherlands)

    Vissers, Anne M.

    2017-01-01

    Upon extraction of proteins from sugar beet leaves (Beta vulgaris L.) and oarweed (Laminaria digitata) for animal food and feed purposes, endogenous phenolics and proteins can interact with each other, which might affect the protein’s applicability. Sugar beet leaf proteins

  8. Anaerobic degradation of veratrylglycerol-beta-guaiacyl ether and guaiacoxyacetic acid by mixed rumen bacteria.

    OpenAIRE

    Chen, W; Supanwong, K; Ohmiya, K; Shimizu, S; Kawakami, H

    1985-01-01

    Veratrylglycerol-beta-guaiacyl ether (0.2 g/liter), a lignin model compound, was found to be degraded by mixed rumen bacteria in a yeast extract medium under strictly anaerobic conditions to the extent of 19% within 24 h. Guaiacoxyacetic acid, 2-(o-methoxyphenoxy)ethanol, vanillic acid, and vanillin were detected as degradation products of veratrylglycerol-beta-guaiacyl ether by thin-layer chromatography, gas chromatography, and gas chromatography-mass spectrometry. Guaiacoxyacetic acid (0.25...

  9. Understanding the chemical and structural transformations of lignin macromolecule during torrefaction

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  10. A novel multifunctional O-methyltransferase implicated in a dual methylation pathway associated with lignin biosynthesis in loblolly pine.

    Science.gov (United States)

    Li, L; Popko, J L; Zhang, X H; Osakabe, K; Tsai, C J; Joshi, C P; Chiang, V L

    1997-05-13

    S-adenosyl-L-methionine (SAM)-dependent O-methyltransferases (OMTs) catalyze the methylation of hydroxycinnamic acid derivatives for the synthesis of methylated plant polyphenolics, including lignin. The distinction in the extent of methylation of lignins in angiosperms and gymnosperms, mediated by substrate-specific OMTs, represents one of the fundamental differences in lignin biosynthesis between these two classes of plants. In angiosperms, two types of structurally and functionally distinct lignin pathway OMTs, caffeic acid 3-O-methyltransferases (CAOMTs) and caffeoyl CoA 3-O-methyltransferases (CCoAOMTs), have been reported and extensively studied. However, little is known about lignin pathway OMTs in gymnosperms. We report here the first cloning of a loblolly pine (Pinus taeda) xylem cDNA encoding a multifunctional enzyme, SAM:hydroxycinnamic Acids/hydroxycinnamoyl CoA Esters OMT (AEOMT). The deduced protein sequence of AEOMT is partially similar to, but clearly distinguishable from, that of CAOMTs and does not exhibit any significant similarity with CCoAOMT protein sequences. However, functionally, yeast-expressed AEOMT enzyme catalyzed the methylation of CAOMT substrates, caffeic and 5-hydroxyferulic acids, as well as CCoAOMT substrates, caffeoyl CoA and 5-hydroxyferuloyl CoA esters, with similar specific activities and was completely inactive with substrates associated with flavonoid synthesis. The lignin-related substrates were also efficiently methylated in crude extracts of loblolly pine secondary xylem. Our results support the notion that, in the context of amino acid sequence and biochemical function, AEOMT represents a novel SAM-dependent OMT, with both CAOMT and CCoAOMT activities and thus the potential to mediate a dual methylation pathway in lignin biosynthesis in loblolly pine xylem.

  11. A novel multifunctional O-methyltransferase implicated in a dual methylation pathway associated with lignin biosynthesis in loblolly pine

    Science.gov (United States)

    Li, Laigeng; Popko, Jacqueline L.; Zhang, Xing-Hai; Osakabe, Keishi; Tsai, Chung-Jui; Joshi, Chandrashekhar P.; Chiang, Vincent L.

    1997-01-01

    S-adenosyl-l-methionine (SAM)-dependent O-methyltransferases (OMTs) catalyze the methylation of hydroxycinnamic acid derivatives for the synthesis of methylated plant polyphenolics, including lignin. The distinction in the extent of methylation of lignins in angiosperms and gymnosperms, mediated by substrate-specific OMTs, represents one of the fundamental differences in lignin biosynthesis between these two classes of plants. In angiosperms, two types of structurally and functionally distinct lignin pathway OMTs, caffeic acid 3-O-methyltransferases (CAOMTs) and caffeoyl CoA 3-O-methyltransferases (CCoAOMTs), have been reported and extensively studied. However, little is known about lignin pathway OMTs in gymnosperms. We report here the first cloning of a loblolly pine (Pinus taeda) xylem cDNA encoding a multifunctional enzyme, SAM:hydroxycinnamic Acids/hydroxycinnamoyl CoA Esters OMT (AEOMT). The deduced protein sequence of AEOMT is partially similar to, but clearly distinguishable from, that of CAOMTs and does not exhibit any significant similarity with CCoAOMT protein sequences. However, functionally, yeast-expressed AEOMT enzyme catalyzed the methylation of CAOMT substrates, caffeic and 5-hydroxyferulic acids, as well as CCoAOMT substrates, caffeoyl CoA and 5-hydroxyferuloyl CoA esters, with similar specific activities and was completely inactive with substrates associated with flavonoid synthesis. The lignin-related substrates were also efficiently methylated in crude extracts of loblolly pine secondary xylem. Our results support the notion that, in the context of amino acid sequence and biochemical function, AEOMT represents a novel SAM-dependent OMT, with both CAOMT and CCoAOMT activities and thus the potential to mediate a dual methylation pathway in lignin biosynthesis in loblolly pine xylem. PMID:9144260

  12. 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

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

    Directory of Open Access Journals (Sweden)

    Xue-Fei Cao

    2013-12-01

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

  14. {6,6′-Dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne]diphenolato-1κ4O1,O1′,O6,O6′:2κ4O1,N,N′,O1′}(ethanol-1κO-μ-nitrato-1:2κ2O:O′-dinitrato-1κ4O,O′-samarium(IIIzinc(II

    Directory of Open Access Journals (Sweden)

    Qiang Huang

    2009-10-01

    Full Text Available In the title heteronuclear ZnII–SmIII complex, [SmZn(C18H18N2O4(NO33(CH3CH2OH], with the hexadentate Schiff base compartmental ligand N,N′-bis(3-methoxysalicylideneethylenediamine (H2L, the SmIII and ZnII ions are triply bridged by two phenolate O atoms from the Schiff base ligand and one nitrate anion. The five-coordinate ZnII ion is in a square-pyramidal geometry formed by the donor centers of two imine N atoms, two phenolate O atoms and one of the bridging nitrate O atoms. The SmIII center is in a ten-fold coordination of O atoms, involving the phenolate O atoms, two methoxy O atoms, one ethanol O atom, and two O atoms from two nitrate anions and one from the bridging nitrate anion. In the crystal, intermolecular O—H...O and C—H...O interactions generate a layer structure extending parallel to (101.

  15. Gene expression in the lignin biosynthesis pathway during soybean seed development.

    Science.gov (United States)

    Baldoni, A; Von Pinho, E V R; Fernandes, J S; Abreu, V M; Carvalho, M L M

    2013-02-28

    The study of gene expression in plants is fundamental, and understanding the molecular mechanisms involved in important biological processes, such as biochemical pathways or signaling that are used or manipulated in improvement programs, are key for the production of high-quality soybean seeds. Reports related to gene expression of lignin in seeds are scarce in the literature. We studied the expression of the phenylalanine ammonia-lyase (PAL), cinnamate 4-hydroxylase, 4-hydroxycinnamate 3-hydroxylase, and cinnamyl alcohol dehydrogenase genes involved in lignin biosynthesis during the development of soybean (Glycine max L. Merrill) seeds. As the endogenous control, the eukaryotic elongation factor 1-beta gene was used in two biological replicates performed in triplicate. Relative quantitative expression of these genes during the R4, R5, R6, and R7 development stages was analyzed. Real-time polymerase chain reaction was used for the gene expression study. The analyses were carried out in an ABI PRISM 7500 thermocycler using the comparative Ct method and SYBR Green to detect amplification. The seed samples at the R4 stage were chosen as calibrators. Increased expression of the cinnamate-4-hydroxylase and PAL genes occurred in soybean seeds at the R5 and R6 development stages. The cinnamyl alcohol dehydrogenase gene was expressed during the final development phases of soybean seeds. In low-lignin soybean cultivars, the higher expression of the PAL gene occurs at development stages R6 and R7. Activation of the genes involved in the lignin biosynthesis pathway occurs at the beginning of soybean seed development.

  16. Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts

    NARCIS (Netherlands)

    Guvenatam, Burcu; Kursun, Osman; Heeres, Hero; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2014-01-01

    The influence of reaction conditions (temperature, acidity) on the catalytic performance of supported Pt, Pd and Ru catalysts for the aqueous phase hydrodeoxygenation (HDO) of lignin model compounds was systematically investigated. Phenol conversion proceeds via hydrogenation of the aromatic ring

  17. Efficient photocatalytic reductive dechlorination of 4-chlorophenol to phenol on {0 0 1}/{1 0 1} facets co-exposed TiO_2 nanocrystals

    International Nuclear Information System (INIS)

    Jiang, Guodong; Wei, Meng; Yuan, Songdong; Chang, Qing

    2016-01-01

    Graphical abstract: - Highlights: • 4-Chlorophenol is dechlorinated over {0 0 1}/{1 0 1} co-exposed TiO_2 nanocrystals. • Photo-electrons are accumulated on {1 0 1} facets due to surface heterojunction. • Fluorine will trap photoelectrons to depress the dechlorination performance. • Sufficient isopropanol promotes the dechlorination activity and selectivity. - Abstract: 4-chlorophenol could be efficiently photoreductively dechlorinated over anatase TiO_2 nanocrystals with co-exposed {0 0 1} and {1 0 1} facets, which were synthesized and further characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Although fluorine could adsorb on {0 0 1} facets to decrease their surface energy, enabling TiO_2 to expose high energy {0 0 1} facets, the surface bonded fluorine might depress the photoreductive dechlorination efficiency of 4-chlorophenol, attributed to the electron trapping role of surface ≡Ti−F groups. Due to the formation of a surface heterojunction between {1 0 1} and {0 0 1} facets in a single TiO_2 nanocrystal, electrons and holes were spontaneously self-separated and selectively migrate to {1 0 1} and {0 0 1} facets, respectively. Electron trapping experiments demonstrated that photogenerated electrons are the responsible for the reductive dechlorinaton of 4-chlorophenol to phenol. To avoid the oxidative degradation of 4-chlorophenol by holes and ensure sufficient electrons to reductively dechlorinate the substrate, moderate scavengers were required in the reaction system and dissolved oxygen, which might deplete electron on TiO_2, also should be removed. With the optimal scavengers, the conversion efficiency of 4-chlorophenol (4-CP) achieved 97.5% and the selectivity for phenol was 92.5%, which were much higher than that of commercial TiO_2 P25.

  18. 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...

  19. Effect of processing on antioxidant potential and total phenolics content in beet (Beta vulgaris L.

    Directory of Open Access Journals (Sweden)

    Dorivaldo da Silva Raupp

    2011-09-01

    Full Text Available The antioxidant capacity of beet is associated with non-nutritive constituents, such as phenolic compounds. The purpose of this research was to evaluate the effect of two different heat-processing techniques (drying and canned on the antioxidant potential (ABTS and phenolics content of beets. A forced air circulation dehydrator was used for the drying. Drying at high temperatures (100 + 90 °C/5.6 hours; 90 °C/6 hours increased the antioxidant potential of the processed products while mild drying conditions decreased it (80 °C/6 hours; 100 + 70 °C/6 hours or had no effect on it (70 °C/7 hours; 100 + 80 °C/6 hours. For the canned products, the antioxidant potential did not differ according to the pH (4.2 to 3.8 for any of the four acids tested. Some processing methods influenced the antioxidant potential of the processed products, and this was also dependent on changes in the total phenolics content.

  20. 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.

  1. 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.

  2. 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.

  3. Efficient photocatalytic degradation of phenol in aqueous solution by SnO{sub 2}:Sb nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Al-Hamdi, Abdullah M., E-mail: Abdullah.Al.Hamdi@lut.fi [Laboratory of Green Chemistry, Lappeenranta University of Technology, Sammonkatu 12, 50130 Mikkeli (Finland); Chemistry Department, Sultan Qaboos University, P.O. Box 17, 123 Al-Khoudh (Oman); Chair in Nanotechnology, Water Research Center, Sultan Qaboos University, P.O. Box 17, 123 Al-Khoudh (Oman); Sillanpää, Mika [Laboratory of Green Chemistry, Lappeenranta University of Technology, Sammonkatu 12, 50130 Mikkeli (Finland); Bora, Tanujjal [Chair in Nanotechnology, Water Research Center, Sultan Qaboos University, P.O. Box 17, 123 Al-Khoudh (Oman); Dutta, Joydeep [Chair in Nanotechnology, Water Research Center, Sultan Qaboos University, P.O. Box 17, 123 Al-Khoudh (Oman); Functional Materials Division, ICT, KTH Royal Institute of Technology, Isafjordsgatan 22, SE-164 40 KistaStockholm (Sweden)

    2016-05-01

    Highlights: • Sb doped SnO{sub 2} nanoparticles were synthesized using sol–gel process. • Photocatalytic degradation of phenol were studies using SnO{sub 2}:Sb nanoparticles. • Under solar light phenol was degraded within 2 h. • Phenol mineralization and intermediates were investigated by using HPLC. - Abstract: Photodegradation of phenol in the presence of tin dioxide (SnO{sub 2}) nanoparticles under UV light irradiation is known to be an effective photocatalytic process. However, phenol degradation under solar light is less effective due to the large band gap of SnO{sub 2}. In this study antimony (Sb) doped tin dioxide (SnO{sub 2}) nanoparticles were prepared at a low temperature (80 °C) by a sol–gel method and studied for its photocatalytic activity with phenol as a test contaminant. The catalytic degradation of phenol in aqueous media was studied using high performance liquid chromatography and total organic carbon measurements. The change in the concentration of phenol affects the pH of the solution due to the by-products formed during the photo-oxidation of phenol. The photoactivity of SnO{sub 2}:Sb was found to be a maximum for 0.6 wt.% Sb doped SnO{sub 2} nanoparticles with 10 mg L{sup −1} phenol in water. Within 2 h of photodegradation, more than 95% of phenol could be removed under solar light irradiation.

  4. Template-mediated synthesis and bio-functionalization of flexible lignin-based nanotubes and nanowires

    Science.gov (United States)

    Caicedo, Hector M.; Dempere, Luisa A.; Vermerris, Wilfred

    2012-03-01

    Limitations of cylindrical carbon nanotubes based on the buckminsterfullerene structure as delivery vehicles for therapeutic agents include their chemical inertness, sharp edges and toxicological concerns. As an alternative, we have developed lignin-based nanotubes synthesized in a sacrificial template of commercially available alumina membranes. Lignin is a complex phenolic plant cell wall polymer that is generated as a waste product from paper mills and biorefineries that process lignocellulosic biomass into fuels and chemicals. We covalently linked isolated lignin to the inner walls of activated alumina membranes and then added layers of dehydrogenation polymer onto this base layer via a peroxidase-catalyzed reaction. By using phenolic monomers displaying different reactivities, we were able to change the thickness of the polymer layer deposited within the pores, resulting in the synthesis of nanotubes with a wall thickness of approximately 15 nm or nanowires with a nominal diameter of 200 nm. These novel nanotubes are flexible and can be bio-functionalized easily and specifically, as shown by in vitro assays with biotin and Concanavalin A. Together with their intrinsic optical properties, which can also be varied as a function of their chemical composition, these lignin-based nanotubes are expected to enable a variety of new applications including as delivery systems that can be easily localized and imaged after uptake by living cells.

  5. Template-mediated synthesis and bio-functionalization of flexible lignin-based nanotubes and nanowires

    International Nuclear Information System (INIS)

    Caicedo, Hector M; Vermerris, Wilfred; Dempere, Luisa A

    2012-01-01

    Limitations of cylindrical carbon nanotubes based on the buckminsterfullerene structure as delivery vehicles for therapeutic agents include their chemical inertness, sharp edges and toxicological concerns. As an alternative, we have developed lignin-based nanotubes synthesized in a sacrificial template of commercially available alumina membranes. Lignin is a complex phenolic plant cell wall polymer that is generated as a waste product from paper mills and biorefineries that process lignocellulosic biomass into fuels and chemicals. We covalently linked isolated lignin to the inner walls of activated alumina membranes and then added layers of dehydrogenation polymer onto this base layer via a peroxidase-catalyzed reaction. By using phenolic monomers displaying different reactivities, we were able to change the thickness of the polymer layer deposited within the pores, resulting in the synthesis of nanotubes with a wall thickness of approximately 15 nm or nanowires with a nominal diameter of 200 nm. These novel nanotubes are flexible and can be bio-functionalized easily and specifically, as shown by in vitro assays with biotin and Concanavalin A. Together with their intrinsic optical properties, which can also be varied as a function of their chemical composition, these lignin-based nanotubes are expected to enable a variety of new applications including as delivery systems that can be easily localized and imaged after uptake by living cells. (paper)

  6. 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

  7. Ab initio atomistic thermodynamics calculations of the initial deposition of epitaxial MgO film on GaAs(001)-{beta}2(2 Multiplication-Sign 4)

    Energy Technology Data Exchange (ETDEWEB)

    Tamarany, Rizcky; Lee, Seung-Cheol [Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of); Department of Nanomaterials Science and Engineering, University of Science and Technology, Daejeon 305-350 (Korea, Republic of); Kim, Hyung-Jun; Choi, Jung-Hae [Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of)

    2013-02-07

    Ab initio calculations were performed to investigate the initial deposition of epitaxial MgO on GaAs(001)-{beta}2(2 Multiplication-Sign 4). The differences between the chemical bonding of Mg-As and O-As were characterized by the adsorption energies of atomic O and Mg at several symmetrically distinct sites, and O bonding was substantially stronger than that of Mg. Thermodynamics were analyzed through the introduction of environmental chemical potentials simulating in situ growth conditions by the sputtering of a stoichiometric MgO target. A surface phase diagram was generated under Mg and O environments with constrained equilibrium, and the results explained the initial formation of an epitaxial MgO phase on GaAs(001)-{beta}2(2 Multiplication-Sign 4).

  8. 3-Nitro-phenol-1,3,5-triazine-2,4,6-tri-amine (2/1).

    Science.gov (United States)

    Sangeetha, V; Kanagathara, N; Chakkaravarthi, G; Marchewka, M K; Anbalagan, G

    2013-06-01

    The asymmetric unit of the title compound, C3H6N6·2C6H5NO3, contains one melamine and two 3-nitro-phenol mol-ecules. The mean planes of the 3-nitro-phenol mol-ecules are almost orthogonal to the plane of melamine, making dihedral angles of 82.77 (4) and 88.36 (5)°. In the crystal, mol-ecules are linked via O-H⋯N, N-H⋯N and N-H⋯O hydrogen bonds, forming a three-dimensional network. The crystal also features weak C-H⋯π and π-π inter-actions [centroid-centroid distance = 3.9823 (9) Å].

  9. Natural Phenol Polymers: Recent Advances in Food and Health Applications.

    Science.gov (United States)

    Panzella, Lucia; Napolitano, Alessandra

    2017-04-14

    Natural phenol polymers are widely represented in nature and include a variety of classes including tannins and lignins as the most prominent. Largely consumed foods are rich sources of phenol polymers, notably black foods traditionally used in East Asia, but other non-edible, easily accessible sources, e.g., seaweeds and wood, have been considered with increasing interest together with waste materials from agro-based industries, primarily grape pomace and other byproducts of fruit and coffee processing. Not in all cases were the main structural components of these materials identified because of their highly heterogeneous nature. The great beneficial effects of natural phenol-based polymers on human health and their potential in improving the quality of food were largely explored, and this review critically addresses the most interesting and innovative reports in the field of nutrition and biomedicine that have appeared in the last five years. Several in vivo human and animal trials supported the proposed use of these materials as food supplements and for amelioration of the health and production of livestock. Biocompatible and stable functional polymers prepared by peroxidase-catalyzed polymerization of natural phenols, as well as natural phenol polymers were exploited as conventional and green plastic additives in smart packaging and food-spoilage prevention applications. The potential of natural phenol polymers in regenerative biomedicine as additives of biomaterials to promote growth and differentiation of osteoblasts is also discussed.

  10. 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.)

  11. Soil type-depending effect of paddy management: composition and distribution of soil organic matter

    Science.gov (United States)

    Urbanski, Livia; Kölbl, Angelika; Lehndorff, Eva; Houtermans, Miriam; Schad, Peter; Zhang, Gang-Lin; Rahayu Utami, Sri; Kögel-Knabner, Ingrid

    2016-04-01

    Paddy soil management is assumed to promote soil organic matter accumulation and specifically lignin caused by the resistance of the aromatic lignin structure against biodegradation under anaerobic conditions during inundation of paddy fields. The present study investigates the effect of paddy soil management on soil organic matter composition compared to agricultural soils which are not used for rice production (non-paddy soils). A variety of major soil types, were chosen in Indonesia (Java), including Alisol, Andosol and Vertisol sites (humid tropical climate of Java, Indonesia) and in China Alisol sites (humid subtropical climate, Nanjing). This soils are typically used for rice cultivation and represent a large range of soil properties to be expected in Asian paddy fields. All topsoils were analysed for their soil organic matter composition by solid-state 13C nuclear magnetic resonance spectroscopy and lignin-derived phenols by CuO oxidation method. The soil organic matter composition, revealed by solid-state 13C nuclear magnetic resonance, was similar for the above named different parent soil types (non-paddy soils) and was also not affected by the specific paddy soil management. The contribution of lignin-related carbon groups to total SOM was similar in the investigated paddy and non-paddy soils. A significant proportion of the total aromatic carbon in some paddy and non-paddy soils was attributed to the application of charcoal as a common management practise. The extraction of lignin-derived phenols revealed low VSC (vanillyl, syringyl, cinnamyl) values for all investigated soils, being typical for agricultural soils. An inherent accumulation of lignin-derived phenols due to paddy management was not found. Lignin-derived phenols seem to be soil type-dependent, shown by different VSC concentrations between the parent soil types. The specific paddy management only affects the lignin-derived phenols in Andosol-derived paddy soils which are characterized by

  12. Export of Dissolved Lignin from Coastal Wetlands to the Louisiana Shelf

    Science.gov (United States)

    Bianchi, T. S.; Dimarco, S. F.; Smith, R. W.; Schreiner, K. M.

    2008-12-01

    Here we report on spatial and temporal changes in the concentration and composition of dissolved lignin- phenols in surface and bottom waters off the Louisiana coast (USA). Samples were collected at 7 stations on 2 cruises (April, and July, 2008) along a transect that spanned from inside Terrebonne Bay, Louisiana (12 m water depth) to the outer-most station on the inner Louisiana shelf (21 m water depth). The highest average concentration of dissolved organic carbon (DOC) and dissolved lignin, during both cruises, occurred at the interface between Terrebonne Bay and the inner shelf. Average DOC and dissolved lignin concentrations were significantly higher in April than in July across most stations. Based on hydrologic data, these higher concentrations clearly reflect a combined mixing of DOM from plume waters to the west and local marsh inputs. The cinnamyl/vanillyl (C/V) and syringyl/vanillyl (S/V) ratios indicated that the predominant source of lignin was from non-woody angiosperms - likely the dominant species of wetland plants Spartina alterniflora and S. patens (Spartina spp.) that border the entire bay. The high vanillic acid to vanillin (Ad/Al)v ratios for all stations were typical of that found near estuarine boundaries, where biologically- and photochemically-mediated lignin decay processes are important. This preliminary data indicates that wetlands provide another source of dissolved organic matter (DOM) to the Louisiana shelf that likely contributes to microbial food resources and hence hypoxia, especially in the context of the instability and extensive erosion of these marshes over the past ca. 50 years. This has important implications for the current management plan to reduce hypoxia in the GOM, particularly in those regions that extend west of the nutrient-rich highly productive near-field zones of Atchafalaya-Mississippi river plumes.

  13. Efficient photocatalytic reductive dechlorination of 4-chlorophenol to phenol on {0 0 1}/{1 0 1} facets co-exposed TiO{sub 2} nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Guodong; Wei, Meng; Yuan, Songdong [College of Chemistry and chemical engineering, Hubei Collaborative Innovation Center for High Efficient Utilization of Solar Energy, Hubei University of Technology, Wuhan 430068 (China); Chang, Qing, E-mail: changqinghust@163.com [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan 430074 (China)

    2016-01-30

    Graphical abstract: - Highlights: • 4-Chlorophenol is dechlorinated over {0 0 1}/{1 0 1} co-exposed TiO{sub 2} nanocrystals. • Photo-electrons are accumulated on {1 0 1} facets due to surface heterojunction. • Fluorine will trap photoelectrons to depress the dechlorination performance. • Sufficient isopropanol promotes the dechlorination activity and selectivity. - Abstract: 4-chlorophenol could be efficiently photoreductively dechlorinated over anatase TiO{sub 2} nanocrystals with co-exposed {0 0 1} and {1 0 1} facets, which were synthesized and further characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Although fluorine could adsorb on {0 0 1} facets to decrease their surface energy, enabling TiO{sub 2} to expose high energy {0 0 1} facets, the surface bonded fluorine might depress the photoreductive dechlorination efficiency of 4-chlorophenol, attributed to the electron trapping role of surface ≡Ti−F groups. Due to the formation of a surface heterojunction between {1 0 1} and {0 0 1} facets in a single TiO{sub 2} nanocrystal, electrons and holes were spontaneously self-separated and selectively migrate to {1 0 1} and {0 0 1} facets, respectively. Electron trapping experiments demonstrated that photogenerated electrons are the responsible for the reductive dechlorinaton of 4-chlorophenol to phenol. To avoid the oxidative degradation of 4-chlorophenol by holes and ensure sufficient electrons to reductively dechlorinate the substrate, moderate scavengers were required in the reaction system and dissolved oxygen, which might deplete electron on TiO{sub 2}, also should be removed. With the optimal scavengers, the conversion efficiency of 4-chlorophenol (4-CP) achieved 97.5% and the selectivity for phenol was 92.5%, which were much higher than that of commercial TiO{sub 2} P25.

  14. Biosynthesis of phenolic compounds in hypocotyl callus cultures of fenugreek (Trigonella foenum graecum L. )

    Energy Technology Data Exchange (ETDEWEB)

    Dhandapani, M; Antony, A; Subba Rao, P V [Indian Inst. of Science, Bangalore. Dept. of Biochemistry

    1977-03-01

    Hypocotyl callus cultures of fenugreek were studied to determine their potential for synthesizing phenolics, particularly those which are intermediates in lignin and flavonoid biosynthesis. The cultures were found to be capable of synthesizing an array of phenolic compounds characteristic of higher plants. Both phenylalanine-U-/sup 14/C and cinnamic acid-U-/sup 14/C were found to be efficient precursors of these phenolics.

  15. Extração, análise e distribuição dos ácidos fenólicos em genótipos pigmentados e não pigmentados de arroz (Oryza sativa L. Extraction, analysis and distribution of phenolic acids in pigmented and non-pigmented genotypes of rice (Oryza sativa L.

    Directory of Open Access Journals (Sweden)

    Nádia Valéria Mussi de Mira

    2008-12-01

    Full Text Available Neste estudo, avaliaram-se a distribuição dos Compostos Fenólicos Totais (CFT e o perfil de ácidos fenólicos, presentes nas frações, solúvel e insolúvel de dez genótipos de arroz (Oryza sativa L. de pericarpo pigmentado e não pigmentado. Devido à sua elevada capacidade antioxidante, os compostos fenólicos vem sendo apontados como possíveis promotores da saúde. Grande parte corresponde aos ácidos fenólicos presentes no grão sob a forma solúvel (livre e conjugada e insolúvel (ligada. Na literatura há poucas informações sobre a contribuição dos compostos fenólicos ligados, cujos teores são costumeiramente subestimados. Os CFT foram quantificados pelo método de Folin-Ciocalteau, enquanto os ácidos fenólicos por RP-HPLC. Na fração solúvel dos genótipos pigmentados, os teores de CFT foram variáveis, mas, em média, 5,7 vezes maiores do que nos não pigmentados (média de 3468 e 602 µg eq. Ácido Ferúlico (AF/g arroz, respectivamente, principalmente devido à presença de antocianinas e proantocianidinas. Na fração insolúvel, os pigmentados apresentaram duas vezes mais CFT do que os não pigmentados (825 e 378 µg eq. AF/g arroz, respectivamente, provavelmente devido à retenção de antocianinas e proantocianidinas, mesmo após cinco extrações consecutivas. Dentre os ácidos fenólicos, o ácido ferúlico foi o principal componente em todos os genótipos estudados, exceto no arroz preto, no qual predominou o ácido protocatecóico.This study was conducted to evaluate the distribution of total phenolic compounds and phenolic acids in the soluble and insoluble fractions of 10 rice (Oryza sativa L. genotypes with pigmented or non-pigmented pericarp. These compounds were reported to exert beneficial effects on human health due to their high antioxidant activities. The total phenolic compounds (CFT in both fractions was determined by the Folin-Ciocalteau method and phenolic acids RP-HPLC with Diode-Array Detection

  16. Atualizações sobre beta-hidroxi-beta-metilbutirato: suplementação e efeitos sobre o catabolismo de proteínas New findings on beta-hydroxy-beta-methylbutyirate: supplementation and effects on the protein catabolism

    Directory of Open Access Journals (Sweden)

    Everson Araújo Nunes

    2008-04-01

    Full Text Available O beta-hidroxi-beta-metilbutirato, metabólito do aminoácido leucina, vem sendo utilizado como suplemento alimentar, em situações específicas, com o intuito de aumentar ou manter a massa isenta de gordura. Os relatos dos efeitos do beta-hidroxi-beta-metilbutirato em estudos recentes fizeram crescer as expectativas sobre sua utilização em casos patológicos. Também foram demonstrados melhores resultados, quando da sua ingestão, no treinamento de força em indivíduos iniciantes e em idosos. Em humanos o beta-hidroxi-beta-metilbutirato tem sido usado como agente anti-catabólico, e em modelos animais foi demonstrado ser eficaz em inibir a atividade de vias proteolíticas em células musculares de indivíduos caquéticos in vitro e in vivo. Os mecanismos participantes desses processos envolvem: a inibição da atividade do sistema ubiquitina proteossoma ATP-dependente, a inibição de vias de sinalização com participação da proteína quinase C-alfa e a diminuição da concentração citoplasmática do fator nuclear - kappa B livre, eventos relacionados ao decréscimo da proteólise em células musculares.The leucine metabolite beta-hydroxy-beta-methylbutyrate has been used as a nutritional supplement in specific situations to prevent losing or to increase lean mass. Recent studies showed interesting results of beta-hydroxy-beta-methylbutyrate supplementation in certain disease states. Better results have also been demonstrated when it is taken by starters or old individuals doing strength training. In humans, beta-hydroxy-beta-methylbutyrate has been used as an anticatabolic agent and in animal models it has been demonstrated to be effective in inhibiting the activity of the proteolytic pathways in muscle cells of extremely weak individuals in vivo and in vitro. The mechanisms that participate in this process involve: inhibition of the ATP-ubiquitin-proteasome pathway, inhibition of the signalization pathways involving protein kinase C

  17. Efeito do conteúdo e da natureza da lignina residual na eficiência e na seletividade do branqueamento com ozônio Effect of residual lignin content and nature on the efficiency and selectivity of ozone bleaching

    Directory of Open Access Journals (Sweden)

    Elenice Pereira Maia

    2003-04-01

    Full Text Available Neste estudo foram avaliados os efeitos do conteúdo e da natureza da lignina residual na eficiência e na seletividade do branqueamento com ozônio de polpa kraft convencional (kraft e pré-deslignificada com oxigênio (kraft-O. Constatou-se que a eficiência do branqueamento com ozônio se eleva com o aumento do conteúdo de lignina residual da polpa. O tratamento com ozônio é mais seletivo para polpas kraft-O, mas para um mesmo tipo de polpa a seletividade de branqueamento com ozônio se eleva com o aumento de lignina residual. A eficiência do branqueamento com ozônio aumenta com o teor de lignina fenólica na polpa, entretanto a seletividade é negativamente afetada pela presença destas estruturas.This study aimed to evaluate the effect of residual lignin content and nature on the efficiency and selectivity of ozone bleaching of conventional (kraft and oxygen delignified (kraft-O pulps. Ozone bleaching efficiency was found to be enhanced by increasing pulp residual lignin content. Ozone treatment is more selective for kraft-O pulps, but for a given type of pulp (kraft or kraft-O, ozone bleaching selectivity increases with increasing pulp lignin content. Ozone bleaching efficiency increases with increasing pulp lignin phenolic hydroxyl content whereas selectivity is negatively affected by these structures.

  18. Lignin biodegradation: experimental evidence, molecular, biochemical and physiological mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Monties, B

    1985-01-01

    A critical review is presented of English, French and some German language literature, mainly from 1983 onwards. It examines experimental evidence on the behaviour as barriers to biodegradation of lignins and phenolic polymers such as tannins and suberins. The different molecular mechanisms of lignolysis by fungi (mainly), actinomycetes and bacteria are examined. A new biochemical approach to the physiological mechanism of regulation of lignolytic activities is suggested based on the discoveries of ligniolytic enzymes: effects of nitrogen, oxygen and substrate are discussed. It is concluded that a better knowledge of the structure and reactivity of phenolic barriers is needed in order to control the process of lignolysis.

  19. Anionic chromogenic chemosensors highly selective for fluoride or cyanide based on 4-(4-Nitrobenzylideneamine)phenol

    Energy Technology Data Exchange (ETDEWEB)

    Nicoleti, Celso R; Marini, Vanderleia G; Zimmermann, Lizandra M; Machado, Vanderlei G., E-mail: vanderlei.machado@ufsc.br [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil)

    2012-08-15

    4-(4-Nitrobenzylideneamine)phenol was used in two strategies allowing the highly selective detection of F{sup -} and CN{sup -}. Firstly, the compound in acetonitrile acts as a chromogenic chemosensor based on the idea that more basic anions cause its deprotonation (colorless solution), generating a colored solution containing phenolate. The discrimination of CN{sup -} over F{sup -} was obtained by adding 1.4% water to acetonitrile: water preferentially solvates F{sup -}, leaving the CN{sup -} free to deprotonate the compound. Another strategy involved an assay comprised of the competition between phenolate dye and the analyte for calyx[4]pyrrole in acetonitrile, a receptor highly selective for F{sup -}. Phenolate and calyx[4]pyrrole form a hydrogen-bonded complex, which changes the color of the medium. On the addition of various anions, only F{sup -} was able to restore the original color corresponding to phenolate in solution due to the fact that the anion dislodges phenolate from the complexation site. (author)

  20. Anionic chromogenic chemosensors highly selective for fluoride or cyanide based on 4-(4-Nitrobenzylideneamine)phenol

    International Nuclear Information System (INIS)

    Nicoleti, Celso R.; Marini, Vanderleia G.; Zimmermann, Lizandra M.; Machado, Vanderlei G.

    2012-01-01

    4-(4-Nitrobenzylideneamine)phenol was used in two strategies allowing the highly selective detection of F - and CN - . Firstly, the compound in acetonitrile acts as a chromogenic chemosensor based on the idea that more basic anions cause its deprotonation (colorless solution), generating a colored solution containing phenolate. The discrimination of CN - over F - was obtained by adding 1.4% water to acetonitrile: water preferentially solvates F - , leaving the CN - free to deprotonate the compound. Another strategy involved an assay comprised of the competition between phenolate dye and the analyte for calyx[4]pyrrole in acetonitrile, a receptor highly selective for F - . Phenolate and calyx[4]pyrrole form a hydrogen-bonded complex, which changes the color of the medium. On the addition of various anions, only F - was able to restore the original color corresponding to phenolate in solution due to the fact that the anion dislodges phenolate from the complexation site. (author)

  1. Clean production of corn stover pulp using KOH+NH4OH solution and its kinetic during delignification

    OpenAIRE

    Sun Yong; Yang Gang; Zhang Jin-Ping; Yao Ming-Shun

    2012-01-01

    The self-made KOH together with NH4OH pulping of corn stover was investigated. The combined alkaline system could effectively remove lignin during pulping. There are three stages of lignin removal during delginification. Approximately 90% of lignin could be removed after temperature reached 150ºC for over 30 minutes. The p-hydroxyl phenol groups in lignin could be completely removed during the delignification reaction. The tendency of the increase of the crystalline degree of cellulose ...

  2. CATALYTIC PERFORMANCES OF Fe2O3/TS-1 CATALYST IN PHENOL HYDROXYLATION REACTION

    Directory of Open Access Journals (Sweden)

    Didik Prasetyoko

    2010-07-01

    Full Text Available Hydroxylation reaction of phenol into diphenol, such as hydroquinone and catechol, has a great role in many industrial applications. Phenol hydroxylation reaction can be carried out using Titanium Silicalite-1 (TS-1 as catalyst and H2O2 as an oxidant. TS-1 catalyst shows high activity and selectivity for phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be low. Addition of metal oxide Fe2O3 enhanced hydrophilicity of TS-1 catalyst. Liquid phase catalytic phenol hydroxylation using hydrogen peroxide as oxidant was carried out over iron (III oxide-modified TS-1 catalyst (Fe2O3/TS-1, that were prepared by impregnation method using iron (III nitrate as precursor and characterized by X-ray diffraction, infrared spectroscopy, nitrogen adsorption, pyridine adsorption, and hydrophilicity techniques. Catalysts 1Fe2O3/TS-1 showed maximum catalytic activity of hydroquinone product. In this research, the increase of hydroquinone formation rate is due to the higher hydrophilicity of Fe2O3/TS-1 catalysts compare to the parent catalyst, TS-1.   Keywords: Fe2O3/TS-1, hydrophilic site, phenol hydroxylation

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

    Science.gov (United States)

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

    2018-01-26

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

  4. Beta decay of 22O

    International Nuclear Information System (INIS)

    Hubert, F.; Dufour, J.P.; Moral, R. del; Fleury, A.; Jean, D.; Pravikoff, M.S.; Delagrange, H.; Geissel, H.; Schmidt, K.H.; Hanelt, E.

    1989-01-01

    The beta-gamma spectroscopic study of 22 O is presented. This nucleus, produced as a projectile-like fragment from the interaction of a 60 MeV/n 40 Ar beam with a Be target, has been separated by the LISE spectrometer. Several gamma rays from 22 O decay have been observed, from which a half-life of (2.25±0.15) s has been determined. Accurate excitation energies have been deduced for several states in 22 F. A partial beta decay scheme of 22 O has been established. Experimental results have been compared with shell model calculations. (orig.)

  5. Study on adsorption of rhodamine B onto Beta zeolites by tuning SiO2/Al2O3 ratio.

    Science.gov (United States)

    Cheng, Zhi-Lin; Li, Yan-Xiang; Liu, Zan

    2018-02-01

    The exploration of the relationship between zeolite composition and adsorption performance favored to facilitate its better application in removal of the hazardous substances from water. The adsorption capacity of rhodamine B (RB) onto Beta zeolite from aqueous solution was reported. The relationship between SiO 2 /Al 2 O 3 ratio and adsorption capacity of Beta zeolite for RB was explored. The structure and physical properties of Beta zeolites with various SiO 2 /Al 2 O 3 ratios were determined by XRD, FTIR, TEM, BET, UV-vis and so on characterizations. The adsorption behavior of rhodamine B onto Beta zeolite matched to Langmuir adsorption isotherm and more suitable description for the adsorption kinetics was a pseudo-second-order reaction model. The maximum adsorption capacity of the as-prepared Beta zeolite with SiO 2 /Al 2 O 3 = 18.4 was up to 27.97mg/g. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. The O-H Bond Dissociation Energies of Substituted Phenols and Proton Affinities of Substituted Phenoxide Ions: A DFT Study

    Directory of Open Access Journals (Sweden)

    Tadafumi Uchimaru

    2002-04-01

    Full Text Available Abstract: The accurate O-H bond dissociation enthalpies for a series of meta and para substituted phenols (X-C6H4-OH, X=H, F, Cl, CH3, OCH3, OH, NH2, CF3, CN, and NO2 have been calculated by using the (ROB3LYP procedure with 6-311G(d,p and 6-311++G(2df,2p basis sets. The proton affinities of the corresponding phenoxide ions (XC6H4-O- have also been computed at the same level of theory. The effect of change of substituent position on the energetics of substituted phenols has been analyzed. The correlations of Hammett’s substituent constants with the bond dissociation enthalpies of the O-H bonds of phenols and proton affinities of phenoxide ions have been explored.

  7. Removal of Phenol and o-Cresol by Adsorption onto Activated Carbon

    Directory of Open Access Journals (Sweden)

    A. Edwin Vasu

    2008-01-01

    Full Text Available A commercial activated carbon was utilized for the adsorptive removal of phenol and o-cresol from dilute aqueous solutions. Batch mode adsorption studies were performed by varying parameters such as concentration of phenol solution, time, pH and temperature. The well known Freundlich, Langmuir and Redlich-Peterson isotherm equations were applied for the equilibrium adsorption data and the various isotherm parameters were evaluated. The Langmuir monolayer adsorption capacities were found to be 0.7877 and 0.5936 mmole/g, respectively, for phenol and o-cresol. Kinetic studies performed indicate that the sorption processes can be better represented by the pseudo-second order kinetics. The processes were found to be endothermic and the thermodynamic parameters were evaluated. Desorption studies performed indicate that the sorbed phenol molecules can be desorbed with dil. HCl.

  8. 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.

  9. Avaliação da atividade antioxidante dos compostos fenólicos naturalmente presentes em subprodutos do pseudofruto de caju (Anacardium occidentale L. Evaluation of the Antioxidant Activity of Phenolic Compounds Naturally Contained in By-products of the Cashew Apple (Anacardium occidentale L.

    Directory of Open Access Journals (Sweden)

    Priscila Regina Bolelli Broinizi

    2007-12-01

    Full Text Available O presente trabalho teve como proposta avaliar a capacidade antioxidante do bagaço e do extrato bruto concentrado (EBC do pedúnculo de caju, tendo em vista o seu aproveitamento. O potencial antioxidante dos extratos aquoso (EAq e alcoólico (EAlc e das frações de ácidos fenólicos livres (AFL e esterificadas (solúvel AFS e insolúvel AFI desses subprodutos do pedúnculo de caju clone CCP-76 foi avaliado em sistema beta-caroteno/ácido linoléico, pelo teste de varredura de radical livre [2,2 difenil-1-pricril-hidrazil (DPPH•] e de Rancimat. Além do mais, o conteúdo de fenólicos totais e o perfil de ácidos fenólicos foram determinados usando-se o reagente de Folin-Ciocateau e por cromatografia gasosa, respectivamente. O EAq e a fração AFL dos subprodutos apresentaram o maior conteúdo de fenólicos. As frações de ácidos fenólicos exibiram expressiva atividade antioxidante, superior aos extratos estudados nos sistemas beta-caroteno e DPPH. Entretanto no teste Rancimat, os extratos apresentaram maior proteção à oxidação em relação às frações e ao BHT. Nas frações foram identificados os ácidos gálico, ferúlico, caféico, protocatecuico, quínico, cinâmico, gentíssico, p-cumárico e salicílico, os quais lhes conferem o potencial antioxidante. Estes resultados caracterizaram in vitro o potencial antioxidante do bagaço e do EBC do pedúnculo de caju clone CCP-76.This study aimed to determine the antioxidant capacity of cashew apple pulp and raw concentrated extract. The antioxidant potential of aqueous (EAq and alcoholic (EAlc extracts and of free phenolic acids (FPA and esterified (soluble - SPA and insoluble - IPA fractions of the by-products of the cashew apple clone CCP-76 were evaluated in a beta-carotene-linoleate system by the free radical [2,2-diphenyl-1-picrylhydrazyl (DPPH•] scavenging assay and the Rancimat test. In addition, the total phenolic content and phenolic acid profile were determined using

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

    Energy Technology Data Exchange (ETDEWEB)

    Abdul-Rahman, M.M.

    1988-01-01

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

  11. 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.

  12. Composição centesimal e teor de beta-glucanas em cereais e derivados Nutrient profile and beta-glucans content in cereal seeds and foodstuffs contain them

    Directory of Open Access Journals (Sweden)

    Alexandre H. Fujita

    2003-08-01

    Full Text Available Foi utilizado o método enzimático recomendado pela AOAC para determinação de beta-glucanas em cereais e alimentos que os contém. O método, utiliza liquenase (EC 3.2.1.73 e beta-glucosidase (EC 3.2.1.21 para hidrólise debeta-glucanas, é rápido, fácil de executar e específico para beta-glucanas com ligações beta(1->3 e beta(1->4. As sementes analisadas foram subministradas pelo Instituto Agronômico de Campinas (IAC e os alimentos adquiridos nos supermercados. Aveia e cevada são os grãos com maior conteúdo de beta-glucanas. Na aveia os teores determinados foram 6,48 e 5,94%. Nos 10 cultivares de cevada os teores de beta-glucanas oscilaram entre 2,04 e 9,68%. Trigo e triticale apresentaram teores de b-glucanas menores que 1%. Nos produtos comerciais o teor de beta-glucanas estava relacionado ao tipo de cereal da fórmula. O produto comercial de maior conteúdo de beta-glucanas é o farelo de aveia. As beta-glucanas são ingredientes funcionais em potencial e a conveniência ou não de estimular sua incorporação em alimentos deve ser mais estudada. Quanto à composição centesimal dos grãos de cereais, o teor de proteínas foi o que apresentou a maior variação e isso se reflete na composição dos produtos comerciais.The method employed was the enzymatic one recommended by de AOAC for the determination of beta-glucans in cereals and in foodstuffs containing cereals in their formulation. The method, using lichenase (EC 3.2.1.73 and beta-glucosidase (EC 3.2.1.21 for the hydrolysis of beta-glucans, is quick and easy to execute, but is specific for beta-glucans with beta(1->3 and beta(1->4 bonds. The Agronomic Institute of Campinas (IAC supplied the seeds analyzed, and the foodstuffs were acquired in supermarkets. Oat and barley are the grains with the highest content of beta-glucans. In the oats, the determined values were 6.48 and 5.94%. In the 10 cultivars of barley, the content of beta-glucans varied between 2.04 and 9

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

    Directory of Open Access Journals (Sweden)

    Elumalai Sasikumar

    2012-08-01

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

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

    Science.gov (United States)

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

    2016-10-01

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

  15. Depolymerization and hydrodeoxygenation of switchgrass lignin with formic acid.

    Science.gov (United States)

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

    2012-04-01

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

  16. A powder neutron diffraction study of stoichiometric silver beta alumina at 4.2 K

    International Nuclear Information System (INIS)

    Newsam, J.M.; Tofield, B.C.

    1980-10-01

    The low-temperature structure of stoichiometric silver beta alumina, AgAl 11 O 17 , is described for the first time. A powder neutron diffraction study at 4.2 K reveals that there is a single three-fold silver location of unit occupancy in each mirror plane. The silver site lies between the mid-oxygen and Beevers-Ross positions where the Ag-O contact distances can be minimised. The Ag-O interactions, in particular the cooperative movement of the spacer oxygens, are responsible for the superlattice which has been described previously. The Beevers-Ross, anti-Beevers-Ross and interstitial aluminium sites are vacant and the c-axis constant is expanded relative to the non-stoichiometric parent. (author)

  17. Seasonal variation of phenolic content in galled and non-galled tissues of Calliandra brevipes Benth (Fabaceae: Mimosoidae Variação sazonal do conteúdo fenólico em tecidos galhados e não-galhados de Calliandra brevipes Benth (Fabaceae: Mimosoidae

    Directory of Open Access Journals (Sweden)

    Michelle de Lima Detoni

    2011-09-01

    Full Text Available Two species, Tanaostigmodes ringueleti and T. mecanga, induce distinct galls on Calliandra brevipes Benth (Fabaceae: Mimosoidae, a globose and a fusiform gall morphotype. Seasonal changes of phenolic content in the tissues of the two distinct galls were compared to those of non-galled leaves and stems of the host plants over one year. The variation in the phenolic content profiles was similar in both non-galled and galled tissues, and was primarily associated with changes in the levels of rainfall, indicating a direct response to hydric stress. In periods of drastic changes in water precipitation, the alterations were significantly higher in non-galled than in galled tissues suggesting that the gall inducers might limit the variation in the phenolic concentration for their own benefit.Duas espécies, Tanaostigmodes ringueleti e T. mecanga, induzem galhas distintas em Calliandra brevipes Benth (Fabaceae: Mimosoidae, um morfotipo globoso e um fusiforme. Mudanças sazonais no conteúdo fenólico nos tecidos das duas galhas foram comparadas àquelas de folha e caule não galhados das plantas hospedeiras por um ano. A variação no perfil de conteúdo fenólico foi similar em tecidos galhados e não galhados, sendo associada primariamente às mudanças nos níveis de chuva, constituindo uma resposta direta ao estresse hídrico. Nos períodos de mudanças drásticas na precipitação de água, as alterações foram significativamente maiores em tecido não galhados do que em tecidos galhados, sugerindo que os galhadores estariam limitando a variação do conteúdo fenólico em seu próprio benefício.

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

    Science.gov (United States)

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

    2013-03-13

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

  19. 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.

  20. Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Kasakov, Stanislav; Shi, Hui; Camaioni, Donald M.; Zhao, Chen; Barath, Eszter; Jentys, Andreas; Lercher, Johannes A.

    2015-11-01

    Mechanistic aspects of deconstruction and hydrodeoxygenation of organosolv lignin using supported Ni catalysts with (Ni/HZSM-5 and Ni/HBEA) and without Brønsted acid sites (Ni/SiO2) are reported. Lignin was deconstructed and converted to saturated cyclic hydrocarbons ranging from C5 to C14. In the one-stage reaction, full conversion with total yield of 70 ± 5 wt.% saturated hydrocarbons was achieved at 593 K and 20 bar H2. The organosolv lignin used consists of seven to eight monolignol subunits and has an average molecular weight of ca. 1200 g mol-1. The monolignols were mainly guaiacyl, syringyl and phenylcoumaran, randomly interconnected through β-O-4, 4-O-5, β-1, 5-5’ and β-β ether bonds. In situ IR spectroscopy was used to follow the changes in lignin constituents during reaction. The proposed reaction pathways for the catalytic transformation of this organosolv lignin to alkanes start with the hydrogenolysis of aryl alkyl ether bonds, followed by hydrogenation of the aromatic compounds on Ni to cyclic alcohols. Oxygen is removed from the alcohols via dehydration on Brønsted acid sites to yield cyclic alkenes that are further hydrogenated to alkanes. Formation of condensation products may occur via intermolecular recombination of aromatic monomers or alkylation of aromatic compounds by alkenes. The financial support from TUM-PNNL cooperation project “Development of new methods for in situ characterization in liquid phase reactions” (CN-177939) is highly appreciated. The work by S.K., H.S., and J.A.L was partially supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

  1. Effects of non-ionic surfactants on the interactions between cellulases and tannic acid

    DEFF Research Database (Denmark)

    Olsen, Søren Nymand; Bohlin, Christina Helena; Murphy, Leigh

    2011-01-01

    of cellulases to lignin. In the current work we address this hypothesis using tannic acid (TAN) as a general poly-phenolic model compound (for lignin and soluble phenolics) and measure the mutual interactions of cellulases (CBHI, CBHII, EGI, EGII and BG), TAN and NIS (Triton X-100) using isothermal titration...

  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. 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.

  4. Decomposition of lignin model compounds by Lewis acid catalysts in water and ethanol

    NARCIS (Netherlands)

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

    2015-01-01

    The conversion of benzyl phenyl ether, diphenyl ether, diphenyl methane and biphenyl as representative model compounds for alpha-O-4, 5-O-4, alpha(1) (methylene bridges) and 5-5' lignin linkages was investigated. We compared the use of metal chlorides and acetates. The reactions were studied in sub-

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

    Science.gov (United States)

    Waggoner, Derek Charles

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

  6. Cyclodextrin-facilitated bioconversion of 17 beta-estradiol by a phenoloxidase from Mucuna pruriens cell cultures

    NARCIS (Netherlands)

    Woerdenbag, H.J.; Pras, N.; Frijlink, H.W.; Lerk, C.F.; Malingré, T.M.

    1990-01-01

    After complexation with beta-cyclodextrin, the phenolic steroid 17 beta-estradiol could be ortho-hydroxylated into a catechol, mainly 4-hydroxyestradiol, by a phenoloxidase from in vitro grown cells of Mucuna pruriens. By complexation with beta-cyclodextrin the solubility of the steroid increased

  7. 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...

  8. 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

  9. Lignin in the Organic Matter of the Soils of the Russian Plain as Biomarker of Palaeoenvironment

    Science.gov (United States)

    Kovalev, I. V.; Kovaleva, N. O.

    2018-01-01

    It has been shown by the methods of biochemistry, nuclear magnetic resonance, and isotope geochemistry that the proportions of lignin phenols may be used as molecular traces of paleovegetation due to their biochemical and physiological specificity and high resistance to decomposition. Lignin structures have been detected in soils and in iron-manganese concretions. The comparison of the 13C NMR spectra of native lignin preparations isolated from different woody and herbaceous species with those of soil humic acids makes it possible to identify many characteristic shifts of lignin nature in humic acids at 56, 102, 115, 119, 131, 147, 151-152, 160, and 166 ppm. The information role of biomarker has been tested at the reconstruction of paleovegetation in the uplands of the Russian Plain. The representativeness of information has been increased using the isotope analysis (δ13C) and the radiocarbon dating; a new parameter—the composition of lignin phenols—has been introduced to the existing system of biomarkers.

  10. 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.

  11. 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

  12. Cross-class resistance to non-beta-lactam antimicrobials in extended-spectrum beta-lactamase-producing Klebsiella pneumoniae.

    Science.gov (United States)

    Procop, Gary W; Tuohy, Marion J; Wilson, Deborah A; Williams, Delisa; Hadziyannis, Emilia; Hall, Gerri S

    2003-08-01

    Extended spectrum beta-lactamases are modified beta-lactamase enzymes that impart resistance to third-generation cephalosporins and make all beta-lactam antibiotics and cephalosporins useless for therapy. We compared the antimicrobial susceptibility profiles of extended-spectrum beta-lactamase (ESBL)-producing and non-ESBL-producing isolates of Klebsiella pneumoniae. The ESBL producers had significantly diminished susceptibility compared with the non-ESBL producers for gentamicin (P < .001), tobramycin (P < .001), amikacin (P < .005), trimethoprim-sulfamethoxazole (P < .01), ciprofloxacin (P < .001), and nitrofurantoin (P < .001). All isolates were susceptible to imipenem. ESBL-producing K pneumoniae may also be resistant to non-beta-lactam antibiotics. Therefore, susceptibility testing of these isolates is critical for guiding therapy.

  13. Structural characterization of Kraft lignins from different spent cooking liquors by 1D and 2D Nuclear Magnetic Resonance spectroscopy

    International Nuclear Information System (INIS)

    Fernández-Costas, C.; Gouveia, S.; Sanromán, M.A.; Moldes, D.

    2014-01-01

    Three Kraft lignins isolated from black liquors of several paper pulp mills of the North of Spain and Portugal were structurally characterized by using monodimensional ( 1 H and 13 C) and bidimensional Nuclear Magnetic Resonance (NMR) spectrometry. From the latter, 13 C– 1 H heteronuclear single quantum correlation (HSQC) and heteronuclear multiple bond correlation (HMBC) were employed. Lignins from black liquors are usually burned for power generation. Nevertheless, they could become high value added products within a biorefinery context. In that case, a good understanding of their structure is a prior step to transform them. From all the NMR techniques studied, HSQC has risen as the most powerful tool in lignin characterization. Kraft cooking conditions and the type of wood seem to be the main factors that determine the differences observed in the lignins. All the samples have shown an important decrease in the number of β–O–4′ linkages, due to the Kraft process, and resinol has become the most resistant linkage to the process. Moreover, all samples seem to be mainly linked to a one polysaccharide: xylan. Several parameters like S/G ratio, portion of phenolic and aliphatic hydroxyls, amount of aromatic protons and other structural aspects were also estimated. - Highlights: • Lignins from three Kraft spent liquors were obtained by acid precipitation. • Structural characterization of the dissolved lignins was performed by NMR. • Wood source and pulping conditions determine the lignin characteristics. • Kraft process implies cleavage of β–O–4 linkages and survival of resinol linkages. • Comparison of the samples would aid decisions on its future revalorization

  14. 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.

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

    Science.gov (United States)

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

    2010-12-10

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

  16. Quantitative structural analysis of lignin by diffuse reflectance fourier transform infrared spectrometry

    International Nuclear Information System (INIS)

    Schultz, T.P.; Glasser, W.G.

    1986-01-01

    Empirical quantitative relationships were established between infrared (IR) spectral information and several structural features in lignins as determined by conventional methods. The structural composition of average phenylpropane (C g ) units which significantly correlated (0.01 level) with IR peak intensities included methoxy content, aromatic hydrogen content, phenolic hydroxy content, guaiacyl/syringyl ratio, and ''hydrolysis'' and ''condensation'' ratios

  17. Postharvest changes in the phenolic profile of watercress induced by post-packaging irradiation and modified atmosphere packaging.

    Science.gov (United States)

    Pinela, José; Barros, Lillian; Barreira, João C M; Carvalho, Ana Maria; Oliveira, M Beatriz P P; Santos-Buelga, Celestino; Ferreira, Isabel C F R

    2018-07-15

    The effects of γ-ray irradiation and modified atmosphere packaging (MAP) on watercress (Nasturtium officinale R. Br.) phenolic compounds were evaluated after 7-day storage at 4 °C. Irradiation doses of 1, 2 and 5 kGy were tested, as well as vacuum-packaging and MAP enriched with 100% N 2 and Ar. A non-irradiated, air-packaged control was included in all experiments. p-Coumaric acid was the most abundant compound in fresh watercress, followed by quercetin-3-O-sophoroside and isorhamnetin-O-hydroxyferuloylhexoside-O-hexoside. Four kaempferol glycoside derivatives were identified for the first time in this species. In general, flavonoids predominated over phenolic acids. Samples stored under vacuum and irradiated at 2 kGy revealed lower phenolic levels. Ar-enriched MAP and control conditions preserved the initial phenolic content. The 5 kGy dose also maintained concentrations of flavonoids and total phenolic compounds, but increased the phenolic acids content. Additionally, flavonoids were found strongly correlated to DPPH scavenging activity and β-carotene bleaching inhibition capacity. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Steam gasification of a thermally pretreated high lignin corn stover simultaneous saccharification and fermentation digester residue

    Energy Technology Data Exchange (ETDEWEB)

    Howe, Daniel T.; Taasevigen, Danny; Garcia-Perez, Manuel; McDonald, Armando G.; Li, Guosheng; Wolcott, Michael

    2017-01-01

    Efficient conversion of all components in lignocellulosic biomass is essential to realizing economic feasibility of biorefineries. However, when utilizing biochemical pathways, lignin cannot be fermented. Furthermore, the high lignin and high ash residue resulting from simultaneous saccharification and fermentation (SSF) reactors is difficult to thermochemically process due to feed line plugging and bed agglomeration. In this study a corn stover SSF digester residue was thermally pretreated at 300°C for 22.5 minutes (min) and then gasified in a bubbling fluidized bed gasifier to study the effect of thermal pretreatment on its processing behavior. Untreated, pelletized SSF residue was gasified at the same conditions to establish the baseline processing behavior. Results indicate that the thermal pretreatment process removes a substantial portion of the polar and non-polar extractives, with a resultant increase in the concentration of lignin, cellulose, and ash. Feed line plugging was not observed, although bed agglomeration was occurring at similar rates for both feedstocks, suggesting that overall ash content is the most important factor affecting bed agglomeration. Benzene, phenol, and polyaromatic hydrocarbons in the tar were present at higher concentrations in the treated material, with higher tar loading in the product gas. Total product gas generation is lower for the treated material, although the overall gas composition does not change.

  19. 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.

  20. 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.

  1. Methylene blue and 4-chloro phenol degradation by photo catalysis with ultraviolet light, using TiO2 as catalyst

    International Nuclear Information System (INIS)

    Martinez H, A.

    2010-01-01

    Within the decontamination and remediation processes of the contaminated waters, as the refining or tertiary processes are the Advanced Oxidation Technologies. Among this technology is the heterogeneous photo catalysis, which is the object of this work to de grate 4-chloro phenol and methylene blue, using as semiconductor commercial titanium dioxide (TiO 2 ). On the degradation the combination is exposed in the use of TiO 2 under gamma irradiation of 60 Co at different doses 400, 500, 800, 1000 and 1500 kGy. The organic compounds degradation was determined and the results show that to more radiation dose, the material is modified in such way that shows a major absorption of the organic compound, in the same way it is determined that to more dose which undergoes the TiO 2 generally a major degradation is observed, but also it is has to give a more time of previous stabilization, for that the degradation is observed of better way. (Author)

  2. Phenolics from Kalanchoe marmorata Baker, Family Crassulaceae

    Directory of Open Access Journals (Sweden)

    Abdel Nasser Badawy Singab

    2011-06-01

    Full Text Available In search of plants rich in phenolics in Egypt, Kalanchoe marmorata Baker was subjected to phytochemical study. The preliminary phytochemical screening revealed its richness in phenolics. Fractionation of the lyophilized aqueous extract of the leaves of K. marmorata by different organic solvents successively resulted in the isolation and purification of five compounds from the ethyl acetate soluble fraction. These compounds namely; E1 isorhamnetin-3-O-α-l-1C4-rhamnopyranoside; E2 quercitin; E3 4′-methoxy-myricetin-3-O-α-l-1C4-rhamnopyranoside; E4 Quercitin-3-O-β-d-4C1-glucopyranoside and E5 protocatechuic-4′-O-β-d-4C1-glucopyranoside, were identified by analysis of their spectral data including 1H NMR and 13C NMR.

  3. 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...

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  5. 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...

  6. KRAFT PULPING CHARACTERISTICS OF THREE MOROCCAN EUCALYPTI. PART 2. COMPARISON OF THE GUAIACYL FRACTION OF THE NATIVE LIGNINS BY A NOVEL METHOD

    Directory of Open Access Journals (Sweden)

    Ericka F. Alves,

    2012-02-01

    Full Text Available In Part 1 of this series it was observed that one of the eucalypti (EGC 39 was more reactive than the other two in kraft and soda-AQ (SAQ cooking. However, the lignin in EGC 39 contained equal or less syringyl (S units than the other two eucalypti. In the present research an attempt was made to compare the guaiacyl (G fraction of the three lignins. The approach was to use SAQ treatment to cleave β-O-4 bonds in dimeric units containing uncondensed guaiacyl A-rings (those rearranging to quinone methides. The coniferyl alcohol, vinylguaiacol and isoeugenol generated from β-O-4 cleavage are then trapped as dimers by ethylguaiacol that is included in the SAQ liquor. Research with sugar maple (Acer saccharum showed that the estimate of these structures (uncondensed G-β-O-4 by this approach was in close agreement with traditional but more tedious methods such as permanganate oxidation and 31P NMR. It was also shown that the lignin in the EGC 39 hybrid contained a higher concentration of uncondensed G-β-O-4 structures than the other two eucalypti lignins.

  7. Conditions for selective degradation of lignin by the fungus Ganoderma australis

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-08-01

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

  8. Conversion of alkaline pretreated empty palm fruit bunch (EPFB) to phenols

    International Nuclear Information System (INIS)

    Nor Aishah Saidina Amin; Roslindawati Haron

    2010-01-01

    Various efforts on green chemistry are being directed at producing renewable chemicals. Chemicals derived from biomass can be the basis for building blocks in the chemicals industry. Phenols, traditionally produced from petroleum, can be derived from biomass for naturally-sourced solvents. Lignocellulose biomass consists of cellulose, hemicelluloses and lignin. Lignocellulose components can be altered by various chemical pretreatment methods. EFB contains about 60% cellulose and almost equal portions of lignin and hemicelluloses. Pretreatment of EFB fragmentized and degraded the lignocellulose structure in order to produce chemicals under thermochemical process. In this work, EFB was chemically pretreated with different sodium hydroxide (NaOH) concentrations to concentrated lignocellulose before being pyrolyzed to produce solid, gas and liquid products. Pyrolysis was conducted after the pretreatment step to evaluate the effects of pretreatment process on production and compositions of the bio-oil. The conversions of EFB were reported to be 61wt%, 47wt% and 42 wt%, after pretreatment with 5 wt%, 15 wt% and 25 wt%,NaOH concentrations, respectively. GCMS analysis results revealed the crude bio-oil contained dominantly phenol. Pyrolysis of the alkaline pretreated EFB seemed potential to produce biomass-based phenols. (author)

  9. Lignin engineering in field-grown poplar trees affects the endosphere bacterial microbiome.

    Science.gov (United States)

    Beckers, Bram; Op De Beeck, Michiel; Weyens, Nele; Van Acker, Rebecca; Van Montagu, Marc; Boerjan, Wout; Vangronsveld, Jaco

    2016-02-23

    Cinnamoyl-CoA reductase (CCR), an enzyme central to the lignin biosynthetic pathway, represents a promising biotechnological target to reduce lignin levels and to improve the commercial viability of lignocellulosic biomass. However, silencing of the CCR gene results in considerable flux changes of the general and monolignol-specific lignin pathways, ultimately leading to the accumulation of various extractable phenolic compounds in the xylem. Here, we evaluated host genotype-dependent effects of field-grown, CCR-down-regulated poplar trees (Populus tremula × Populus alba) on the bacterial rhizosphere microbiome and the endosphere microbiome, namely the microbiota present in roots, stems, and leaves. Plant-associated bacteria were isolated from all plant compartments by selective isolation and enrichment techniques with specific phenolic carbon sources (such as ferulic acid) that are up-regulated in CCR-deficient poplar trees. The bacterial microbiomes present in the endosphere were highly responsive to the CCR-deficient poplar genotype with remarkably different metabolic capacities and associated community structures compared with the WT trees. In contrast, the rhizosphere microbiome of CCR-deficient and WT poplar trees featured highly overlapping bacterial community structures and metabolic capacities. We demonstrate the host genotype modulation of the plant microbiome by minute genetic variations in the plant genome. Hence, these interactions need to be taken into consideration to understand the full consequences of plant metabolic pathway engineering and its relation with the environment and the intended genetic improvement.

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

    Directory of Open Access Journals (Sweden)

    Gabriel Valim Cardoso

    2011-03-01

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

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

    Directory of Open Access Journals (Sweden)

    Lucky Risanto

    2014-10-01

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

  12. 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.

  13. Enhancement of photocatalytic properties of TiO2 nanoparticles doped with CeO2 and supported on SiO2 for phenol degradation

    International Nuclear Information System (INIS)

    Hao, Chunjing; Li, Jing; Zhang, Zailei; Ji, Yongjun; Zhan, Hanhui; Xiao, Fangxing; Wang, Dan; Liu, Bin; Su, Fabing

    2015-01-01

    Highlights: • CeO 2 -TiO 2 /SiO 2 composites were prepared via a facile co-precipitation method. • Introduction of SiO 2 support increases the dispersion of CeO 2 -TiO 2 . • CeO 2 -TiO 2 /SiO 2 exhibits an enhanced photocatalytic efficiency for phenol degradation. • Ce 3+ /Ce 4+ pair coexisting in CeO 2 improves electron–hole pairs separation efficiency. - Abstract: A series of CeO 2 -TiO 2 and CeO 2 -TiO 2 /SiO 2 composites were prepared with TiCl 4 and Ce (NO 3 ) 3 ·6H 2 O as precursors via a facile co-precipitation method. The obtained samples were characterized by various techniques such as X-ray diffraction (XRD), nitrogen adsorption (N 2 -BET), Fourier transformation infrared spectrum (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV–Vis spectroscopy measurements. The results indicated that TiO 2 doped with CeO 2 and supported on SiO 2 could reduce the crystallite size, inhibit the phase transformation, enhance the thermal stability, and effectively extend the spectral response from UV to visible range. When applied to the phenol photodegradation on a homemade batch reactor with an external cooling jacket, the CeO 2 -TiO 2 /SiO 2 catalysts exhibited significantly enhanced photodegradation efficiency in comparison with commercial Degussa P25 and CeO 2 -TiO 2 . The unique catalytic properties of CeO 2 -TiO 2 /SiO 2 were ascribed to improved electron–hole pairs separation efficiency and formation of more reactive oxygen species owing to the presence of Ce 3+ /Ce 4+ , as well as high dispersion of active component of CeO 2 -TiO 2 as a result of the introduction of SiO 2 support. Furthermore, the catalysts can be easily recovered from the reaction solution by centrifugation and reused for four cycles without significant loss of activity

  14. Effect of the molecular structure of phenolic novolac precursor resins on the properties of phenolic fibers

    International Nuclear Information System (INIS)

    Ying, Yong-Gang; Pan, Yan-Ping; Ren, Rui; Dang, Jiang-Min; Liu, Chun-Ling

    2013-01-01

    A series of phenolic resins with different weight-average molecular weights (M w ) and ortho/para (O/P) ratios were prepared. The effect of the phenolic precursor resin structure on the structure and properties of the resulting phenolic fibers was investigated. The structures of the resins and fibers were characterized by nuclear magnetic resonance spectroscopy, gel permeation chromatography, melt rheometry, dynamic mechanical analysis, and thermogravimetric analysis. The results show that the O/P ratio, unsubstituted ortho and para carbon ratio (O u /P u ), and M w of the phenolic resins play an important role in determining the properties of the phenolic fibers. The tensile strength of the phenolic fibers increases with increasing novolac precursor O u /P u ratios, corresponding to low O/P ratios, at comparable resin M w values. Also, the tensile strength of the phenolic fibers increases with increasing novolac M w values at comparable O/P ratios. Phenolic fibers with high tensile strength and good flame resistance characteristics were generated from a phenolic precursor resin, possessing a high weight-average molecular weight and a low O/P value. - Highlights: • Phenolic resins with different weight-average molecular weights and ortho/para ratios have been prepared. • The tensile strength of the phenolic fibers increases with reducing novolac O/P ratio. • The tensile strength of the phenolic fibers increases with increasing novolac M w

  15. 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.

  16. 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)

  17. Variação no conteúdo de beta-glucanas em cultivares brasileiros de aveia Beta-glucan content variation in brasilian oat cultivars

    Directory of Open Access Journals (Sweden)

    Roberta M. de SÁ

    2000-04-01

    Full Text Available Com o crescente interesse em alimentos funcionais e nutracêuticos, a aveia (Avena sativa L. tem se destacado, devido ao seu teor de fibras alimentares e principalmente às beta-glucanas. As (1,3(1,4-beta-D-glucanas, fibras alimentares na maioria solúveis, atuam na redução do colesterol em indivíduos com hipercolesterolemia. Existem estudos para determinar as causas de variação do teor desta fibra em aveia, porém, pouco se sabe sobre a aveia cultivada no Brasil. O objetivo deste trabalho foi verificar se existem diferenças no conteúdo de beta-glucanas entre cultivares brasileiros e se há variação na porcentagem desta fibra devido ao ano de cultivo. Os cultivares IAC7, UFRGS14, UPF16 e UPF17 (3 amostras de cada, e ainda três amostras do cultivar IAC7 para cada ano de cultivo (97 e 98, foram analisados segundo os métodos da AACC (American Association of Cereal Chemists. Os teores médios (peso seco de beta-glucanas foram 6,50% (IAC7, 4,30% (UFRGS14, 3,51% (UPF16 e 3,78% (UPF17, com erro padrão de ±0,084 e coeficiente de variação de 7,89 %. Observou-se efeito significativo dos cultivares (p=0,03 e grande variabilidade entre as amostras (p=0,0001. O cultivar IAC7 apresentou média de beta-glucanas de 5,11% em 97 e 6,50 % em 98 (erro padrão ±0,14; CV=10,53% e observou-se efeito significativo do ano de cultivo.With the increasing interest in functional foods and nutraceuticals, oats (Avena sativa L. have received special attention because of their dietary fiber contents, and specially of their beta-glucans. The mostly soluble dietary fibers (1,3(1,4-beta-D-glucans, reduce serum cholesterol in individuals with hypercholesterolemia. There are studies about the causes of variation in the contents of this fiber in oats, however, very little is known about Brazilian cultivars. The objective of this work was to verify if there were differences in the beta-glucan contents among brazilian cultivars and if there was variation in the

  18. 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.

  19. 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.

  20. Phenolic compounds from the leaf extract of artichoke (Cynara scolymus L.) and their antimicrobial activities.

    Science.gov (United States)

    Zhu, Xianfeng; Zhang, Hongxun; Lo, Raymond

    2004-12-01

    A preliminary antimicrobial disk assay of chloroform, ethyl acetate, and n-butanol extracts of artichoke (Cynara scolymus L.) leaf extracts showed that the n-butanol fraction exhibited the most significant antimicrobial activities against seven bacteria species, four yeasts, and four molds. Eight phenolic compounds were isolated from the n-butanol soluble fraction of artichoke leaf extracts. On the basis of high-performance liquid chromatography/electrospray ionization mass spectrometry, tandem mass spectrometry, and nuclear magnetic resonance techniques, the structures of the isolated compounds were determined as the four caffeoylquinic acid derivatives, chlorogenic acid (1), cynarin (2), 3,5-di-O-caffeoylquinic acid (3), and 4,5-di-O-caffeoylquinic acid (4), and the four flavonoids, luteolin-7-rutinoside (5), cynaroside (6), apigenin-7-rutinoside (7), and apigenin-7-O-beta-D-glucopyranoside (8), respectively. The isolated compounds were examined for their antimicrobial activities on the above microorganisms, indicating that all eight phenolic compounds showed activity against most of the tested organisms. Among them, chlorogenic acid, cynarin, luteolin-7-rutinoside, and cynaroside exhibited a relatively higher activity than other compounds; in addition, they were more effective against fungi than bacteria. The minimum inhibitory concentrations of these compounds were between 50 and 200 microg/mL.

  1. The roles of plant phenolics in defence and communication during Agrobacterium and Rhizobium infection.

    Science.gov (United States)

    Bhattacharya, Amita; Sood, Priyanka; Citovsky, Vitaly

    2010-09-01

    Phenolics are aromatic benzene ring compounds with one or more hydroxyl groups produced by plants mainly for protection against stress. The functions of phenolic compounds in plant physiology and interactions with biotic and abiotic environments are difficult to overestimate. Phenolics play important roles in plant development, particularly in lignin and pigment biosynthesis. They also provide structural integrity and scaffolding support to plants. Importantly, phenolic phytoalexins, secreted by wounded or otherwise perturbed plants, repel or kill many microorganisms, and some pathogens can counteract or nullify these defences or even subvert them to their own advantage. In this review, we discuss the roles of phenolics in the interactions of plants with Agrobacterium and Rhizobium.

  2. 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.

  3. Rapid determination of total phenols in seawater by 4-aminoantipyrine colorimetry

    Digital Repository Service at National Institute of Oceanography (India)

    Kadam, A.N.; Bhangale, V.P.

    A rapid and efficient 4-aminoantipyrine (4-AAP) colorimetric method without any cleanup step to determine total phenols in seawater is described. Efficiency of the method for seawater using external addition of phenol concentrations with working...

  4. Clean production of corn stover pulp using KOH+NH4OH solution and its kinetic during delignification

    Directory of Open Access Journals (Sweden)

    Sun Yong

    2012-01-01

    Full Text Available The self-made KOH together with NH4OH pulping of corn stover was investigated. The combined alkaline system could effectively remove lignin during pulping. There are three stages of lignin removal during delginification. Approximately 90% of lignin could be removed after temperature reached 150ºC for over 30 minutes. The p-hydroxyl phenol groups in lignin could be completely removed during the delignification reaction. The tendency of the increase of the crystalline degree of cellulose is observed with increase of reaction temperature. The kinetics of delignification is found to be the first order with respect to the remained lignin and the 0.4 order with respect to the remained hydroxide concentration. The activation energy of delignification is 23 kJ/mol. The solution obtained from precipitation of lignin is rich in nitrogen, phosphorous, potassium elements and organic matters. Various techniques including FT-IR, GPC, DSC, were applied to characterize the acid precipitated lignin. The result shows that the lignin with the polydispersity of 1.4 still maintains the p-coumaryl, coniferyl, and sinapyl units in its matrix.

  5. Photocatalytic Removal of Phenol under Natural Sunlight over N-TiO2-SiO2 Catalyst: The Effect of Nitrogen Composition in TiO2-SiO2

    Directory of Open Access Journals (Sweden)

    Viet-Cuong Nguyen

    2009-01-01

    Full Text Available In this present work, high specific surface area and strong visible light absorption nitrogen doped TiO2-SiO2 photocatalyst was synthesized by using sol-gel coupled with hydrothermal treatment method. Nitrogen was found to improve the specific surface area while it also distorted the crystal phase of the resulting N-TiO2-SiO2 catalyst. As the N/ (TiO2-SiO2 molar ratio was more than 10%, the derived catalyst presented the superior specific surface area up to 260 m2/g. Nevertheless, its photoactivity towards phenol removal was observed to significantly decrease, which could results from the too low crystallinity. The nitrogen content in N-TiO2-SiO2 catalyst was therefore necessary to be optimized in terms of phenol removal efficiency and found at ca. 5%. Under UVA light and natural sunlight irradiation of 80 min, N(5%-TiO2-SiO2 catalyst presented the phenol decomposition efficiencies of 68 and 100%, respectively. It was also interestingly found in this study that the reaction rate was successfully expressed using a Langmuir-Hinshelwood (L-H model, indicating the L-H nature of photocatalytic phenol decomposition reaction on the N-TiO2-SiO2 catalyst.

  6. Bio-phenolic resin from oil palm empty fruit bunches

    Science.gov (United States)

    Zakaria, Zuhaili; Zakaria, Sarani; Roslan, Rasidi; Chia, Chin Hua; Jaafar, Sharifah Nabihah Syed; Amran, Umar Adli

    2018-04-01

    Utilization of oil palm empty fruit bunches (EFB) in the production of bio-phenolic resin is an alternative way to reduce the dependency of petroleum-based phenol. In this study, resol type bio-phenolic resin (BPR) was synthesized from EFB fibers using sulfuric acid as the catalyst to produce liquefied empty fruit bunches (LEFB) followed by resinification reaction with formaldehyde in alkaline condition. The SEM image of LEFB residue showed separation of fiber bundles into individual fibers. This indicate that lignin was destroyed during the liquefaction process. The increased of formaldehyde/LEFB molar ratio has resulted an increase of viscosity, solid content and pH of the resin. The obtained FTIR spectra confirmed that functional groups of BPR resins was almost similar with commercial resin.

  7. Sol-gel synthesis of TiO{sub 2}-SiO{sub 2} photocatalyst for {beta}-naphthol photodegradation

    Energy Technology Data Exchange (ETDEWEB)

    Qourzal, S., E-mail: samir_qourzal@yahoo.fr [Equipe de Materiaux Photocatalyse et Environnement, Departement de Chimie, Faculte des Sciences, Universite Ibn Zohr, B. P. 8106 Cite Dakhla, Agadir (Morocco); Barka, N.; Tamimi, M.; Assabbane, A. [Equipe de Materiaux Photocatalyse et Environnement, Departement de Chimie, Faculte des Sciences, Universite Ibn Zohr, B. P. 8106 Cite Dakhla, Agadir (Morocco); Nounah, A. [Ecole Superieure de Technologie, Avenue Prince Heritier Sidi Mohamed, B. P. 227, Sale-Medina (Morocco); Ihlal, A. [Laboratoire de Physique des Semi-conducteurs et Energie Solaire, Departement de Physique, Faculte, des Sciences, Universite Ibn Zohr, B. P. 8106 Cite Dakhla, Agadir (Morocco); Ait-Ichou, Y. [Equipe de Materiaux Photocatalyse et Environnement, Departement de Chimie, Faculte des Sciences, Universite Ibn Zohr, B. P. 8106 Cite Dakhla, Agadir (Morocco)

    2009-06-01

    Silica gel supported titanium dioxide particles (TiO{sub 2}-SiO{sub 2}) prepared by sol-gel method was as photocatalyst in the degradation of {beta}-naphthol in water under UV-illumination. The prepared sample has been characterized by powder X-ray diffraction (XRD), infrared spectroscopy (IR) and scanning electron microscopy (SEM). The supported catalyst had large surface area and good sedimentation ability. The photodegradation rate of {beta}-naphthol under UV-irradiation depended strongly on adsorption capacity of the catalyst, and the photoactivity of the supported catalyst was much higher than that of the pure titanium dioxides. The experiments were measured by high performance liquid chromatography (HPLC). The photodegradation rate of {beta}-naphthol using 60% TiO{sub 2}-SiO{sub 2} particles was faster than that using TiO{sub 2} 'Degussa P-25', TiO{sub 2} 'PC-50' and TiO{sub 2} 'Aldrich' as photocatalyst by 2.7, 4 and 7.8 times, respectively. The kinetics of photocatalytic {beta}-naphthol degradation was found to follow a pseudo-first-order rate law. The effect of the TiO{sub 2} loading on the photoactivity of TiO{sub 2}-SiO{sub 2} particles was also discussed. With good photocatalytic activity under UV-irradiation and the ability to be readily separated from the reaction system, this novel kind of catalyst exhibited the potential effective in the treatment of organic pollutants in aqueous systems.

  8. 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

    A comprehensive assessment of lignin configuration in transgenic and mutant plants is long overdue. This review thus undertook the systematic analysis of trends manifested through genetic and mutational manipulations of the various steps associated with monolignol biosynthesis; this included consideration of the downstream effects on organized lignin assembly in the various cell types, on vascular function/integrity, and on plant growth and development. As previously noted for dirigent protein (homologs), distinct and sophisticated monolignol forming metabolic networks were operative in various cell types, tissues and organs, and form the cell-specific guaiacyl (G) and guaiacyl-syringyl (G-S) enriched lignin biopolymers, respectively. Regardless of cell type undergoing lignification, carbon allocation to the different monolignol pools is apparently determined by a combination of phenylalanine availability and cinnamate-4-hydroxylase/"p-coumarate-3-hydroxylase" (C4H/C3H) activities, as revealed by transcriptional and metabolic profiling. Downregulation of either phenylalanine ammonia lyase or cinnamate-4-hydroxylase thus predictably results in reduced lignin levels and impaired vascular integrity, as well as affecting related (phenylpropanoid-dependent) metabolism. Depletion of C3H activity also results in reduced lignin deposition, albeit with the latter being derived only from hydroxyphenyl (H) units, due to both the guaiacyl (G) and syringyl (S) pathways being blocked. Apparently the cells affected are unable to compensate for reduced G/S levels by increasing the amounts of H-components. The downstream metabolic networks for G-lignin enriched formation in both angiosperms and gymnosperms utilize specific cinnamoyl CoA O-methyltransferase (CCOMT), 4-coumarate:CoA ligase (4CL), cinnamoyl CoA reductase (CCR) and cinnamyl alcohol dehydrogenase (CAD) isoforms: however, these steps neither affect carbon allocation nor H/G designations, this being determined by C4H/C3H

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

    Science.gov (United States)

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

    2011-10-26

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

  10. A computational study of pyrolysis reactions of lignin model compounds

    Science.gov (United States)

    Thomas Elder

    2010-01-01

    Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...

  11. Texture Of Zircaloy-4 Result Of Beta-Quenching, Cold Rolling And Recrystallization

    International Nuclear Information System (INIS)

    Futichah; Sulistioso

    1998-01-01

    Differences of crystallographic texture of zircaloy-4 plate depends on cold working and heat treatment.To determine the change of zircaloy-4 textures, the solid solution treatment process at beta phase which was followed by quenching on water was employed for this sample. The next step was cold rolling until deformation epsilon = 1.62. The specimens were recrystallized at 750 o C, for 2 hours. The result of beta-quench gave a spread and different orientations and the main orientation occurred at (0001)[1010] and (0001)[1120]. Result of cold rolling with epsilon = 1.39 and epsilon 1.62 is the deformation texture at the main orientation of (0001)[1010] with the angle of inclination was around 38 o. However, the result of Recrystallization process on 750 o C for 2 hours gave annealing textures with orientations of (0001)[1120]. It means that the recrystallization process of zircaloy-4 plate can not remove the deformation textures, but can change the crystallographic orientation

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

    Science.gov (United States)

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

    2014-10-09

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

  13. Phenol degradation by TiO2 photocatalysts combined with different pulsed discharge systems.

    Science.gov (United States)

    Zhang, Yi; Lu, Jiani; Wang, Xiaoping; Xin, Qing; Cong, Yanqing; Wang, Qi; Li, Chunjuan

    2013-11-01

    Films of TiO2 nanotubes distributed over the inner surface of a discharge reactor cylinder (CTD) or adhered to a stainless steel electrode surface (PTD) in a discharge reactor were compared with a single-discharge (SD) system to investigate their efficiencies in phenol degradation. Morphology studies indicated that the TiO2 film was destroyed in the PTD system, but that there was no change in the CTD system after discharge. X-ray diffraction results revealed that the anatase phase of the original sample was preserved in the CTD system, but that an anatase-to-rutile phase transformation occurred in the PTD system after discharge. The highest efficiencies of phenol degradation and total organic carbon (TOC) mineralization were observed in the CTD system, and there was no decrease in phenol degradation efficiency upon reuse of a TiO2 film, indicating high catalysis activity and stability of the TiO2 photocatalysts in the combined treatment. TiO2 photocatalysts favored the formation of hydrogen peroxide and disfavored the formation of ozone. A greater degree of oxidation of intermediates and higher energy efficiency in phenol oxidation were observed with the TiO2-plasma systems, especially in the CTD system, compared to those with the SD system. Copyright © 2013 Elsevier Inc. All rights reserved.

  14. A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

    Science.gov (United States)

    Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

    2017-06-16

    The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K₂CO₃ base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.

  15. Effects of lignin-derived phenolic compounds on xylitol production and key enzyme activities by a xylose utilizing yeast Candida athensensis SB18.

    Science.gov (United States)

    Zhang, Jinming; Geng, Anli; Yao, Chuanyi; Lu, Yinghua; Li, Qingbiao

    2012-10-01

    Candida athensensis SB18 is potential xylitol producing yeast isolated in Singapore. It has excellent xylose tolerance and is able to produce xylitol in high titer and yield. However, by-products, such as phenolic compounds, derived in lignocellulosic biomass hydrolysate might negatively influence the performance of this strain for xylitol production. In this work, four potential phenolic inhibitors, such as vanillin, syringaldehyde, 4-hydroxybenzaldehyde and phenol, were evaluated for their inhibitory effects on xylitol production by C. athensensis SB18. Phenol was shown to be the most toxic molecule on this microorganism followed by syringaldehyde. Vanillin and 4-hydroxylbenzaldehyde was less toxic than phenol and syringaldehyde, with vanillin being the least toxic. Inhibition was insignificant when the total content of inhibitors was below 1.0 g/L. The presence of phenolic compounds affected the activity of xylose reductase, however not on that of xylitol dehydrogenase. C. athensensis SB18 is therefore a potential xylitol producer from hemicellulosic hydrolysate due to its assimilation of such phenolic inhibitors. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Initial Reactivity of Linkages and Monomer Rings in Lignin Pyrolysis Revealed by ReaxFF Molecular Dynamics.

    Science.gov (United States)

    Zhang, Tingting; Li, Xiaoxia; Guo, Li

    2017-10-24

    The initial conversion pathways of linkages and their linked monomer units in lignin pyrolysis were investigated comprehensively by ReaxFF MD simulations facilitated by the unique VARxMD for reaction analysis. The simulated molecular model contains 15 920 atoms and was constructed on the basis of Adler's softwood lignin model. The simulations uncover the initial conversion ratio of various linkages and their linked aryl monomers. For linkages and their linked monomer aryl rings of α-O-4, β-O-4 and α-O-4 & β-5, the C α /C β ether bond cracking dominates the initial pathway accounting for at least up to 80% of their consumption. For the linkage of β-β & γ-O-α, both the C α -O ether bond cracking and its linked monomer aryl ring opening are equally important. Ring-opening reactions dominate the initial consumption of other 4-O-5, 5-5, β-1, β-2, and β-5 linkages and their linked monomers. The ether bond cracking of C α -O and C β -O occurs at low temperature, and the aryl ring-opening reactions take place at relatively high temperature. The important intermediates leading to the stable aryl ring opening are the phenoxy radicals, the bridged five-membered and three-membered rings and the bridged six-membered and three-membered rings. In addition, the reactivity of a linkage and its monomer aryl ring may be affected by other linkages. The ether bond cracking of α-O-4 and β-O-4 linkages can activate its neighboring linkage or monomer ring through the formed phenoxy radicals as intermediates. The important intermediates revealed in this article should be of help in deepening the understanding of the controlling mechanism for producing aromatic chemicals from lignin pyrolysis.

  17. Discriminated release of phenolic substances from red wine grape skins (Vitis vinifera L.) by multicomponent enzymes treatment

    DEFF Research Database (Denmark)

    Arnous, Anis; Meyer, Anne S.

    2010-01-01

    Detailed insight into the effects of enzymatic treatments on grape phenolics is of significant importance for grape processing for wine making. This study examined the release of phenols during enzymatic (pectinolytic and cellulolytic) degradation of the cell wall polysaccharides in skins of Merlot...... the enzymatic treatment; phenolic acids, including hydroxybenzoic acids and hydroxycinnamic acids, were released as a function of monosaccharides liberation, i.e. as a function of the enzyme catalyzed cell wall degradation of the skins, and with some of the phenolic acids perhaps released from the lignin...

  18. Elimination of Phenol and Color from Pulping Black Liquor Using Electrocoagulation Process

    Directory of Open Access Journals (Sweden)

    Nahid Rastegarfar

    2013-08-01

    Full Text Available There are many non-wood lignocelluloses resources such as wheat, rice straw and other agriculture by- products with appropriate feature for pulp production in Iran. The most major deterrent to their use is presence of pulping black liquor that due to lignin of lignocelluloses solution contains significant amounts of color and phenol compounds. The aim of this paper was investigation of the ability to remove phenol and color as the most important organic pollutants from back liquor of agri-based pulping process using electrocoagulation method. In the electrocoagulation process aluminium electrode was used and cell potential and current intensity were adjusted on 16 V and 1700 mA respectively. The effect of various treatment time (10, 25, 40, 55, 70 min and initial pH (3, 5, 7, 9, 10/5 of black liquor were investigated.The results showed that maximum of decrease obtained at pH 5 that has led to a remove capacity 78% of phenol and 98% of color in treatment time 70 min. electrocoagulation method can be used for black liquor treatment because of simple, effective and its low investment cost compared to other technologies.

  19. 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.

  20. Solvent consumption in non-catalytic alcohol solvolysis of biorefinery lignin

    DEFF Research Database (Denmark)

    Nielsen, J. B.; Jensen, A.; Schandel, Christian Bækhøj

    2017-01-01

    Lignin solvolysis in supercritical alcohols provides a method for producing a deoxygenated liquid bio-oil. Solvent consumption is however inevitable and due to the high cost of alcohols, relative to a bio-oil product, it can hinder commercial viability. In order to investigate the reactions...... of solvent consumption we studied solvolysis of biorefinery lignin in several primary alcohols. Lignin solvolysis in methanol, ethanol, 1-propanol and 1-butanol performed similarly with respect to bio-oil composition; however, methanol gave much lower bio-oil yield. Solvent consumption increases...... with reaction temperature for all alcohols and from 10 wt% at 300 °C to 35 wt% at 400 °C when using ethanol. The mechanism for solvent consumption was found mainly to take place through three different reactions: direct decomposition to gas through decarbonylation, formation of light condensation products...

  1. Fe-containing nanoparticles used as effective catalysts of lignin reforming to syngas and hydrogen assisted by microwave irradiation

    Science.gov (United States)

    Tsodikov, M. V.; Ellert, O. G.; Nikolaev, S. A.; Arapova, O. V.; Bukhtenko, O. V.; Maksimov, Yu. V.; Kirdyankin, D. I.; Vasil'kov, A. Yu.

    2018-03-01

    Active iron-containing nanosized components have been formed on the lignin surface. The metal was deposited on the lignin from an ethanol solution of Fe(acac)3 and from a colloid solution of iron metal particles obtained beforehand by metal vapor synthesis. These active components are able to absorb microwave radiation and are suitable for microwave-assisted high-rate dehydrogenation and dry reforming of lignin without addition of a carbon adsorbent, as a supplementary radiation absorbing material, to the feedstock. The dependence of the solid lignin heating dynamics on the concentration of supported iron particles was investigated. The threshold Fe concentration equal to 0.5 wt.%, providing the highest rate of sample heating up to the reforming and plasma generation temperature was identified. The microstructure and magnetic properties of iron-containing nanoparticles supported on lignin were studied before and after the reforming. The Fe3O4 nanoparticles and also core-shell Fe3O4@γ-Fe-C nanostructures are formed during the reforming of lignin samples. The catalytic performance of iron-based nanoparticles toward the lignin conversion is manifested as increasing selectivity to hydrogen and syngas, which reaches 94% at the Fe concentration of 2 wt.%. It was found that with microwave irradiation under argon, hydrogen predominates in the gas. In the CO2 atmosphere, dry reforming takes place to give syngas with the CO/H2 ratio of 0.9. In both cases, the degree of hydrogen recovery from lignin reaches 90-94%. [Figure not available: see fulltext.

  2. 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.

  3. Localization of thymosin beta-4 in tumors

    DEFF Research Database (Denmark)

    Larsson, L. -I.; Holck, Susanne

    2007-01-01

    in colorectal carcinomas. The degree of staining of breast cancer cells for thymosin beta-4 correlated neither to histological grade nor to endothelial cell staining. However, there was a tendency toward correlation (P = 0.07) between staining of endothelial cells and histological grade. Treatment of cultured......Overexpression of thymosin beta-4 has been linked to malignant progression but the localization of this polypeptide within tumors is incompletely known. We therefore examined breast cancers for thymosin beta-4 using immunofluorescence. Reactive cells were identified with monoclonal cell marker...... breast cancer cells (SK-BR-3) with 1-4 microg thymosin beta-4/mL significantly increased cell numbers, as determined by MTT-assays. These data reveal an unexpected cellular heterogeneity of thymosin beta-4 expression in breast and colonic carcinomas and suggest that local release of this polypeptide...

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

    Science.gov (United States)

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

    2015-01-01

    In wheat straw based composting, enabling growth of Agaricus bisporus mushrooms, it is unknown to which extent the carbohydrate-lignin matrix changes and how much is metabolized. In this paper we report yields and remaining structures of the major components. During the Phase II of composting 50% of both xylan and cellulose were metabolized by microbial activity, while lignin structures were unaltered. During A. bisporus’ mycelium growth (Phase III) carbohydrates were only slightly consumed and xylan was found to be partially degraded. At the same time, lignin was metabolized for 45% based on pyrolysis GC/MS. Remaining lignin was found to be modified by an increase in the ratio of syringyl (S) to guaiacyl (G) units from 0.5 to 0.7 during mycelium growth, while fewer decorations on the phenolic skeleton of both S and G units remained. PMID:26436656

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

    Science.gov (United States)

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

    2017-12-01

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

  6. 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.

  7. Generation and reactivity of ketyl radicals with lignin related structures. On the importance of the ketyl pathway in the photoyellowing of lignin containing pulps and papers.

    Science.gov (United States)

    Fabbri, Claudia; Bietti, Massimo; Lanzalunga, Osvaldo

    2005-04-01

    [reaction: see text] Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pKa = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k2 = 1.8-2.7 x 10(9) M(-1) s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation of the reduced acceptor (methyl viologen radical cation, MV+*), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2*))(OH)CH2(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled

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

    Directory of Open Access Journals (Sweden)

    José I Santos

    2015-07-01

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

  9. Hydrodeoxygenation of guaiacol over Ni2P/SiO2–reaction mechanism and catalyst deactivation

    NARCIS (Netherlands)

    Lan, X.; Hensen, E.J.M.; Weber, T.

    2018-01-01

    The catalytic hydrodeoxygenation of guaiacol, a phenolic model compound of biomass lignin pyrolysis products, has been investigated under atmospheric pressure in H2 utilizing a Ni2P/SiO2 catalyst. Reaction networks are proposed based on the product distribution as a function of contact time and the

  10. Production of phenolic-rich bio-oil from catalytic fast pyrolysis of biomass using magnetic solid base catalyst

    International Nuclear Information System (INIS)

    Zhang, Zhi-bo; Lu, Qiang; Ye, Xiao-ning; Li, Wen-tao; Hu, Bin; Dong, Chang-qing

    2015-01-01

    Highlights: • Phenolic-rich bio-oil was selectively produced from catalytic fast pyrolysis of biomass using magnetic solid base catalyst. • The actual yield of twelve major phenolic compounds reached 43.9 mg/g. • The peak area% of all phenolics reached 68.5% at the catalyst-to-biomass ratio of 7. • The potassium phosphate/ferroferric oxide catalyst possessed promising recycling properties. - Abstract: A magnetic solid base catalyst (potassium phosphate/ferroferric oxide) was prepared and used for catalytic fast pyrolysis of poplar wood to selectively produce phenolic-rich bio-oil. Pyrolysis–gas chromatography/mass spectrometry experiments were conducted to investigate the effects of pyrolysis temperature and catalyst-to-biomass ratio on the product distribution. The actual yields of important pyrolytic products were quantitatively determined by the external standard method. Moreover, recycling experiments were performed to determine the re-utilization abilities of the catalyst. The results showed that the catalyst exhibited promising activity to selectively produce phenolic-rich bio-oil, due to its capability of promoting the decomposition of lignin to generate phenolic compounds and meanwhile inhibiting the devolatilization of holocellulose. The maximal phenolic yield was obtained at the pyrolysis temperature of 400 °C and catalyst-to-biomass ratio of 2. The concentration of the phenolic compounds increased monotonically along with the increasing of the catalyst-to-biomass ratio, with the peak area% value increasing from 28.1% in the non-catalytic process to as high as 68.5% at the catalyst-to-biomass ratio of 7. The maximal total actual yield of twelve quantified major phenolic compounds was 43.9 mg/g, compared with the value of 29.0 mg/g in the non-catalytic process. In addition, the catalyst could be easily recovered and possessed promising recycling properties.

  11. Electrochemical synthesis and characterization of bilayers of poly(O-aminophenol/ polypyrrole/lignin composites for enhanced charge storage in supercapacitors

    Directory of Open Access Journals (Sweden)

    S. Admassie

    2016-02-01

    Full Text Available Using simple electrosynthesis methods a single and bilayer of conducting polymers, polypyrrole and poly(o-aminophenol with biopolymer lignin hybrid composites were formed on gold electrodes. The specific capacitance of the single polymer-lignin composite value of 400 F/g obtained from galvanostatic charge-discharge experiment at 1 A/g is improved to a value of 514 F/g in the bilayer polymer-lignin composite systems. The charge capacity is also improved from 61 mAh/g to 121 mAh/g by forming a bilayer of conducting polymers. Moreover, the charge retention during self-discharge is improved in the bilayer system. DOI: http://dx.doi.org/10.4314/bcse.v30i1.15

  12. Identification and characterization of 4 missense mutations in brown midrib 12 (Bmr12); the caffeic O-methyltranferase (COMT) of sorghum

    Science.gov (United States)

    Modifying lignin content and composition are targets to improve bioenergy crops for cellulosic conversion to biofuels. In sorghum and other C4 grasses, the brown midrib mutants have been shown to reduce lignin content and alter its composition. Bmr12 encodes the sorghum caffeic O-methyltransferase...

  13. A Xylenol Orange-Based Screening Assay for the Substrate Specificity of Flavin-Dependent para-Phenol Oxidases

    Directory of Open Access Journals (Sweden)

    Tom A. Ewing

    2018-01-01

    Full Text Available Vanillyl alcohol oxidase (VAO and eugenol oxidase (EUGO are flavin-dependent enzymes that catalyse the oxidation of para-substituted phenols. This makes them potentially interesting biocatalysts for the conversion of lignin-derived aromatic monomers to value-added compounds. To facilitate their biocatalytic exploitation, it is important to develop methods by which variants of the enzymes can be rapidly screened for increased activity towards substrates of interest. Here, we present the development of a screening assay for the substrate specificity of para-phenol oxidases based on the detection of hydrogen peroxide using the ferric-xylenol orange complex method. The assay was used to screen the activity of VAO and EUGO towards a set of twenty-four potential substrates. This led to the identification of 4-cyclopentylphenol as a new substrate of VAO and EUGO and 4-cyclohexylphenol as a new substrate of VAO. Screening of a small library of VAO and EUGO active-site variants for alterations in their substrate specificity led to the identification of a VAO variant (T457Q with increased activity towards vanillyl alcohol (4-hydroxy-3-methoxybenzyl alcohol and a EUGO variant (V436I with increased activity towards chavicol (4-allylphenol and 4-cyclopentylphenol. This assay provides a quick and efficient method to screen the substrate specificity of para-phenol oxidases, facilitating the enzyme engineering of known para-phenol oxidases and the evaluation of the substrate specificity of novel para-phenol oxidases.

  14. A Xylenol Orange-Based Screening Assay for the Substrate Specificity of Flavin-Dependent para-Phenol Oxidases.

    Science.gov (United States)

    Ewing, Tom A; van Noord, Aster; Paul, Caroline E; van Berkel, Willem J H

    2018-01-14

    Vanillyl alcohol oxidase (VAO) and eugenol oxidase (EUGO) are flavin-dependent enzymes that catalyse the oxidation of para -substituted phenols. This makes them potentially interesting biocatalysts for the conversion of lignin-derived aromatic monomers to value-added compounds. To facilitate their biocatalytic exploitation, it is important to develop methods by which variants of the enzymes can be rapidly screened for increased activity towards substrates of interest. Here, we present the development of a screening assay for the substrate specificity of para -phenol oxidases based on the detection of hydrogen peroxide using the ferric-xylenol orange complex method. The assay was used to screen the activity of VAO and EUGO towards a set of twenty-four potential substrates. This led to the identification of 4-cyclopentylphenol as a new substrate of VAO and EUGO and 4-cyclohexylphenol as a new substrate of VAO. Screening of a small library of VAO and EUGO active-site variants for alterations in their substrate specificity led to the identification of a VAO variant (T457Q) with increased activity towards vanillyl alcohol (4-hydroxy-3-methoxybenzyl alcohol) and a EUGO variant (V436I) with increased activity towards chavicol (4-allylphenol) and 4-cyclopentylphenol. This assay provides a quick and efficient method to screen the substrate specificity of para -phenol oxidases, facilitating the enzyme engineering of known para- phenol oxidases and the evaluation of the substrate specificity of novel para -phenol oxidases.

  15. Coupling and reactions of 5- hydroxyconiferyl alcohol in lignin formation

    Science.gov (United States)

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

    2016-01-01

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-...

  16. Antioxidant capacity and phenolic acids of virgin coconut oil.

    Science.gov (United States)

    Marina, A M; Man, Y B Che; Nazimah, S A H; Amin, I

    2009-01-01

    The antioxidant properties of virgin coconut oil produced through chilling and fermentation were investigated and compared with refined, bleached and deodorized coconut oil. Virgin coconut oil showed better antioxidant capacity than refined, bleached and deodorized coconut oil. The virgin coconut oil produced through the fermentation method had the strongest scavenging effect on 1,1-diphenyl-2-picrylhydrazyl and the highest antioxidant activity based on the beta-carotene-linoleate bleaching method. However, virgin coconut oil obtained through the chilling method had the highest reducing power. The major phenolic acids detected were ferulic acid and p-coumaric acid. Very high correlations were found between the total phenolic content and scavenging activity (r=0.91), and between the total phenolic content and reducing power (r=0.96). There was also a high correlation between total phenolic acids and beta-carotene bleaching activity. The study indicated that the contribution of antioxidant capacity in virgin coconut oil could be due to phenolic compounds.

  17. Selective phenol methylation to 2,6-dimethylphenol in a fluidized bed of iron-chromium mixed oxide catalyst with o-cresol circulation.

    Science.gov (United States)

    Zukowski, Witold; Berkowicz, Gabriela; Baron, Jerzy; Kandefer, Stanisław; Jamanek, Dariusz; Szarlik, Stefan; Wielgosz, Zbigniew; Zielecka, Maria

    2014-01-01

    2,6-dimethylphenol (2,6-DMP) is a product of phenol methylation, especially important for the plastics industry. The process of phenol methylation in the gas phase is strongly exothermic. In order to ensure good temperature equalization in the catalyst bed, the process was carried out using a catalyst in the form of a fluidized bed - in particular, the commercial iron-chromium catalyst TZC-3/1. Synthesis of 2,6-dimethylphenol from phenol and methanol in fluidized bed of iron-chromium catalyst was carried out and the fluidization of the catalyst was examined. Stable state of fluidized bed of iron-chromium catalyst was achieved. The measured velocities allowed to determine the minimum flow of reactants, ensuring introduction of the catalyst bed in the reactor into the state of fluidization. Due to a high content of o-cresol in products of 2,6-dimethylphenol synthesis, circulation in the technological node was proposed. A series of syntheses with variable amount of o-cresol in the feedstock allowed to determine the parameters of stationary states. A stable work of technological node with o-cresol circulation is possible in the temperature range of350-380°C, and o-cresolin/phenolin molar ratio of more than 0.48. Synthesis of 2,6-DMP over the iron-chromium catalyst is characterized by more than 90% degree of phenol conversion. Moreover, the O-alkylation did not occur (which was confirmed by GC-MS analysis). By applying o-cresol circulation in the 2,6-DMP process, selectivity of more than 85% degree of 2,6-DMP was achieved. The participation levels of by-products: 2,4-DMP and 2,4,6-TMP were low. In the optimal conditions based on the highest yield of 2,6-DMP achieved in the technological node applying o-cresol circulation, there are 2%mol. of 2,4-DMP and 6%mol. of 2,4,6-TMP in the final mixture, whereas 2,4,6-TMP can be useful as a chain stopper and polymer's molar mass regulator during the polymerization of 2,6-DMP.

  18. Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag"+/TiO_2: Influence of electron donating and withdrawing substituents

    International Nuclear Information System (INIS)

    Xiao, Jiadong; Xie, Yongbing; Han, Qingzhen; Cao, Hongbin; Wang, Yujiao; Nawaz, Faheem; Duan, Feng

    2016-01-01

    Highlights: • A weak EWG benefited photocatalytic oxidation of phenols the most. • Phenolic compounds were dominantly oxidized by ·O_2"−, rather than ·OH, "1O_2 or h"+. • ·O_2"− preferred to nucleophilically attack EDG substituted phenols. • ·O_2"− more likely electrophilically attacked EWG substituted phenols. • ·O_2"− simultaneously nucleophilically and electrophilically assaulted p-chlorophenol. - Abstract: A comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag"+/TiO_2 suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (·O_2"−) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between ·O_2"− and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of ·O_2"− and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by ·O_2"−, while ·O_2"− preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by ·O_2"− could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate constant. Possible reactive positions on the phenolic compounds were also detailedly uncovered.

  19. Quick photo-Fenton degradation of phenolic compounds by Cu/Al2O3-MCM-41 under visible light irradiation: small particle size, stabilization of copper, easy reducibility of Cu and visible light active material.

    Science.gov (United States)

    Pradhan, Amaresh C; Nanda, Binita; Parida, K M; Das, Mira

    2013-01-14

    The present study reports the photo-Fenton degradation of phenolic compounds (phenol, 2-chloro-4-nitrophenol and 4-chloro-2-nitrophenol) in aqueous solution using mesoporous Cu/Al(2)O(3)-MCM-41 nanocomposite as a heterogeneous photo-Fenton-like catalyst. The in situ incorporation of mesoporous Al(2)O(3) (MA) into the framework of MCM-41 (sol-gel method) forms Al(2)O(3)-MCM-41 and wetness impregnation of Cu(II) on Al(2)O(3)-MCM-41 generates mesoporous Cu/Al(2)O(3)-MCM-41 composite. The effects of pH and H(2)O(2) concentration on degradation of phenol, 2-chloro-4-nitrophenol and 4-chloro-2-nitrophenol are studied. Kinetics analysis shows that the photocatalytic degradation reaction follows a first-order rate equation. Mesoporous 5 Cu/Al(2)O(3)-MCM-41 is found to be an efficient photo-Fenton-like catalyst for the degradation of phenolic compounds. It shows nearly 100% degradation in 45 min at pH 4. The combined effect of small particle size, stabilization of Cu(2+) on the support Al(2)O(3)-MCM-41, ease reducibility of Cu(2+) and visible light activeness are the key factors for quick degradation of phenolic compounds by Cu/Al(2)O(3)-MCM-41.

  20. Involvement of tyrosine residues, N-terminal amino acids, and beta-alanine in insect cuticular sclerotization.

    Science.gov (United States)

    Andersen, Svend Olav

    2007-09-01

    During sclerotization of insect cuticle the acyldopamines, N-acetyldopamine (NADA) and N-beta-alanyldopamine (NBAD), are oxidatively incorporated into the cuticular matrix, thereby hardening and stabilizing the material by forming crosslinks between the proteins in the cuticular matrix and by forming polymers filling the intermolecular spaces in the cuticle. Sclerotized cuticle from the locust, Schistocerca gregaria, and the beetle, Tenebrio molitor, was hydrolyzed in dilute hydrochloric acid, and from the hydrolysates some components presumably degradation products of cuticular crosslinks were isolated. In two of the components, the sidechain of 3,4-dihydroxyacetophenone was linked to the amino groups of glycine and beta-alanine, respectively, and in the third component to the phenolic group of tyrosine. These three compounds, glycino-dihydroxyacetophenone, beta-alanino-dihydroxyacetophenone, and O-tyrosino-dihydroxyacetophenone, as well as the previously reported compound, lysino-dihydroxyacetophenone [Andersen, S.O., Roepstorff, P., 2007. Aspects of cuticular sclerotization in the locust, Schistocerca gregaria, and the beetle, Tenebrio molitor. Insect Biochem. Mol. Biol. 37, 223-234], are suggested to be degradation products of cuticular crosslinks, in which amino acid residues formed linkages to both the alpha- and beta-positions of the sidechain of acyldopamines.

  1. 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.

  2. Phenolic compounds in Ross Sea water

    Science.gov (United States)

    Zangrando, Roberta; Barbaro, Elena; Gambaro, Andrea; Barbante, Carlo; Corami, Fabiana; Kehrwald, Natalie; Capodaglio, Gabriele

    2016-04-01

    Phenolic compounds are semi-volatile organic compounds produced during biomass burning and lignin degradation in water. In atmospheric and paleoclimatic ice cores studies, these compounds are used as biomarkers of wood combustion and supply information on the type of combusted biomass. Phenolic compounds are therefore indicators of paleoclimatic interest. Recent studies of Antarctic aerosols highlighted that phenolic compounds in Antarctica are not exclusively attributable to biomass burning but also derive from marine sources. In order to study the marine contribution to aerosols we developed an analytical method to determine the concentration of vanillic acid, vanillin, p-coumaric acid, syringic acid, isovanillic acid, homovanillic acid, syringaldehyde, acetosyringone and acetovanillone present in dissolved and particle phases in Sea Ross waters using HPLC-MS/MS. The analytical method was validated and used to quantify phenolic compounds in 28 sea water samples collected during a 2012 Ross Sea R/V cruise. The observed compounds were vanillic acid, vanillin, acetovanillone and p-coumaric acid with concentrations in the ng/L range. Higher concentrations of analytes were present in the dissolved phase than in the particle phase. Sample concentrations were greatest in the coastal, surficial and less saline Ross Sea waters near Victoria Land.

  3. 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.

  4. 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

  5. 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.

  6. Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations

    NARCIS (Netherlands)

    Bonnet, Fanny; Dyer, Hellen E.; El Kinani, Yassine; Dietz, Carin; Roussel, Pascal; Bria, Marc; Visseaux, Marc; Zinck, Philippe; Mountford, Philip

    2015-01-01

    New bis(phenolate)amine-supported neodymium borohydride complexes and their previously reported samarium analogues were tested as catalysts for the polymerisation of styrene and isoprene. Reaction of Na2O2NL (L = py, OMe, NMe2) with Nd(BH4)3(THF)3 afforded the borohydride complexes

  7. 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.

  8. 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.

  9. Crystallization behavior of (1 - x)Li{sub 2}O.xNa{sub 2}O.Al{sub 2}O{sub 3}.4SiO{sub 2} glasses

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Moo-Chin [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Cheng, Chih-Wei; Chang, Kuo-Ming [Department of Mechanical Engineering, National Kaohsiung University of Applied Sciences, 415 Chien-Kung Road, Kaohsiung 80782, Taiwan (China); Hsi, Chi-Shiung, E-mail: chsi@nuu.edu.t [Department of Materials Science and Engineering, National United University, 1 Lien-Da, Kung-Ching Li, Miao-Li 36003, Taiwan (China)

    2010-07-02

    The crystallization behavior of the (1 - x)Li{sub 2}O.xNa{sub 2}O.Al{sub 2}O{sub 3}.4SiO{sub 2} glasses has been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron diffraction (ED) and energy dispersive spectroscopy (EDS). The crystalline phase was composed of {beta}-spodumene. The isothermal crystallization kinetics of {beta}-spodumene from the (1 - x)Li{sub 2}O.xNa{sub 2}O.Al{sub 2}O{sub 3}.4SiO{sub 2} glasses has also been studied by a quantitative X-ray diffraction method. The activation energy of {beta}-spodumene formation decreases from 359.2 to 317.8 kJ/mol when the Na{sub 2}O content increases from 0 to 0.4 mol and it increases from 317.8 to 376.9 kJ/mol when the Na{sub 2}O content increases from 0.4 to 0.6 mol. The surface nucleation and plate-like growth were dominant in the crystallization of the (1 - x)Li{sub 2}O.xNa{sub 2}O.Al{sub 2}O{sub 3}.4SiO{sub 2} glasses.

  10. Synthesis of 4-O-glycosylated 1,5-anhydro-D-fructose and of 1,5-anhydro-D-tagatose from a common intermediate 2,3-O-isopropylidene-D-fructose.

    Science.gov (United States)

    Agoston, Károly; Dékány, Gyula; Lundt, Inge

    2009-05-26

    Four novel disaccharides of glycosylated 1,5-anhydro-D-ketoses have been prepared: 1,5-anhydro-4-O-beta-D-glucopyranosyl-D-fructose, 1,5-anhydro-4-O-beta-D-galactopyranosyl-D-fructose, 1,5-anhydro-4-O-beta-D-glucopyranosyl-D-tagatose, and 1,5-anhydro-4-O-beta-D-galactopyranosyl-D-tagatose. The common intermediate, 1,5-anhydro-2,3-O-isopropylidene-beta-D-fructopyranose, was prepared from D-fructose and was converted into the D-tagatose derivative by oxidation followed by stereoselective reduction to the 4-epimer. The anhydroketoses thus prepared were glycosylated and deprotected to give the disaccharides.

  11. Phenolic profiling of caffeic acid O-methyltransferase-deficient poplar reveals novel benzodioxane oligolignols.

    Science.gov (United States)

    Morreel, Kris; Ralph, John; Lu, Fachuang; Goeminne, Geert; Busson, Roger; Herdewijn, Piet; Goeman, Jan L; Van der Eycken, Johan; Boerjan, Wout; Messens, Eric

    2004-12-01

    Caffeic acid O-methyltransferase (COMT) catalyzes preferentially the methylation of 5-hydroxyconiferaldehyde to sinapaldehyde in monolignol biosynthesis. Here, we have compared HPLC profiles of the methanol-soluble phenolics fraction of xylem tissue from COMT-deficient and control poplars (Populus spp.), using statistical analysis of the peak heights. COMT down-regulation results in significant concentration differences for 25 of the 91 analyzed peaks. Eight peaks were exclusively detected in COMT-deficient poplar, of which four could be purified for further identification using mass spectrometry/mass spectrometry, nuclear magnetic resonance, and spiking of synthesized reference compounds. These new compounds were derived from 5-hydroxyconiferyl alcohol or 5-hydroxyconiferaldehyde and were characterized by benzodioxane moieties, a structural type that is also increased in the lignins of COMT-deficient plants. One of these four benzodioxanes amounted to the most abundant oligolignol in the HPLC profile. Furthermore, all of the differentially accumulating oligolignols involving sinapyl units were either reduced in abundance or undetectable. The concentration levels of all identified oligolignols were in agreement with the relative supply of monolignols and with their chemical coupling propensities, which supports the random coupling hypothesis. Chiral HPLC analysis of the most abundant benzodioxane dimer revealed the presence of both enantiomers in equal amounts, indicating that they were formed by radical coupling reactions under simple chemical control rather than guided by dirigent proteins.

  12. Decomposition mechanisms and non-isothermal kinetics of LiHC_2O_4·H_2O

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were characterized by X-ray diffraction (XRD), which indicated the decompositions at 150, 170, and 420℃, relating to LiHC2O4, Li2C2O4, Li2C2O4, and Li2CO3, respectively. Reaction mechanisms in the whole sintering process were determined, and the model fitting kinetic approaches were applied to data for non...

  13. Effects of elevated concentrations of atmospheric CO{sub 2} and tropospheric O{sub 3} on leaf litter production and chemistry in trembling aspen and paper birch communities

    Energy Technology Data Exchange (ETDEWEB)

    Liu, L.; King, J.S. [Michigan Technological Univ., Houghton, MI (United States). School of Forest Resources and Environmental Science; Giardina, C.P. [United States Dept. of Agriculture Forest Service, Houghton, MI (United States)

    2005-12-01

    This study examined the effects of elevated carbon dioxide (CO{sub 2}) and elevated ozone (O{sub 3}) on the quantity and timing of nutrient release to plants and on soil carbon formation rates, and how they are influenced by the combined change in litter quality and quantity. The changes in leaf litter in response to environmental changes was characterized in order to understand the influence of global change on forests. Free-air CO{sub 2} enrichment (FACE) technology was used to examine leaf litter production and biochemical input to soil in response to elevated CO{sub 2} and O{sub 3} treatments. The study involved collecting litter from aspen and birch-aspen communities that had been exposed to FACE and O{sub 3} treatments for 6 years. The hypothesis of growth differentiation balance was used as the basis to develop other hypotheses regarding litter chemistry responses to elevated levels of carbon dioxide and ozone. It was assumed that environmental factors that increase the net balance of plant carbon sources relative to growth sinks will increase the allocation of photosynthate to the production of carbon-based secondary compounds. Litter was analyzed for concentrations of carbon, nitrogen, soluble sugars, lipids, lignin, cellulose, hemicellulose and carbon-based defensive compounds such as soluble phenolics and condensed tannins. The study showed that high levels of ozone greatly increased litter concentrations of soluble sugars, soluble phenolics and condensed tannins, but there were no major effects of elevated carbon dioxide or elevated ozone on the concentrations of individual carbon structural carbon hydrates such as cellulose, hemicellulose and lignin. It was concluded that in the future, the inputs of nitrogen, soluble sugars, condensed tannins, soluble phenolics, cellulose and lignin to forest soils can change as a result of small changes in litter chemistry resulting from elevated CO{sub 2}, tropospheric O{sub 3}, and changes in litter biomass

  14. Thymosin beta 4 and thymosin beta 10 expression in hepatocellular carcinoma

    Directory of Open Access Journals (Sweden)

    W. Theunissen

    2014-03-01

    Full Text Available Thymosin beta 4 (Tβ4 and thymosin beta 10 (Tβ10 are two members of the beta-thymosin family involved in many cellular processes such as cellular motility, angiogenesis, inflammation, cell survival and wound healing. Recently, a role for beta-thymosins has been proposed in the process of carcinogenesis as both peptides were detected in several types of cancer. The aim of the present study was to investigate the expression pattern of Tβ4 and Tβ10 in hepatocellular carcinoma (HCC. To this end, the expression pattern of both peptides was analyzed in liver samples obtained from 23 subjects diagnosed with HCC. Routinely formalin-fixed and paraffin-embedded liver samples were immunostained by indirect immunohistochemistry with polyclonal antibodies to Tβ4 and Tβ10. Immunoreactivity for Tβ4 and Tβ10 was detected in the liver parenchyma of the surrounding tumor area. Both peptides showed an increase in granular reactivity from the periportal to the periterminal hepatocytes. Regarding HCC, Tβ4 reactivity was detected in 7/23 cases (30% and Tβ10 reactivity in 22/23 (97% cases analyzed, adding HCC to human cancers that express these beta-thymosins. Intriguing finding was seen looking at the reactivity of both peptides in tumor cells infiltrating the surrounding liver. Where Tβ10 showed a strong homogeneous expression, was Tβ4 completely absent in cells undergoing stromal invasion. The current study shows expression of both beta-thymosins in HCC with marked differences in their degree of expression and frequency of immunoreactivity. The higher incidence of Tβ10 expression and its higher reactivity in tumor cells involved in stromal invasion indicate a possible major role for Tβ10 in HCC progression.

  15. Aqueous phase hydrogenation of phenol catalyzed by Pd and PdAg on ZrO 2

    Energy Technology Data Exchange (ETDEWEB)

    Resende, Karen A.; Hori, Carla E.; Noronha, Fabio B.; Shi, Hui; Gutierrez, Oliver Y.; Camaioni, Donald M.; Lercher, Johannes A.

    2017-11-01

    Hydrogenation of phenol in aqueous phase was studied over a series of ZrO2-supported Pd catalysts in order to explore the effects of particle size and of Ag addition on the activity of Pd. Kinetic assessments were performed in a batch reactor, on monometallic Pd/ZrO2 samples with different Pd loadings (0.5%, 1% and 2%), as well as on a 1% PdAg/ZrO2 sample. The turnover frequency (TOF) increases with the Pd particle size. The reaction orders in phenol and H2 indicate that the surface coverages by phenol, H2 and their derived intermediates are higher on 0.5% Pd/ZrO2 than on other samples. The activation energy was the lowest on the least active sample (0.5% Pd/ZrO2), while being identical on 1% and 2% Pd/ZrO2 catalysts. Thus, the significantly lower activity of the small Pd particles (1-2 nm on average) in 0.5%Pd/ZrO2 is explained by the unfavorable activation entropies for the strongly bound species. The presence of Ag increases considerably the TOF of the reaction by decreasing the Ea and increasing the coverages of phenol and H2.

  16. 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...

  17. Response of Fusarium thapsinum to sorghum brown midrib lines and to phenolic metabolites

    Science.gov (United States)

    Presentation type: poster Presentation title: Response of Fusarium thapsinum to sorghum brown midrib lines and to phenolic metabolites Sorghum lines were bred for reduced lignin for cellulosic bioenergy uses, through the incorporation of brown midrib (bmr) bmr6 and/or 12 into two gen...

  18. Perioperative beta blockers in patients having non-cardiac surgery

    DEFF Research Database (Denmark)

    Bangalore, Sripal; Wetterslev, Jørn; Pranesh, Shruthi

    2008-01-01

    American College of Cardiology and American Heart Association (ACC/AHA) guidelines on perioperative assessment recommend perioperative beta blockers for non-cardiac surgery, although results of some clinical trials seem not to support this recommendation. We aimed to critically review the evidence...... to assess the use of perioperative beta blockers in patients having non-cardiac surgery....

  19. 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.

  20. 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.

  1. Anionic chromogenic chemosensors highly selective for fluoride or cyanide based on 4-(4-Nitrobenzylideneamine)phenol

    OpenAIRE

    Nicoleti,Celso R.; Marini,Vanderléia G.; Zimmermann,Lizandra M.; Machado,Vanderlei G.

    2012-01-01

    4-(4-Nitrobenzylideneamine)phenol was used in two strategies allowing the highly selective detection of F- and CN-. Firstly, the compound in acetonitrile acts as a chromogenic chemosensor based on the idea that more basic anions cause its deprotonation (colorless solution), generating a colored solution containing phenolate. The discrimination of CN- over F- was obtained by adding 1.4% water to acetonitrile: water preferentially solvates F-, leaving the CN- free to deprotonate the compound. A...

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

    Science.gov (United States)

    2012-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Li Muyang

    2012-06-01

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

  4. Reliability of Czochralski-grown {beta}-BaB{sub 2}O{sub 4}(BBO) devices

    Energy Technology Data Exchange (ETDEWEB)

    Umezu, Nobuhiko; Fukui, Tatsuo; Okamoto, Tsutomu; Wada, Hiroyuki; Tatsuki, Kouichi; Kondo, Kenji; Kubota, Shigeo [Sony Corp., Tokyo (Japan)

    1998-03-01

    We have achieved more than 1000 hours-operation in 266 nm-continuous wave (CW), 100 mW-generation of all-solid-state-UV laser system using Czochralski (Cz)-grown {beta}-BaB{sub 2}O{sub 4}(BBO) crystal devices. Absorption of the Cz-grown crystal for e-ray at 266 nm was improved to 1%/cm, which is one-third lower than that of the crystal grown by top seeded solution growth (TSSG) method. Degradation rate of 266 nm generation, using 7 kHz repetition rate laser diode pumped Q switched Nd:YAG laser as a fundamental light source, was one order of magnitude lower than that of TSSG-crystal. Surface roughness of the crystal was better than 0.3 rms.-nm. HfO{sub 2} film with extremely high adhesion was deposited on the surfaces using reactive low voltage ion plating method. Our devices can be put to practical use in areas of photolithography, micro fabrication, material processing and ultra high density optical disk mastering. (author)

  5. Phenol-formaldehyde reactivity with lignin in the wood cell wall

    Science.gov (United States)

    Daniel J. Yelle; John Ralph

    2016-01-01

    Latewood from Pinus taeda was reacted with alkaline phenol–formaldehyde (PF) adhesive and characterised using two-dimensional 1H–13C solution-state nuclear magnetic resonance (NMR) spectroscopy so that chemical modification of the wood cell wall polymers, after PF resol curing, could be elucidated. The...

  6. Two-dimensional NMR evidence for cleavage of lignin and xylan substituents in wheat straw through hydrothermal pretreatment and enzymatic hydrolysis

    DEFF Research Database (Denmark)

    Yelle, Daniel J.; Kaparaju, Laxmi-Narasimha Prasad; Hunt, Christopher G.

    2013-01-01

    correlation spectroscopy, via an heteronuclear single quantum coherence experiment, revealed substantial lignin β-aryl ether cleavage, deacetylation via cleavage of the natural acetates at the 2-O- and 3-O-positions of xylan, and uronic acid depletion via cleavage of the (1 → 2)-linked 4-O....... g., further deacylation revealed by the depletion in ferulate and p-coumarate structures). Supplementary chemical analyses showed that the hydrothermal pretreatment increased the cellulose and lignin concentration with partial removal of extractives and hemicelluloses. The subsequent enzymatic...

  7. 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.

  8. Phenol Removal by a Novel Non-Photo-Dependent Semiconductor Catalyst in a Pilot-Scaled Study: Effects of Initial Phenol Concentration, Light, and Catalyst Loading

    Directory of Open Access Journals (Sweden)

    Xiao Chen

    2014-01-01

    Full Text Available A novel non-photo-dependent semiconductor catalyst (CT was employed to degrade phenol in the present pilot-scaled study. Effect of operational parameters such as phenol initial concentration, light area, and catalyst loading on phenol degradation, was compared between CT catalyst and the conventional photocatalyst titanium dioxide. CT catalyst excelled titanium dioxide in treating and mineralizing low-level phenol, under both mild UV radiation and thunder conditions of nonphoton. The result suggested that CT catalyst could be applied in circumstances when light is not easily accessible in pollutant-carrying media (e.g., particles, cloudy water, and colored water.

  9. Valorization of lignin and cellulose in acid-steam-exploded corn stover by a moderate alkaline ethanol post-treatment based on an integrated biorefinery concept.

    Science.gov (United States)

    Yang, Sheng; Zhang, Yue; Yue, Wen; Wang, Wei; Wang, Yun-Yan; Yuan, Tong-Qi; Sun, Run-Cang

    2016-01-01

    Due to the unsustainable consumption of fossil resources, great efforts have been made to convert lignocellulose into bioethanol and commodity organic compounds through biological methods. The conversion of cellulose is impeded by the compactness of plant cell wall matrix and crystalline structure of the native cellulose. Therefore, appropriate pretreatment and even post-treatment are indispensable to overcome this problem. Additionally, an adequate utilization of coproduct lignin will be important for improving the economic viability of modern biorefinery industries. The effectiveness of moderate alkaline ethanol post-treatment on the bioconversion efficiency of cellulose in the acid-steam-exploded corn stover was investigated in this study. Results showed that an increase of the alcoholic sodium hydroxide (NaOH) concentration from 0.05 to 4% led to a decrease in the lignin content in the post-treated samples from 32.8 to 10.7%, while the cellulose digestibility consequently increased. The cellulose conversion of the 4% alcoholic NaOH integrally treated corn stover reached up to 99.3% after 72 h, which was significantly higher than that of the acid steam exploded corn stover without post-treatment (57.3%). In addition to the decrease in lignin content, an expansion of cellulose I lattice induced by the 4% alcoholic NaOH post-treatment played a significant role in promoting the enzymatic hydrolysis of corn stover. More importantly, the lignin fraction (AL) released during the 4% alcoholic NaOH post-treatment and the lignin-rich residue (EHR) remained after the enzymatic hydrolysis of the 4% alcoholic NaOH post-treated acid-steam-exploded corn stover were employed to synthesize lignin-phenol-formaldehyde (LPF) resins. The plywoods prepared with the resins exhibit satisfactory performances. An alkaline ethanol system with an appropriate NaOH concentration could improve the removal of lignin and modification of the crystalline structure of cellulose in acid

  10. 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.

  11. Enzymatic Browning in Sugar Beet Leaves (Beta vulgaris L.)

    NARCIS (Netherlands)

    Vissers, Anne; Kiskini, Alexandra; Hilgers, Roelant; Marinea, Marina; Wierenga, Peter Alexander; Gruppen, Harry; Vincken, Jean Paul

    2017-01-01

    Sugar beet (Beta vulgaris L.) leaves of 8 month (8m) plants showed more enzymatic browning than those of 3 month (3m). Total phenolic content increased from 4.6 to 9.4 mg/g FW in 3m and 8m, respectively, quantitated by

  12. Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water.

    Science.gov (United States)

    Hao, Xiao Long; Zhou, Ming Hua; Lei, Le Cheng

    2007-03-22

    TiO(2) photocatalyst (P-25) (50mgL(-1)) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO(2) were obviously increased. Pulsed high-voltage discharge process with TiO(2) had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10x10(-6) to 1.50x10(-6)Ms(-1), the ozone formation rate from 1.99x10(-8) to 2.35x10(-8)Ms(-1), respectively. In addition, this process had no influence on the photocatalytic properties of TiO(2). The introduction of TiO(2) photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants.

  13. Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water

    International Nuclear Information System (INIS)

    Hao Xiaolong; Zhou Ming Hua; Lei Lecheng

    2007-01-01

    TiO 2 photocatalyst (P-25) (50 mg L -1 ) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO 2 were obviously increased. Pulsed high-voltage discharge process with TiO 2 had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10 x 10 -6 to 1.50 x 10 -6 M s -1 , the ozone formation rate from 1.99 x 10 -8 to 2.35 x 10 -8 M s -1 , respectively. In addition, this process had no influence on the photocatalytic properties of TiO 2 . The introduction of TiO 2 photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants

  14. 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

  15. Determination of Insulin Resistance and Beta Cell Function in Healthy Obese and Non-obese Individuals

    International Nuclear Information System (INIS)

    Kazmi, A.; Sattar, A.; Tariq, K. M.; Najamussahar; Hashim, R.; Almani, M. I.

    2013-01-01

    Objective: To determine insulin resistance and beta cell function in healthy obese and nonobese individuals of the local population. Study Design: Case control study. Place and Duration of Study: AFIP Rawalpindi in collaboration with department of medicine military hospital(MH) Rawalpindi, from Aug 2008 to Mar 2009. Methods: Eighty obese(n=40) and non-obese(n=40) subjects were selected by non-probability convenience sampling. Plasma insulin, glucose, and serum total cholestrol were estimated in fasting state. Insulin resistance was calculated by HOMA-IR and beta cell function by HOMA- equation. Results: Significant differences were observed between obese and non-obese individuals regarding insulin resistance, beta cell function, and BMI and serum total cholesterol. Mean insulin resistance in obese group was found to be 11.1 +- 5.1(range 7.0-16.2) and in non-obese group it was 0.9+-0.4 (range 0.5-1.3). This difference was highly significant (p=0.001). There was a highly significant difference between the two groups in term of beta cell function with mean rank 60.1 for obese group and 20.9 non obese groups (Asym sig. 2 tailed 0.000). Also the correlation (r = 0.064) between insulin resistance and beta cell function in obese group is highly significant (p = 0.000). Mean serum leptin levels were lower (6.3 ng/ml) in non-obese, and high (57.2 ng/ml) in the obese group. Conclusions: Insulin resistance is found higher in obese individuals. Beta cell function is significantly different between obese and non-obese groups. (author)

  16. Cocoa Phenolic Extract Protects Pancreatic Beta Cells against Oxidative Stress

    Directory of Open Access Journals (Sweden)

    Laura Bravo

    2013-07-01

    Full Text Available Diabetes mellitus is associated with reductions in glutathione, supporting the critical role of oxidative stress in its pathogenesis. Antioxidant food components such as flavonoids have a protective role against oxidative stress-induced degenerative and age-related diseases. Flavonoids constitute an important part of the human diet; they can be found in most plant foods, including green tea, grapes or cocoa and possess multiple biological activities. This study investigates the chemo-protective effect of a cocoa phenolic extract (CPE containing mainly flavonoids against oxidative stress induced by tert-butylhydroperoxide (t-BOOH on Ins-1E pancreatic beta cells. Cell viability and oxidative status were evaluated. Ins-1E cells treatment with 5–20 μg/mL CPE for 20 h evoked no cell damage and did not alter ROS production. Addition of 50 μM t-BOOH for 2 h increased ROS and carbonyl groups content and decreased reduced glutathione level. Pre-treatment of cells with CPE significantly prevented the t-BOOH-induced ROS and carbonyl groups and returned antioxidant defences to adequate levels. Thus, Ins-1E cells treated with CPE showed a remarkable recovery of cell viability damaged by t-BOOH, indicating that integrity of surviving machineries in the CPE-treated cells was notably protected against the oxidative insult.

  17. Purification, characterization and gene cloning of thermostable O-acetyl-L-serine sulfhydrylase forming {beta}-cyano-L-alanine

    Energy Technology Data Exchange (ETDEWEB)

    Omura, Hironori; Yoshida, Toyokazu; Nagasawa, Toru [Gifu Univ. (Japan). Dept. of Biomolecular Science; Kuroda, Masako [Ikeda Food Research Co., Ltd., Fukuyama, Hiroshima (Japan); Kobayashi, Michihiko; Shimizu, Sakayu [Kyoto Univ. (Japan). Agricultural Sciences

    2003-10-01

    A thermophilic and cyanide ion-tolerant bacterium, Bacillus stearothermophilus CN3 isolated from a hot spring in Japan, was found to produce thermostable {beta}-cyano-L-alanine synthase. The enzyme catalyzes the synthesis of {beta}-cyano-L-alanine from O-acetyl-L-serine and cyanide ions. The purified enzyme has a molecular mass of approximately 70 kDa and consists of two identical sub-units. It was stable in the pH range of 6.0 to 10.0 and up to 70degC. The enzyme also catalyzes the synthesis of various {beta}-substituted-L-alanine derivatives from O-acetyl-L-serine and nucleophilic reagents. The gene encoding the {beta}-cyano-L-alanine synthase was isolated from B. stearothermophilus CN3. Sequence homology analysis revealed that the {beta}-cyano-L-alanine synthase of the bacterium is O-acetyl-L-serine sulfhydrylase. A recombinant plasmid, constructed by ligation of the cloned gene and an expression vector, pKK223-3, was introduced into E. coli JM109. The transformed E. coli cells overexpressed {beta}-cyano-L-alanine synthase. Heat stable {beta}-cyano-L-alanine synthase can be applied to the synthesis of [4-{sup 11}C]L-2,4-diaminobutyric acid as a tracer for positron emission tomography. (author)

  18. 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.

  19. Phenolic Profiling of Caffeic Acid O-Methyltransferase-Deficient Poplar Reveals Novel Benzodioxane Oligolignols1

    Science.gov (United States)

    Morreel, Kris; Ralph, John; Lu, Fachuang; Goeminne, Geert; Busson, Roger; Herdewijn, Piet; Goeman, Jan L.; Van der Eycken, Johan; Boerjan, Wout; Messens, Eric

    2004-01-01

    Caffeic acid O-methyltransferase (COMT) catalyzes preferentially the methylation of 5-hydroxyconiferaldehyde to sinapaldehyde in monolignol biosynthesis. Here, we have compared HPLC profiles of the methanol-soluble phenolics fraction of xylem tissue from COMT-deficient and control poplars (Populus spp.), using statistical analysis of the peak heights. COMT down-regulation results in significant concentration differences for 25 of the 91 analyzed peaks. Eight peaks were exclusively detected in COMT-deficient poplar, of which four could be purified for further identification using mass spectrometry/mass spectrometry, nuclear magnetic resonance, and spiking of synthesized reference compounds. These new compounds were derived from 5-hydroxyconiferyl alcohol or 5-hydroxyconiferaldehyde and were characterized by benzodioxane moieties, a structural type that is also increased in the lignins of COMT-deficient plants. One of these four benzodioxanes amounted to the most abundant oligolignol in the HPLC profile. Furthermore, all of the differentially accumulating oligolignols involving sinapyl units were either reduced in abundance or undetectable. The concentration levels of all identified oligolignols were in agreement with the relative supply of monolignols and with their chemical coupling propensities, which supports the random coupling hypothesis. Chiral HPLC analysis of the most abundant benzodioxane dimer revealed the presence of both enantiomers in equal amounts, indicating that they were formed by radical coupling reactions under simple chemical control rather than guided by dirigent proteins. PMID:15563622

  20. Recycling of phenolic compounds in Borneo's tropical peat swamp forests.

    Science.gov (United States)

    Yule, Catherine M; Lim, Yau Yan; Lim, Tse Yuen

    2018-02-07

    Tropical peat swamp forests (TPSF) are globally significant carbon stores, sequestering carbon mainly as phenolic polymers and phenolic compounds (particularly as lignin and its derivatives) in peat layers, in plants, and in the acidic blackwaters. Previous studies show that TPSF plants have particularly high levels of phenolic compounds which inhibit the decomposition of organic matter and thus promote peat accumulation. The studies of phenolic compounds are thus crucial to further understand how TPSF function with respect to carbon sequestration. Here we present a study of cycling of phenolic compounds in five forests in Borneo differing in flooding and acidity, leaching of phenolic compounds from senescent Macaranga pruinosa leaves, and absorption of phenolics by M. pruinosa seedlings. The results of the study show that total phenolic content (TPC) in soil and leaves of three species of Macaranga were highest in TPSF followed by freshwater swamp forest and flooded limestone forest, then dry land sites. Highest TPC values were associated with acidity (in TPSF) and waterlogging (in flooded forests). Moreover, phenolic compounds are rapidly leached from fallen senescent leaves, and could be reabsorbed by tree roots and converted into more complex phenolics within the leaves. Extreme conditions-waterlogging and acidity-may facilitate uptake and synthesis of protective phenolic compounds which are essential for impeded decomposition of organic matter in TPSF. Conversely, the ongoing drainage and degradation of TPSF, particularly for conversion to oil palm plantations, reverses the conditions necessary for peat accretion and carbon sequestration.

  1. 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.

  2. 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...

  3. Biodegradation of phenol-formaldehyde resins modified with commercial lignins

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-07-01

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

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

    Science.gov (United States)

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

    2015-01-01

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

  5. 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.

  6. 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

  7. [Study of alkaline lignin from Arundo donax linn based on FT Raman spectroscopy].

    Science.gov (United States)

    You, Ting-ting; Ma, Jian-feng; Guo, Si-qin; Xu, Feng

    2014-08-01

    Arundo donax linn, as a perennial energy crop, has promising application prospect. In the present study, Fourier transform Raman (FT Raman) spectroscopy was applied to determine the structural information of materials, milled wood lignin (MWL), and alkaline lignins (AL, under different treated time) from A. donax stem nondestructively. The results indicated that, extractable compounds in A. donax had negative contribution to the Raman spectra without rising new Raman peaks. FT Raman spectrum of MWL indicated that MWL from A. donax was HGS type lignins. Compared with the spectra of MWL from wood materials, the peak at 1173 cm(-1) was much higher in intensity for the MWL from A. donax stem, which may be assigned to hydroxycinnamic acid by analyzing the standard. With respect to FT Raman spectra of ALs, the relatively highest intensity of 1173 cm(-1) was found in alkaline lignin (AL2), which was treated for 40 min by alkaline. Moreover, the peak of coniferaldehyde/sinapaldehyde (1630 cm(-1)) was lowest in intensity while the band attributed to coniferyl alcohol/sinapyl alcohol (1660 cm(-1)) was almost disappeared in AL2. It could be inferred that AL2 demonstrated a highest content of phenolic acid, which may improve its potential application, such as for antioxidant activity. Furthermore, the results obtained by FT Raman spectra were verified by two dimensional heteronuclear singlequantum coherence nuclear magnetic resonance analyses. Above all, FT Raman spectroscopy provided alternative safe, rapid, accurate, and nondestructive technology for lignin structure determination.

  8. Photocatalytic Active Coatings for Lignin Degradation in a Continuous Packed Bed Reactor

    Directory of Open Access Journals (Sweden)

    Colin Awungacha Lekelefac

    2014-01-01

    Full Text Available The synthesis of immobilized catalyst on porous glass support material via the sol-gel route is reported. TiO2-P25-SiO2 + Pt, TiO2-P25-SiO2, TiOSO4_30.6 wt%, and ZnO + TiO2-P25-SiO2 catalysts were synthesized and a comparative study is done regarding morphology of coatings, degradation rates, reaction rates, dissolved carbon (DC, formation of peaks, and fluorescence of products formed from the photocatalytic degradation of lignin sulfonate obtained from a local paper plant. Through simultaneous reaction-extraction pathways applying dialysis filtration and highly porous polystyrene divinylbenzene adsorbent resin (HR-P for solid phase extraction (SPE, an attempt has been made to isolate smaller molecules produced from photocatalytic degradation. Moreover relatively high lignin sulfonate (0.5 g/L concentrations are used in the reactions. UV-Vis spectroscopy revealed a faster reduction in the concentration values for the aliphatic moiety compared to the aromatic moiety. Peaks were observed by both fluorescence spectroscopy and HPLC suggesting the production of new substances and fluorophores.

  9. Microbial β-etherases and glutathione lyases for lignin valorisation in biorefineries: current state and future perspectives.

    Science.gov (United States)

    Husarcíková, Jana; Voß, Hauke; Domínguez de María, Pablo; Schallmey, Anett

    2018-05-04

    Lignin is the major aromatic biopolymer in nature, and it is considered a valuable feedstock for the future supply of aromatics. Hence, its valorisation in biorefineries is of high importance, and various chemical and enzymatic approaches for lignin depolymerisation have been reported. Among the enzymes known to act on lignin, β-etherases offer the possibility for a selective cleavage of the β-O-4 aryl ether bonds present in lignin. These enzymes, together with glutathione lyases, catalyse a reductive, glutathione-dependent ether bond cleavage displaying high stereospecificity. β-Etherases and glutathione lyases both belong to the superfamily of glutathione transferases, and several structures have been solved recently. Additionally, different approaches for their application in lignin valorisation have been reported in the last years. This review gives an overview on the current knowledge on β-etherases and glutathione lyases, their biochemical and structural features, and critically discusses their potential for application in biorefineries.

  10. Cinnamic acid 4-hydroxylase of sorghum [Sorghum biocolor (L.) Moench] gene SbC4H1 restricts lignin synthesis in Arabidopsis

    Science.gov (United States)

    Cinnamic acid 4-hydroxylase (C4H) is the first hydroxylase enzyme of the phenylpropanoid pathway, and its content and activity affects the lignin synthesis. In this study, we isolated a C4H gene SbC4H1 from the suppression subtractive hybridization library of brown midrib (bmr) mutants of Sorghum b...

  11. Significance of Lignin S/G Ratio in Biomass Recalcitrance of Populus trichocarpa Variants for Bioethanol Production

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Chang Geun [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Dumitrache, Alexandru [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Muchero, Wellington [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Natzke, Jace [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Akinosho, Hannah [Georgia Inst. of Technology, Atlanta, GA (United States); Li, Mi [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sykes, Robert W. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Brown, Steven D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Davison, Brian [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Tuskan, Gerald A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pu, Yunqiao [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Ragauskas, Arthur J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

    2017-12-11

    Lignin S/G ratio has been investigated as an important factor in biomass recalcitrance to bioethanol production. Because of the complexity and variety of biomass, recalcitrance was also reportedly influenced by several other factors, such as total lignin content, degree of cellulose polymerization, etc. In addition, the effect of S/G ratio on biomass conversion is not uniform across plant species. Herein, 11 Populus trichocarpa natural variants grown under the same conditions with similar total lignin content were selected to minimize the effects of other factors. The lignin S/G ratio of the selected P. trichocarpa natural variants showed negative correlations with p-hydroxybenzoate (PB) and β–5 linkage contents, while it had positive ones with β-O-4 linkage, lignin molecular weight, and ethanol production. In conclusion, this study showed the importance of lignin S/G ratio as an independent recalcitrance factor that may aid future energy crop engineering and biomass conversion strategies.

  12. 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)

  13. Hemoglobina C em homozigose e interação com talassemia beta Homozygous hemoglobin C and its interaction with beta thalassemia

    Directory of Open Access Journals (Sweden)

    Ivan L. Angulo

    2009-01-01

    Full Text Available A hemoglobina C (Hb C é originária do oeste da África e é detectada por migração lenta na eletroforese alcalina em acetato de celulose. Consiste na mutação do gene da globina beta no códon 6 (GAG-AAG, resultando na substituição do sexto aminoácido da cadeia beta da hemoglobina humana, o ácido glutâmico, pelo aminoácido lisina. A cromatografia de alto desempenho (HPLC separa completamente as frações C e A2, permitindo caracterizar a presença da interação com talassemia beta. Esta entidade (Hb CC, em homozigoze é considerada benigna em relação à doença falciforme, já que a falcizaçãoo faz parte de sua fisiopatologia. A raridade do diagnóstico C homozigoto e C talassemia beta nos pacientes portadores de hemoglobinopatias nos alertou para a necessidade de se conhecer melhor e estudar aspectos clínicos e hematológicos dos casos dessa mutação em homozigose e na interação com a talassemia beta no ambulatório de anemias do Centro Regional de Hematologia e Hemoterapia de Ribeirão Preto, SP, Brasil.Hemoglobin C (Hb C originated in the west of Africa and is detected by alkaline electrophoresis by slow migration in cellulose acetate. It consists of a mutation of the beta globin gene in codon 6 (GAG-AAG, resulting in a substitution of glutamic acid, the sixth amino acid of the beta string of the human hemoglobin, for lysine. High performance chromatography (HPLC separates the C and A2 fractions completely, allowing the characterization of the presence of interactions with thalassemia beta. This entity (Hb CC is considered benign in respect to sickle cell disease, as sickle cells are not part of its physiopathology. The rarity of the diagnosis of homozygous C and beta thalassemia in patients with hemoglobinopathies showed the necessity of studying clinical and hematologic aspects of the cases of this mutation in homozygosis carriers and the interaction with beta thalassemia in the anemias clinic of the Regional Blood

  14. Tyloses and phenolic deposits in xylem vessels impede water transport in low-lignin transgenic poplars: a study by cryo-fluorescence microscopy

    Science.gov (United States)

    Peter Kitin; Steven L. Voelker; Frederick C. Meinzer; Hans Beekman; Steven H. Strauss; Barbara. Lachenbruch

    2010-01-01

    Of 14 transgenic poplar genotypes (Populus tremula x Populus alba) with antisense 4-coumarate:coenzynle A ligase that were grown in the field for 2 years, five that had substantial lignin reductions also had greatly reduced xylem-specific conductivity compared with that of control trees and those transgenic events with small...

  15. Anaerobic biogranulation in a hybrid reactor treating phenolic waste

    International Nuclear Information System (INIS)

    Ramakrishnan, Anushyaa; Gupta, S.K.

    2006-01-01

    Granulation was examined in four similar anaerobic hybrid reactors 15.5 L volume (with an effective volume of 13.5 L) during the treatment of synthetic coal wastewater at the mesophilic temperature of 27 ± 5 deg. C. The hybrid reactors are a combination of UASB unit at the lower part and an anaerobic filter at the upper end. Synthetic wastewater with an average chemical oxygen demand (COD) of 2240 mg/L, phenolics concentration of 752 mg/L and a mixture of volatile fatty acids was fed to three hybrid reactors. The fourth reactor, control system, was fed with a wastewater containing sodium acetate and mineral nutrients. Coal waste water contained phenol (490 mg/L); m-, o-, p-cresols (123.0, 58.6, 42 mg/L); 2,4-, 2,5-, 3,4- and 3,5-dimethyl phenols (6.3, 6.3, 4.4 and 21.3 mg/L) as major phenolic compounds. A mixture of anaerobic digester sludge and partially granulated sludge (3:1) were used as seed materials for the start up of the reactors. Granules were observed after 45 days of operation of the systems. The granules ranged from 0.4 to 1.2 mm in diameter with good settling characteristics with an SVI of 12 mL/g SS. After granulation, the hybrid reactor performed steadily with phenolics and COD removal efficiencies of 93% and 88%, respectively at volumetric loading rate of 2.24 g COD/L d and hydraulic retention time of 24 h. The removal efficiencies for phenol and m/p-cresols reached 92% and 93% (corresponding to 450.8 and 153 mg/L), while o-cresol was degraded to 88% (corresponding to 51.04 mg/L). Dimethyl phenols could be removed completely at all the organic loadings and did not contribute much to the residual organics. Biodegradation of o-cresol was obtained in the hybrid-UASB reactors

  16. 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.

  17. Variability of Biological Degradation of Phenolic Hydrocarbons in an Aerobic Aquifer Determined by Laboratory Batch Experiments

    DEFF Research Database (Denmark)

    Nielsen, Per Henning; Christensen, Thomas Højlund

    1994-01-01

    The biological aerobic degradation of 7 phenolic hydrocarbons (phenol, o-cresol, o-nitrophenol, p-nitrophenol, 2,6-dichlorophenol, 2,4-dichlorophenol, 4,6-o-dichlorocresol) and 1 aromatic hydrocarbon (nitrobenzene) was studied for 149 days in replicate laboratory batch microcosms with sediment...... and groundwater from 8 localities representing a 15 m × 30 m section of an aerobic aquifer. Three patterns of variation were found: (1) phenol, o-cresol and in most cases p-nitrophenol showed very fast degradation with no or only short lag phases and with very little variation among localities; (2) 2...

  18. Phenol oxidation with hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Ramiez Cortina, R.C.; Hernadez Perez, I. [Univ. Autonoma Metropolitana - Azcapotzalco, Div. de CBI, Dept. de Energia, Azcapotzalco (Mexico); Ortiz Lozoya, C.E. [Univ. Autonoma Metropolitana - Azcapotzalco, Div. de CBI, Dept. de Energia, Azcapotzalco (Mexico)]|[Inst. Mexicano del Petroleo (Mexico); Alonso Gutierrez, M.S. [Inst. National Polytechnique, ENSCT, Lab. of Chimie Agro-Industrielle, Toulouse (France)

    2003-07-01

    In this work the process application of advanced oxidation is investigated with hydrogen peroxide, for the phenol destruction. The experiments were carried out in a glass reactor of 750 mL. Three phenol concentrations were studied (2000, 1000 and 500 ppm) being oxidized with H{sub 2}O{sub 2} (1, 2 and 3 M). The tests of oxidation had a reaction time of 48 h at ambient temperature and pressure. The phenol degradation was determined as COD at different reaction times and intermediate oxidation products were analyzed by chromatography. The results of this study show that it is possible to degrade phenol (1000 ppm) until 90% with H{sub 2}O{sub 2} 2M. Being achieved the best efficiency with a good molar relationship of H{sub 2}O{sub 2}/phenol. Intends a reaction outline in the degradation of the phenol. (orig.)

  19. Composition of phenols in the primary tar of bituminous brown coal of the Ukrainian S. S. R

    Energy Technology Data Exchange (ETDEWEB)

    Karavaev, N M; Fadeicheva, A G; Kuznetsov, V I

    1957-01-01

    The phenol content in the low-temperature carbonizatin tar of brown coal is higher than in high-temperature coking tar, and the tar obtained in the carbonization of briquets in the Pintsch ovens was investigated after its separation at the carbonization plant. The phenol-containing fraction was extracted with 13 percent NaOH. The phenols were fractionated into narrow fractions at 8- to 9-millimeter pressure, and the fractions were identified by their melting point, n, OH content, analysis, and the melting point of their arylglycolic acids. Lower phenols (44 percent) wre found in the crude-phenol fraction, including 6 percent of crystalline PhOH, melting point 34/sup 0/; o-C/sub 6/H/sub 4/(Me)OH, melting point 27/sup 0/; 9.25 percent m- and o-cresols, with 32 percent m-cresol in the mixture EtC/sub 6/H/sub 4/OH formed 4.5 percent of the crude phenols, and consisted of o-, m-, and p-ethylphenols, 1,4,2-, 1,3,4-, 1,3,5-, and 1,2,4-xylenols.

  20. Preparation of Silver Immobilised TiO2-Hectorite for Phenol Removal and Eschericia coli Desinfection

    Directory of Open Access Journals (Sweden)

    Is Fatimah

    2013-03-01

    Full Text Available Preparation of silver immobilized TiO2-Hectorite and its application in phenol photooxidation and Eschericia coli bacteria desinfection has been conducted. Material was obtained by two steps of synthesis: preparation of TiO2-Hectorite and silver immobilization into TiO2-Hectorite. Physico-chemical characterization to the prepared material compared to raw hectorite was conducted by X-ray Diffraction, gas sorption analyzer, scanning electron microscope and DRUV-Visible spectrophotometry and for photoactivity study, phenol photooxidation and Eschericia coli desinfection were investigated. The results indicated that the modification to hectorite material improve the physico-chemical character related to its role as photo-catalyst. Kinetic study of phenol photooxidation revealed the role of TiO2 pillarization and silver immobilization in enhancing rate of reaction as well as increased photoactivity of the materials in E. coli desinfection. © 2013 BCREC UNDIP. All rights reservedReceived: 28th September 2012; Revised: 7th December 2012; Accepted: 20th Decemberber 2012[How to Cite: I. Fatimah (2013. Preparation of Silver Immobilised TiO2-Hectorite for Phenol Removal and Eschericia coli Desinfection. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (3: 191-197. (doi:10.9767/bcrec.7.3.4047.191-197][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.7.3.4047.191-197 ] View in  |

  1. Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag{sup +}/TiO{sub 2}: Influence of electron donating and withdrawing substituents

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Jiadong [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Xie, Yongbing, E-mail: ybxie@ipe.ac.cn [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Han, Qingzhen [State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Cao, Hongbin [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Wang, Yujiao [Department of Chemical and Biomedical Engineering, University of Science and Technology Beijing (China); Nawaz, Faheem; Duan, Feng [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China)

    2016-03-05

    Highlights: • A weak EWG benefited photocatalytic oxidation of phenols the most. • Phenolic compounds were dominantly oxidized by ·O{sub 2}{sup −}, rather than ·OH, {sup 1}O{sub 2} or h{sup +}. • ·O{sub 2}{sup −} preferred to nucleophilically attack EDG substituted phenols. • ·O{sub 2}{sup −} more likely electrophilically attacked EWG substituted phenols. • ·O{sub 2}{sup −} simultaneously nucleophilically and electrophilically assaulted p-chlorophenol. - Abstract: A comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag{sup +}/TiO{sub 2} suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (·O{sub 2}{sup −}) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between ·O{sub 2}{sup −} and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of ·O{sub 2}{sup −} and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by ·O{sub 2}{sup −}, while ·O{sub 2}{sup −} preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by ·O{sub 2}{sup −} could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate

  2. 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

  3. Comparison of iodine-123 labelled 2{beta}-carbomethoxy-3{beta}-(4-iodophenyl)tropane and 2{beta}-carbomethoxy-3{beta}-(4-iodophenyl)-N-(3-fluoropropyl)nortropane for imaging of the dopamine transporter in the living human brain

    Energy Technology Data Exchange (ETDEWEB)

    Kuikka, J.T. [Dept. of Clinical Physiology, Kuopio Univ. Hospital (Finland); Bergstroem, K.A. [Dept. of Clinical Physiology, Kuopio Univ. Hospital (Finland); Ahonen, A. [Dept. of Clinical Chemistry, Oulu Univ. Central Hospital (Finland); Hiltunen, J. [MAP Medical Technologies Oy, Tikkakoski (Finland); Haukka, J. [MAP Medical Technologies Oy, Tikkakoski (Finland); Laensimies, E. [Dept. of Clinical Physiology, Kuopio Univ. Hospital (Finland); Wang Shaoyin [Research Biochemicals International (RBI), Natick, MA (United States); Neumeyer, J.L. [Research Biochemicals International (RBI), Natick, MA (United States)

    1995-04-01

    Several cocaine congeners are of potential for imaging the dopamine transporter (DAT). Previous studies have shown that iodine-123 labelled 2{beta}-carbomethoxy-3{beta}-(4-iodophenyl)tropane ([{sup 123}I]{beta}-CIT) is a promising radiotracer for imaging the serotonin (5-HT) and dopamine (DA) transporters in the living human brain with single-photon emission tomography (SPET). [{sup 123}I]{beta}-CIT was found to be not very practical for 1-day DAT imaging protocols since peak DAT uptake occurs later than 8 h. Here we report a pilot comparison of [{sup 123}I]{beta}-CIT and 2{beta}-carbomethoxy-3{beta}-(4-iodophenyl)-N-(3-fluoropropyl)nortropane ([{sup 123}I]{beta}-CIT-FP), using SPET imaging in four healthy male subjects. Peak uptake of [{sup 123}I]{beta}-CIT-FP into the basal ganglia occurred earlier (3-4 h after injection of tracer) than that of [{sup 123}I]{beta}-CIT (>8 h). However, the specific DAT binding of [{sup 123}I]{beta}-CIT-FP in the basal ganglia was somewhat less (0.813{+-}0.047) than that of [{sup 123}I]{beta}-CIT (0.922{+-}0.004). Imaging quality is excellent with both tracers and they are potentially of value for brain imaging in various neuropsychiatric disorders. (orig.)

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

    Science.gov (United States)

    Bahl, Kushal

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

  5. 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.

  6. Phenolic profile and antioxidant activity from non-toxic Mexican Jatropha curcas L. shell methanolic extracts.

    Science.gov (United States)

    Perea-Domínguez, Xiomara Patricia; Espinosa-Alonso, Laura Gabriela; Hosseinian, Farah; HadiNezhad, Mehri; Valdez-Morales, Maribel; Medina-Godoy, Sergio

    2017-03-01

    Jatropha curcas seed shells are the by-product obtained during oil extraction process. Recently, its chemical composition has gained attention since its potential applications. The aim of this study was to identify phenolic compounds profile from a non-toxic J. curcas shell from Mexico, besides, evaluate J. curcas shell methanolic extract (JcSME) antioxidant activity. Free, conjugate and bound phenolics were fractionated and quantified (606.7, 193.32 and 909.59 μg/g shell, respectively) and 13 individual phenolic compounds were detected by HPLC. The radical-scavenging activity of JcSME was similar to Trolox and ascorbic acid by DPPH assay while by ABTS assay it was similar to BHT. Effective antioxidant capacity by ORAC was found (426.44 ± 53.39 μmol Trolox equivalents/g shell). The Mexican non-toxic J. curcas shell is rich in phenolic compounds with high antioxidant activity; hence, it could be considerate as a good source of natural antioxidants.

  7. Thermodynamic Study of Adsorption of Phenol, 4-Chlorophenol, and 4-Nitrophenol on Activated Carbon Obtained from Eucalyptus Seed

    Directory of Open Access Journals (Sweden)

    Nelson Giovanny Rincón-Silva

    2015-01-01

    Full Text Available Activated carbons from shell eucalyptus (Eucalyptus globulus were prepared by chemical activation through impregnation with solutions of two activators: sulfuric acid and sodium hydroxide, the surface areas for activated carbons with base were 780 and 670 m2 g−1 and the solids activated with acid were 150 and 80 m2 g−1. These were applying in adsorption of priority pollutants: phenol, 4-nitrophenol, and 4-chlorophenol from aqueous solution. Activated carbon with the highest adsorption capacity has values of 2.12, 2.57, and 3.89 on phenol, 4-nitrophenol, and 4-chlorophenol, respectively, and was activated with base. In general, all carbons adsorption capacity was given in the following order: 4-chlorophenol > 4-nitrophenol > phenol. Adsorption isotherms of phenols on activated carbons were fitted to the Langmuir, Freundlich, and Dubinin-Radusckevisch-Kanager models, finding great association between them and experimental data. A thermodynamic study was performed, the exothermic nature and spontaneous nature of the adsorption process were confirmed, and the favorability of adsorption on activated carbons with NaOH was confirmed by energy relations and concluded that the adsorption process of phenolic compounds from the activated carbon obtained is physical. The pH of solutions and pH at point of zero charge of the solid play an important role in the adsorption process.

  8. Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water

    Energy Technology Data Exchange (ETDEWEB)

    Hao Xiaolong [Institute of Environmental Pollution Control Technologies, Xixi Campus, Zhejiang University, Hangzhou 310028, Zhejiang (China); Zhou Ming Hua [Institute of Environmental Pollution Control Technologies, Xixi Campus, Zhejiang University, Hangzhou 310028, Zhejiang (China); Lei Lecheng [Institute of Environmental Pollution Control Technologies, Xixi Campus, Zhejiang University, Hangzhou 310028, Zhejiang (China)]. E-mail: lclei@zju.edu.cn

    2007-03-22

    TiO{sub 2} photocatalyst (P-25) (50 mg L{sup -1}) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO{sub 2} were obviously increased. Pulsed high-voltage discharge process with TiO{sub 2} had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10 x 10{sup -6} to 1.50 x 10{sup -6} M s{sup -1}, the ozone formation rate from 1.99 x 10{sup -8} to 2.35 x 10{sup -8} M s{sup -1}, respectively. In addition, this process had no influence on the photocatalytic properties of TiO{sub 2}. The introduction of TiO{sub 2} photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants.

  9. Metalo-beta-lactamases Metallo-beta-lactamases

    Directory of Open Access Journals (Sweden)

    Rodrigo Elisandro Mendes

    2006-04-01

    Full Text Available Nos últimos anos tem sido observada maior incidência de bacilos Gram-negativos resistentes a cefalosporinas de espectro ampliado no ambiente hospitalar, ocasionando, assim, maior uso de betalactâmicos mais potentes, como os carbapenens. A utilização de carbapenens exerce maior pressão seletiva sobre a microbiota hospitalar, o que pode ocasionar aumento da resistência a esses agentes. Entre os mecanismos de resistência a carbapenens mais comumente identificados estão a produção de betalactamases, como, por exemplo, as pertencentes à classe D de Ambler e as que pertencem à classe B de Ambler, ou metalo-beta-lactamases (MbetaL. Essas últimas hidrolisam todos betalactâmicos comercialmente disponíveis, sendo a única exceção o monobactam aztreonam. Desde o início da década de 1990, novos genes que codificam MbetaLs têm sido descritos em microrganismos clinicamente importantes, como Pseudomonas spp., Acinetobacter spp. e membros da família Enterobacteriaceae. O encontro desses microrganismos não-sensíveis a carbapenens pode ser submetido a metodologias fenotípicas para detecção da produção de MbetaL com o intuito de auxiliar a Comissão de Controle de Infecção Hospitalar (CCIH e prevenir a disseminação desses determinantes de resistência, uma vez que genes que codificam MbetaLs estão contidos em estruturas genéticas que propiciam sua mobilidade de forma muito efetiva, sendo então facilmente disseminados.Increase isolation of Gram-negative bacilli resistant to broad-spectrum cephalosporin has been observed during the last few years, thus determining the use of more potent beta-lactams, such as carbapenems. The use of these antimicrobial agents may lead to the emergence of carbapenem resistant Gram-negative bacilli in the nosocomial environment. Carbapenem resistance may be due to the production of Ambler class D beta-lactamase or Ambler class B beta-lactamase, also called metallo-beta-lactamase (MbetaL. Apart from

  10. [Production, absorption and excretion of phenols in intestinal obstruction].

    Science.gov (United States)

    Kawamoto, M

    1986-11-01

    In intestinal obstruction, phenols were produced in the distended loop proximal to obstruction by enteric bacteria. Clinically, in 17 cases of non-strangulated intestinal obstruction, phenols were detected in 15 cases and mean concentration of phenols was 4.2 +/- 9.7 micro g/ml(mean +/- 1 SD). In the fraction of phenols, p-cresol was detected in 15 cases and mean concentration was 3.8 +/- 7.7 and phenol was detected in 4 cases and mean concentration was 0.5 +/- 2.6. Phenols were decreased as clinical improvement of intestinal obstruction. Enteric bacteria in enteric juice ranged from 10(4) to 10(10)/ml and its change paralleled to phenols concentration. Mean urinary concentration of phenols in intestinal obstruction was increased to 297 +/- 415 mg/day compared to control (less than 50 mg/day). Its change also paralleled to phenols concentration in enteric juice. Closed ileal loop was made in dogs and phenols were infused in the loop. Phenols were increased in the portal vein 5 min after the infusion and in the femoral vein 60 min after the infusion. Phenols, which was thought to be toxic to the host, were proved to be produced in the distended intestine and excreted from the kidney.

  11. Estudo da produção de beta-galactosidase por fermentação de soro de queijo com Kluyveromyces marxianus Synthesis of beta-galactosidase by fermentation of cheese whey by Kluyveromyces marxianus

    Directory of Open Access Journals (Sweden)

    Patrícia A. Santiago

    2004-12-01

    Full Text Available A hidrólise enzimática da lactose por beta-galactosidase desempenha importante papel no processamento de produtos lácteos, como na obtenção de leite com baixo teor de lactose para consumo por indivíduos intolerantes à mesma e na prevenção da cristalização em produtos de laticínio. Neste trabalho, a enzima beta-galactosidase foi produzida pelo cultivo do microrganismo Kluyveromyces marxianus, em meio de cultura à base de soro de queijo em diferentes concentrações iniciais de lactose e extrato de levedura, de acordo com um planejamento fatorial. As fermentações foram conduzidas em incubador rotativo a 150rpm, a 30°C e pH inicial 5,5. A concentração celular inicial foi de 10(7 células/mL. Para a extração da enzima beta-galactosidase, foi realizada autólise das células utilizando como solvente o clorofórmio em tampão fosfato. No meio de cultura enriquecido com (NH42SO4, KH2PO4 e MgSO4, nas concentrações iniciais de lactose e de extrato de levedura iguais a 50g/L e 12g/L, respectivamente, obteve-se uma atividade de 28,0UGl/mL e uma concentração celular máxima de 5,3g/L.The enzymatic hydrolysis of lactose by beta-galactosidase plays an important role in the processing of milky products such as the production of lactose-hydrolyzed milk for consumption by intolerant person to lactose and the prevention of the crystallization in dairy products. In this work, the influences of nutrient concentrations in the culture medium based on cheese whey were studied with the objective of producing beta-galactosidase from Kluyveromyces marxianus. The fermentations were carried out in a shaker at 30°C and initial pH 5.5 under agitation, starting with an initial cellular concentration of 10(7 cells/mL, varying the initial concentrations of lactose and yeast extract. For extraction of the enzyme of the cells it was used autolysis with chloroform in potassium phosphate buffer. In the medium with a initial lactose concentration of 50g

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

    Science.gov (United States)

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

    2015-08-01

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

  13. The Conjugates of Phenolic Acids in Lichens of the Order Lecanorales

    Directory of Open Access Journals (Sweden)

    T. N. NIKOLAEVA

    2014-06-01

    Full Text Available Lichens are symbiotic associations of a fungus (usually an ascomycete and a photobiont, which may be an alga and/or a cyanobacterium. Lichens dominate on about 6–8% of land surface, mainly in the habitats with severe climatic conditions. Lichenized fungi are among the pioneer vegetation on bare rock or soil. Mat-forming species contribute substantially to the soil cover in tundras and high mountain elevations. Lichens are rich in water-soluble compounds which can be leached-out the lichen thalli with atmospheric depositions. We have recently described the occurrence of water-soluble phenolics in lichens (Zagoskina et al 2013. These compounds can play important role in the ecosystem functioning and primary soil formation (weathering, humification. The aim of this work was to study qualitative composition of water-soluble phenolics in the lichen species widespread in the soil cover of tundra zone. The air-dried thalli of Alectoria ochroleuca, Cetraria islandica, C.nigricans, C.nivalis, Cladonia arbuscula and C.stellaris were homogenized to powder and used for the study. Lichens were collected in Khibiny mountains, Kola Peninsula in August 2013. Phenolic compounds were extracted by distilled water (1h, 30C and analyzed by TLC before and after the acid hydrolysis. It was found that all the lichens under the study contained the conjugates of phenol carboxylic acids. We have identified that non-phenolic part in some of these conjugates was represented by sugars and amino acids. The TLC of the hydrolizates of water extracts revealed occurrence of p-oxybenzoic acid in all of the species studied. The lichens Cetraria islandica, С.nigricans and Cladonia stellaris contained also vanillic acid. These phenolic acids are widespread in plant kingdom and are known as products of lignin decomposition in higher plants. The physiological role of water-soluble phenolics in lichens as well as their environmental role are need to be understood in future studies.

  14. The anisotropic Kerr nonlinear refractive index of the beta-barium borate (β-BaB2O4) nonlinear crystal

    DEFF Research Database (Denmark)

    Bache, Morten; Guo, Hairun; Zhou, Binbin

    2013-01-01

    We study the anisotropic nature of the Kerr nonlinear response in a beta-barium borate (β-BaB2O4, BBO) nonlinear crystal. The focus is on determining the relevant χ(3) cubic tensor components that affect interaction of type I cascaded second-harmonic generation. Various experiments in the literat...... a complete list that we propose as reference of the four major cubic tensor components in BBO. We finally discuss the impact of using the cubic anisotropic response in ultrafast cascading experiments in BBO.......We study the anisotropic nature of the Kerr nonlinear response in a beta-barium borate (β-BaB2O4, BBO) nonlinear crystal. The focus is on determining the relevant χ(3) cubic tensor components that affect interaction of type I cascaded second-harmonic generation. Various experiments...... in the literature are analyzed and we correct the data from some of the experiments for contributions from cascading as well as for updated material parameters. We also perform an additional experimental measurement of the Kerr nonlinear tensor component responsible for self-phase modulation in cascading, and we...

  15. Lignases and aldo-keto reductases for conversion of lignin-containing materials to fermentable products

    Science.gov (United States)

    Scharf, Michael; Sethi, Amit

    2016-09-13

    Termites have specialized digestive systems that overcome the lignin barrier in wood to release fermentable simple sugars. Using the termite Reticulitermes flavipes and its gut symbionts, high-throughput titanium pyrosequencing and proteomics approaches experimentally compared the effects of lignin-containing diets on host-symbiont digestome composition. Proteomic investigations and functional digestive studies with recombinant lignocellulases conducted in parallel provided strong evidence of congruence at the transcription and translational levels and provide enzymatic strategies for overcoming recalcitrant lignin barriers in biofuel feedstocks. Briefly described, therefore, the disclosure provides a system for generating a fermentable product from a lignified plant material, the system comprising a cooperating series of at least two catalytically active polypeptides, where said catalytically active polypeptides are selected from the group consisting of: cellulase Cell-1, .beta.-glu cellulase, an aldo-keto-reductase, a catalase, a laccase, and an endo-xylanase.

  16. Expressão de galectina-3 e beta-catenina em lesões pré-malignas e carcinomatosas de língua de camundongos Galectin-3 and beta-catenin expression in premalignant and carcinomatous lesions in tongue of mice

    Directory of Open Access Journals (Sweden)

    Juliana Moreira de Almeida Sant'ana

    2011-02-01

    Full Text Available INTRODUÇÃO: A galectina-3 (GAL3 apresenta importantes papéis na biologia tumoral e recentemente foi mostrada a sua participação na via de sinalização Wnt, translocando a beta-catenina para o núcleo. Expressão alterada de GAL3 e beta-catenina tem sido descrita em cânceres, mas não há estudos avaliando a expressão de ambas em displasias e carcinomas desenvolvidos em modelos de carcinogênese de língua. OBJETIVOS: Estudar a expressão de GAL3 e beta-catenina em lesões displásicas e carcinomas induzidos experimentalmente em língua de camundongos. MATERIAL E MÉTODOS: Vinte camundongos C57BL/6 machos foram desafiados com 4NQO na água de beber por 16 semanas e sacrificados na semana 16 e 32. Após o sacrifício, as línguas foram removidas, processadas, coradas por hematoxilina e eosina (HE para detecção de displasias e carcinomas. Ensaio imuno-histoquímico foi realizado para determinar o índice de positividade para GAL3 e beta-catenina nessas lesões, bem como uma correlação entre elas em carcinomas. RESULTADOS: O número de camundongos afetados por carcinoma aumentou entre as semanas 16 e 32 (22,2% vs. 88,9% e o de displasia diminuiu (66,7% vs. 11,1%. Um aumento de células positivas para beta-catenina não membranosa e GAL3 citoplasmática foi observado nas displasias e nos carcinomas, mas essa diferença não foi estatisticamente significativa. No entanto, um aumento estatisticamente significativo de GAL3 nuclear foi observado na evolução de displasia para carcinoma (p = 0,04. Nenhuma correlação foi encontrada entre beta-catenina e GAL3. CONCLUSÃO: Tanto nas displasias quanto nos carcinomas a via de sinalização Wnt está ativa, e o aumento de GAL3 nuclear nos carcinomas sugere um papel na transformação maligna do epitélio lingual.INTRODUCTION: Galectin-3 plays pivotal role in tumor biology and its participation in Wnt signaling pathway translocating beta-catenin into the nucleus has been recently demonstrated

  17. 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.

  18. In vitro pharmacological characterization of (+/-)-4-[2-(1-methyl-2-pyrrolidinyl)ethyl]thio]phenol hydrochloride (SIB-1553A), a nicotinic acetylcholine receptor ligand.

    Science.gov (United States)

    Rao, Tadimeti S; Adams, Pamala B; Correa, Lucia D; Santori, Emily M; Sacaan, Aida I; Reid, Richard T; Suto, Carla M; Vernier, Jean Michel

    2003-08-15

    SIB-1553A ((+/-)-4-[2-(1-methyl-2-pyrrolidinyl)ethyl]thio]phenol HCl) is a neuronal nicotinic acetylcholine receptor (nAChR) ligand which displaced the binding of [3H]nicotine (NIC) to the rat brain nAChRs with an IC(50) value of 110 nM with no appreciable affinity to the alpha7 nAhRs. SIB-1553A showed modest affinity for histaminergic (H3) and serotonergic (5-HT1 and 5-HT2) receptors, and sigma binding sites. In calcium flux assays, SIB-1553A (0.1-5 microM), in contrast to nicotine, showed a greater selectivity for beta4-subunit containing recombinant hnAChRs (alpha2beta4, alpha3beta4 and alpha4beta4) vs. beta2-subunit containing nAChRs (alpha4beta2 and alpha3beta2) both in terms of efficacy and potency. While NIC (10-30 microM) and epibatidine (0.01-0.1 microM) fully activated human muscle-type AChRs expressed by RD cell line, SIB-1553A was virtually ineffective for up to >100 microM and elicited less than 10% of the response due to suberyldicholine. SIB-1553A (< or =30 microM) evoked [3H]DA release from striatum, olfactory tubercles and prefrontal cortex (PFC), and [3H]NE release from hippocampus and PFC, and this evoked release was sensitive to mecamylamine (MEC). SIB-1553A-evoked neurotransmitter release exhibited region- and transmitter-specific antagonism by dehydro-beta-erythroidine (DHbetaE). SIB-1553A was less efficacious than NIC at evoking [3H]NE from the rat hippocampus and antagonized NIC response upon co-application implying partial agonist properties. SIB-1553A did not evoke basal [3H]ACh release from the rat striatum or hippocampus, but attenuated NMDA-evoked [3H]ACh release from the rat striatum. SIB-1553A did not inhibit rat brain cholinesterase for up to 1 mM. Multiple receptor affinities and release of several neurotransmitters may underlie the cognitive-enhancing effects of SIB-1553A documented in rodent and primate models.

  19. HPLC-DAD-ESI/MS(n) analysis of phenolic compounds for quality control of Grindelia robusta Nutt. and bioactivities.

    Science.gov (United States)

    Ferreres, Federico; Grosso, Clara; Gil-Izquierdo, Angel; Valentão, Patrícia; Azevedo, Carolina; Andrade, Paula B

    2014-06-01

    The phenolic composition of herbal tea (HT) and hydromethanolic extract (HME) obtained from Grindelia robusta Nutt. was studied by HPLC-DAD-ESI/MS(n). Thirty six flavonoids and hydroxycinnamic acids were detected, from which thirty are described for the first time in this species. Quantification by HPLC-DAD showed that diosmetin-7-O-glucuronide-3'-O-pentoside+apigenin-7-O-glucuronide-4'-O-pentoside, apigenin-7-O-glucuronide+diosmetin-7-O-glucuronide and 3,5-dicaffeoylquinic acid+3,4-dicaffeoylquinic acid were the major compounds. Since the health-promoting effects of natural phenolic compounds against brain disorders is of increasing interest, HT and HME were also tested against oxygen and nitrogen reactive species and against enzymes related with Alzheimer's disease and depression. Extracts displayed strong in vitro scavenging activity and monoamine oxidase-A (MAO-A) inhibitory activity. The anti-MAO-A capacity was observed at non-toxic concentrations for SH-SY5Y human neuroblastoma cell line, reinforcing the benefits of G. robusta HT. However, no protection against hydrogen peroxide treatment was observed. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    NARCIS (Netherlands)

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

    2004-01-01

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

  1. Non-selective beta-blockers decrease thrombotic events in patients with heart failure

    NARCIS (Netherlands)

    De Peuter, Olav R.; Souverein, Patrick C.; Klungel, Olaf H.; Lip, Gregory Y.; Buller, Harry R.; De Boer, Anthonius; Kamphuisen, Pieter W.

    2010-01-01

    Background: Beta-blockers are often prescribed to patients with heart failure (HF) without distinctions between types of beta-blockers. The 2002 COMET study showed superiority of carvedilol (a non-selective beta-blocker) over metoprolol (selective beta-blocker) on mortality and cardiovascular events

  2. Degradation of 4-Chloro phenol by gamma radiation of 137Cs and X-rays

    International Nuclear Information System (INIS)

    Gonzalez J, J. C.; Jimenez B, J.; Cejudo A, J.

    2010-01-01

    This paper presents results of radiolytic degradation of 4-chloro phenol in the presence of TiO 2 , Al 2 O 3 and SiO 2 , using different radiation sources than 60 Co, which is so common in this type of experiment. The radiation sources used were X-rays with energy of 100 keV and radiation from 137 Cs (662 keV). After irradiation with a dose of 50 c Gy X-ray and TiO 2 obtained a degradation of about 5%, no degradation was obtained with 137 Cs source and other oxides. This may be due to the fact that X-rays have a linear energy transfer greater value, and in the case of TiO 2 present a crystalline structure, whereas the other two oxides are amorphous. Both characteristics result in better formation of a reactive species that allows the degradation of the compound. (Author)

  3. Comparative analyses of two thermophilic enzymes exhibiting both beta-1,4 mannosidic and beta-1,4 glucosidic cleavage activities from Caldanaerobius polysaccharolyticus.

    Science.gov (United States)

    Han, Yejun; Dodd, Dylan; Hespen, Charles W; Ohene-Adjei, Samuel; Schroeder, Charles M; Mackie, Roderick I; Cann, Isaac K O

    2010-08-01

    The hydrolysis of polysaccharides containing mannan requires endo-1,4-beta-mannanase and 1,4-beta-mannosidase activities. In the current report, the biochemical properties of two endo-beta-1,4-mannanases (Man5A and Man5B) from Caldanaerobius polysaccharolyticus were studied. Man5A is composed of an N-terminal signal peptide (SP), a catalytic domain, two carbohydrate-binding modules (CBMs), and three surface layer homology (SLH) repeats, whereas Man5B lacks the SP, CBMs, and SLH repeats. To gain insights into how the two glycoside hydrolase family 5 (GH5) enzymes may aid the bacterium in energy acquisition and also the potential application of the two enzymes in the biofuel industry, two derivatives of Man5A (Man5A-TM1 [TM1 stands for truncational mutant 1], which lacks the SP and SLH repeats, and Man5A-TM2, which lacks the SP, CBMs, and SLH repeats) and the wild-type Man5B were biochemically analyzed. The Man5A derivatives displayed endo-1,4-beta-mannanase and endo-1,4-beta-glucanase activities and hydrolyzed oligosaccharides with a degree of polymerization (DP) of 4 or higher. Man5B exhibited endo-1,4-beta-mannanase activity and little endo-1,4-beta-glucanase activity; however, this enzyme also exhibited 1,4-beta-mannosidase and cellodextrinase activities. Man5A-TM1, compared to either Man5A-TM2 or Man5B, had higher catalytic activity with soluble and insoluble polysaccharides, indicating that the CBMs enhance catalysis of Man5A. Furthermore, Man5A-TM1 acted synergistically with Man5B in the hydrolysis of beta-mannan and carboxymethyl cellulose. The versatility of the two enzymes, therefore, makes them a resource for depolymerization of mannan-containing polysaccharides in the biofuel industry. Furthermore, on the basis of the biochemical and genomic data, a molecular mechanism for utilization of mannan-containing nutrients by C. polysaccharolyticus is proposed.

  4. The Paleozoic Origin of Enzymatic Lignin Decomposition Reconstructed from 31 Fungal Genomes

    Science.gov (United States)

    Dimitrios Floudas; Manfred Binder; Robert Riely; Kerrie Barry; Robert A. Blanchette; Bernard Henrissat; Angel T. Martínez; Robert Otillar; Joseph W. Spatafora; Jagjit S. Yadav; Andrea Aerts; Isabelle Benoit; Alex Boyd; Alexis Carlson; Alex Copeland; Pedro M. Coutinho; Ronald P. deVries; Patricia Ferreira; Keisha Findley; Brian Foster; Jill Gaskell; Dylan Glotzer; Pawe³ Górecki; Joseph Heitman; Cedar Hesse; Chiaki Hori; Kiyohiko Igarashi; Joel A. Jurgens; Nathan Kallen; Phil Kersten; Annegret Kohler; Ursula Kües; T. K. ArunKumar; Alan Kuo; Kurt LaButti; Luis F. Larrondo; Erika Lindquist; Albee Ling; Vincent Lombard; Susan Lucas; Taina Lundell; Rachael Martin; David J. McLaughlin; Ingo Morgenstern; Emanuelle Morin; Claude Murat; Laszlo G. Nagy; Matt Nolan; Robin A. Ohm; Aleksandrina Patyshakuliyeva; Antonis Rokas; Francisco J. Ruiz-Dueñas; Grzegorz Sabat; Asaf Salamov; Masahiro Samejima; Jeremy Schmutz; Jason C. Slot; Franz St. John; Jan Stenlid; Hui Sun; Sheng Sun; Khajamohiddin Syed; Adrian Tsang; Ad Wiebenga; Darcy Young; Antonio Pisabarro; Daniel C. Eastwood; Francis Martin; Dan Cullen; Igor V. Grigoriev; David S. Hibbett

    2012-01-01

    Wood is a major pool of organic carbon that is highly resistant to decay, owing largely to the presence of lignin. The only organisms capable of substantial lignin decay are white rot fungi in the Agaricomycetes, which also contains non–lignin-degrading brown rot and ectomycorrhizal species. Comparative analyses of 31 fungal genomes (12 generated for this study)...

  5. The formation mechanism of a textured ceramic of thermoelectric [Ca2CoO3](0.62)[CoO2] on beta-Co(OH)2 templates through in situ topotactic conversion.

    Science.gov (United States)

    Itahara, Hiroshi; Seo, Won-Seon; Lee, Sujeong; Nozaki, Hiroshi; Tani, Toshihiko; Koumoto, Kunihito

    2005-05-04

    We investigated the formation mechanism of thermoelectric [Ca(2)CoO(3)](0.62)[CoO(2)] (CCO) on beta-Co(OH)(2) templates with maintained orientations by identifying the intermediate phases and specifying the relationship between their crystallographic orientations. We mixed beta-Co(OH)(2) templates with the complementary reactant CaCO(3) and prepared a compact by tape casting, with the developed (001) plane of the templates aligned along the casting plane. High-temperature XRD of the compact revealed that beta-Co(OH)(2) decomposed into Co(3)O(4) by 873 K, and Co(3)O(4) reacted with CaO to form CCO by 1193 K via the formation of the newly detected intermediate phase beta-Na(x)()CoO(2)-type Ca(x)()CoO(2) at 913-973 K. Pole figure measurements and SEM and TEM observations revealed that the relationship between the crystallographic planes was (001) beta-Co(OH)(2)//{111} Co(3)O(4)//(001) Ca(x)()CoO(2)//(001) CCO. The crystal structures of the four materials possess the common CoO(2) layer (or similar), which is composed of edge-sharing CoO(6) octahedra, parallel to the planes. The cross-sectional HRTEM analysis of an incompletely reacted specimen showed transient lattice images from Ca(x)()CoO(2) into CCO, in which every other CoO(2) layer of Ca(x)()CoO(2) was preserved. Thus, it was demonstrated that a textured CCO ceramic is produced through a series of in situ topotactic conversion reactions with a preserved CoO(2) layer of its template.

  6. Comparação entre dois métodos analíticos para determinação da lignina de algumas gramíneas forrageiras Comparison between two analytical methods for determining lignin concentration of some grass forages

    Directory of Open Access Journals (Sweden)

    Romualdo Shigueo Fukushima

    1999-06-01

    Full Text Available Foram comparados dois métodos analíticos para a determinação da lignina (lignina em detergente ácido - LDA e lignina permanganato de potássio - LPer bem como para averiguar a possível relação dos teores desse componente com a digestibilidade da fibra dos seguintes fenos: andropogon (Andropogon gayanus; aveia (Avena sativa; e dois tipos de coast-cross (Cynodon dactylon, um bem fenado e outro de baixa qualidade. Os valores de LDA e LPer foram diferentes (p This work was carried out aiming to compare lignin concentration of some grass forages through two analytical methods (acid detergent lignin - ADL and permanganate lignin - PerL as well to verify a possible relationship of lignin concentration with fiber digestion of the following grass hays: andropogon (Andropogon gayanus; oats (Avena sativa; a good quality and another of poor quality coast-cross (Cynodon dactylon. Acid detergent and permanganate lignin values were different (p <= 0.05 among the hays, however PerL concentrations were consistently lower than ADL values. There were differences (p <= 0.05 among the digestibility of neutral and acid detergent fiber fractions, however a clear relationship between these values with lignin concentration could not be assessed. The data suggested that lignin concentration, taken individually, is not the only factor to explain a given value of digestibility.

  7. 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

  8. Immobilized TiO2 for Phenol Degradation in a Pilot-Scale Photocatalytic Reactor

    Directory of Open Access Journals (Sweden)

    Sylwia Mozia

    2012-01-01

    Full Text Available Phenol degradation was carried out in a photocatalytic pilot plant reactor equipped with a UV/vis mercury lamp. The total volume of treated water was equal to 1.35 m3. TiO2 P25 was used as a photocatalyst and it was immobilized on two different supports: (i a steel mesh and (ii a fiberglass cloth. Moreover, the performance of commercially available Photospheres-40 was examined. In addition, an experiment in the absence of a photocatalyst was conducted. The commercially available Photospheres-40 were found to be inadequate for the presented application due to their fragility, which in connection with vigorous mixing and pumping led to their mechanical destruction and loss of floating abilities. The highest effectiveness of phenol decomposition and mineralization was observed in the presence of TiO2 supported on the fiberglass cloth. After 15 h of the process, phenol and total organic carbon concentrations decreased by ca. 80% and 50%, respectively.

  9. Lignin biosynthesis in wheat (Triticum aestivum L.): its response to waterlogging and association with hormonal levels.

    Science.gov (United States)

    Nguyen, Tran-Nguyen; Son, SeungHyun; Jordan, Mark C; Levin, David B; Ayele, Belay T

    2016-01-25

    Lignin is an important structural component of plant cell wall that confers mechanical strength and tolerance against biotic and abiotic stressors; however it affects the use of biomass such as wheat straw for some industrial applications such as biofuel production. Genetic alteration of lignin quantity and quality has been considered as a viable option to overcome this problem. However, the molecular mechanisms underlying lignin formation in wheat biomass has not been studied. Combining molecular and biochemical approaches, the present study investigated the transcriptional regulation of lignin biosynthesis in two wheat cultivars with varying lodging characteristics and also in response to waterlogging. It also examined the association of lignin level in tissues with that of plant hormones implicated in the control of lignin biosynthesis. Analysis of lignin biosynthesis in the two wheat cultivars revealed a close association of lodging resistance with internode lignin content and expression of 4-coumarate:CoA ligase1 (4CL1), p-coumarate 3-hydroxylase1 (C3H1), cinnamoyl-CoA reductase2 (CCR2), ferulate 5-hydroxylase2 (F5H2) and caffeic acid O-methyltransferase2 (COMT2), which are among the genes highly expressed in wheat tissues, implying the importance of these genes in mediating lignin deposition in wheat stem. Waterlogging of wheat plants reduced internode lignin content, and this effect is accompanied by transcriptional repression of three of the genes characterized as highly expressed in wheat internode including phenylalanine ammonia-lyase6 (PAL6), CCR2 and F5H2, and decreased activity of PAL. Expression of the other genes was, however, induced by waterlogging, suggesting their role in the synthesis of other phenylpropanoid-derived molecules with roles in stress responses. Moreover, difference in internode lignin content between cultivars or change in its level due to waterlogging is associated with the level of cytokinin. Lodging resistance, tolerance against

  10. Improvement of macrophage dysfunction by administration of anti-transforming growth factor-beta antibody in EL4-bearing hosts.

    Science.gov (United States)

    Maeda, H; Tsuru, S; Shiraishi, A

    1994-11-01

    An experimental therapy for improvement of macrophage dysfunction caused by transforming growth factor-beta (TGF-beta) was tried in EL4 tumor-bearing mice. TGF-beta was detected in cell-free ascitic fluid from EL4-bearers, but not in that from normal mice, by western blot analysis. The ascites also showed growth-suppressive activity against Mv1Lu cells, and the suppressive activity was potentiated by transient acidification. To investigate whether the functions of peritoneal macrophages were suppressed in EL4-bearers, the abilities to produce nitric oxide and tumor necrosis factor-alpha (TNF-alpha) upon lipopolysaccharide (LPS) stimulation were measured. Both abilities of macrophages in EL4-bearing mice were suppressed remarkably on day 9, and decreased further by day 14, compared with non-tumor-bearing controls. TGF-beta activity was abrogated by administration of anti-TGF-beta antibody to EL4-bearing mice. While a large amount of TGF-beta was detected in ascitic fluid from control EL4-bearers, little TGF-beta was detectable in ascites from EL4-bearers given anti-TGF-beta antibody. Furthermore, while control macrophages exhibited little or no production of nitric oxide and TNF-alpha on LPS stimulation in vitro, macrophages from EL4-bearers administered with anti-TGF-beta antibody showed the same ability as normal macrophages. These results clearly indicate that TGF-beta contributes to macrophage dysfunction and that the administration of specific antibody for TGF-beta reverses macrophage dysfunction in EL4-bearing hosts.

  11. Assessment of the oestrogenic activity of the contraceptive progestin levonorgestrel and its non-phenolic metabolites.

    Science.gov (United States)

    Santillán, R; Pérez-Palacios, G; Reyes, M; Damián-Matsumura, P; García, G A; Grillasca, I; Lemus, A E

    2001-09-14

    Levonorgestrel (13beta-ethyl-17alpha-ethynyl-17beta-hydroxy-4-gonen-3-one), a potent contraceptive progestin stimulates growth and proliferation of cultured breast cancer cells through a receptor-mediated mechanism, even though levonorgestrel does not bind to the oestrogen receptor (ER). To assess whether the oestrogen-like effects induced by this synthetic progestin are exerted via its metabolic conversion products, we studied the binding affinity of three A-ring levonorgestrel derivatives to the ER and their capability to transactivate an oestrogen-dependent yeast system co-transfected with the human ER gene and oestrogen responsive elements fused to a beta-galactosidase reporter vector. The results demonstrated that the 3beta,5alpha reduced levonorgestrel derivative and to a lesser extent its 3alpha isomer interact with the oestrogen receptor, with a significantly lower relative binding affinity (2.4% and 0.4%, respectively) than that of oestradiol (100%), while levonorgestrel does not. Both levonorgestrel metabolites were able to activate, in a dose-dependent manner, the beta-galactosidase reporter gene in the yeast expression system, an effect that was precluded by a steroidal antioestrogen. The oestrogenic potency of levonorgestrel metabolites was significantly lower (750-fold) than that of oestradiol. Furthermore, high doses of 3beta,5alpha levonorgestrel (2.5 mg/day/6 days) induced an increase of oestrogen-dependent progestin receptor in the anterior pituitary of castrated rats. The overall data offer a plausible explanation for the weak oestrogenic effects induced by high, non-pharmacological doses of levonorgestrel.

  12. Effects of chemical form of sodium on the product characteristics of alkali lignin pyrolysis.

    Science.gov (United States)

    Guo, Da-liang; Yuan, Hong-you; Yin, Xiu-li; Wu, Chuang-zhi; Wu, Shu-bin; Zhou, Zhao-qiu

    2014-01-01

    The effects of Na as organic bound form or as inorganic salts form on the pyrolysis products characteristics of alkali lignin were investigated by using thermogravimetric analyzer coupled with Fourier transform infrared spectrometry (TG-FTIR), tube furnace and thermo-gravimetric analyzer (TGA). Results of TG-FTIR and tube furnace indicated that the two chemical forms Na reduced the releasing peak temperature of CO and phenols leading to the peak temperature of the maximum mass loss rate shifted to low temperature zone. Furthermore, organic bound Na obviously improved the elimination of alkyl substituent leading to the yields of phenol and guaiacol increased, while inorganic Na increased the elimination of phenolic hydroxyl groups promoting the formation of ethers. It was also found the two chemical forms Na had different effects on the gasification reactivity of chars. For inorganic Na, the char conversion decreased with increasing the char forming temperature, while organic bound Na was opposite. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

  13. Synthesis of 4-aryl-3,4-dihydrocoumarin derivatives catalyzed by NbCl{sub 5}; Sintese de derivados 4-aril-3,4-di-hidrocuraminicos catalisada por NbCl{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Willian Henrique dos; Siqueira, Mayara de Souza; Silva-Filho, Luiz Carlos da, E-mail: lcsilva@fc.unesp.br [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Bauru, SP (Brazil). Faculdade de Ciencias

    2013-11-01

    Multicomponent reactions between phenols, {beta}-diesters and benzaldehydes for the synthesis of 4-aryl-3,4-dihydrocoumarin derivatives were carried out under mild conditions (room temperature) and presented moderate yields (38-88%) and reasonable reaction times (2-4 days), using niobium pentachloride as a catalyst. (author)

  14. Plant phenolics and absorption features in vegetation reflectance spectra near 1.66 μm

    Science.gov (United States)

    Kokaly, Raymond F.; Skidmore, Andrew K

    2015-01-01

    Past laboratory and field studies have quantified phenolic substances in vegetative matter from reflectance measurements for understanding plant response to herbivores and insect predation. Past remote sensing studies on phenolics have evaluated crop quality and vegetation patterns caused by bedrock geology and associated variations in soil geochemistry. We examined spectra of pure phenolic compounds, common plant biochemical constituents, dry leaves, fresh leaves, and plant canopies for direct evidence of absorption features attributable to plant phenolics. Using spectral feature analysis with continuum removal, we observed that a narrow feature at 1.66 μm is persistent in spectra of manzanita, sumac, red maple, sugar maple, tea, and other species. This feature was consistent with absorption caused by aromatic C-H bonds in the chemical structure of phenolic compounds and non-hydroxylated aromatics. Because of overlapping absorption by water, the feature was weaker in fresh leaf and canopy spectra compared to dry leaf measurements. Simple linear regressions of feature depth and feature area with polyphenol concentration in tea resulted in high correlations and low errors (% phenol by dry weight) at the dry leaf (r2 = 0.95, RMSE = 1.0%, n = 56), fresh leaf (r2 = 0.79, RMSE = 2.1%, n = 56), and canopy (r2 = 0.78, RMSE = 1.0%, n = 13) levels of measurement. Spectra of leaves, needles, and canopies of big sagebrush and evergreens exhibited a weak absorption feature centered near 1.63 μm, short ward of the phenolic compounds, possibly consistent with terpenes. This study demonstrates that subtle variation in vegetation spectra in the shortwave infrared can directly indicate biochemical constituents and be used to quantify them. Phenolics are of lesser abundance compared to the major plant constituents but, nonetheless, have important plant functions and ecological significance. Additional research is needed to advance our understanding of the

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

    Directory of Open Access Journals (Sweden)

    José I. Santos

    2015-01-01

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

  16. Evaluation of Reaction Parameters of the Phenol Steam Reforming over Ni/Co on ZrO2 Using the Full Factorial Experimental Design

    Directory of Open Access Journals (Sweden)

    Walid Nabgan

    2016-08-01

    Full Text Available Full factorial experimental design with 32 runs was used to investigate the significant and interaction variable of the reaction parameters on phenol steam reforming toward hydrogen production. Effects of selected factors on the phenol conversion (Y1 and hydrogen yield (Y2 were evaluated. These factors were as follows: (A temperature (500 and 800 °C; (B feed flow rate (0.16–0.46 mL/min; (C catalyst weight (0.1–0.3 g; (D Ni-Co ratio (0–1; and (E phenol concentration in the feed (2–10 wt %. Ni and Co over ZrO2 support for catalytic performance of phenol steam reforming (SRP was prepared by the impregnation method. The result indicated that all the main independent variables had significant influence on the dependent variable of Y1 and Y2 with a range of 2.7%–96.8% and 21.4%–72.4%, respectively. Additionally, some interaction variables like AE, BE, CE, and DE have also influenced the Y1 and Y2 responses. This design showed that the best initial conditions that produced maximum Y1 and Y2 responses were at 800 °C, 0.16 mL/min feed flow rate, 0.3 g of catalyst, 0 ratio of Ni-Co (Co/ZrO2, and 10 wt % of phenol in the feed, where the phenol conversion was predicted to be 94.98% and the hydrogen yield was predicted to be 67.4%. Within the limits the variables were examined, a regression model which well-fitted the experimental data was proposed. The regression model were reduced to simplify and to get the significant regression coefficient with p-value less than 0.05.

  17. 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.

  18. $\\beta$-asymmetry measurements in nuclear $\\beta$-decay as a probe for non-standard model physics

    CERN Multimedia

    Roccia, S

    2002-01-01

    We propose to perform a series of measurements of the $\\beta$-asymmetry parameter in the decay of selected nuclei, in order to investigate the presence of possible time reversal invariant tensor contributions to the weak interaction. The measurements have the potential to improve by a factor of about four on the present limits for such non-standard model contributions in nuclear $\\beta$-decay.

  19. PIROLISIS LIGNIN DARI LIMBAH INDUSTRI KELAPA SAWIT UNTUK PENGEMBANGAN SURFAKTAN DALAM PROSES ENHANCE OIL RECOVERY (EOR (Pyrolysis of Lignin From Waste of Palm Oil Industries for The Development of Surfactants for Enhance Oil Recovery (EOR

    Directory of Open Access Journals (Sweden)

    Suryo Purwono

    2001-12-01

    Full Text Available ABSTRAK Pirolisis dari lignin yang berasal dari limbah industri kelapa sawit dapat menghasilkan alkohol dan derivatif lainnyd yang dapat digunakan sehagai surfaktan. Prosedur penelitian proses pirolisis ini odalah sebagai berikut: I serabut atau tandan sisa pengolahon kelapa sawit yang sudah dikeringkan dimasukkan kedalam reaktor dengan berat tertentu dan dipanaskan sampai suhu yang diinginkan, 2 produk pirolisis yang keluar dari reoktor kemudian didinginkan sampoi mencapai suhu kamor, 3 hasil cair ditampung didalam gelas ukur dan hasil gasnya ditampung di suatu botol tertentu. Suhu paling baik yang dicapai adalah 4A0 "C untuk lignin yong berasal dari serabut dan 350'C untuk lignin yang berasal dari tandan kelapa sawit. Surfaktan yang dihasilkan sekitar j4 sampai 38% dari produk pirolisis. Pada penelitian ini kecepatan reaksi dianggap order satu. Hasil penelitian menunjukkan bahwa surfakton yang dihasilkan dapat membentuk emulsi dengan minyak menta.h. Hal ini menunjukkon bahwa surfaktan yang dihasilkan dapat digunakan sebagai bahan untuk proses EOR.   ABSTRACT Pyrolysis of lignin from waste of palm oil industries produces alcohol and its derivatives which can be sulfonated to become surfactant. The experimental procedures for the pyrolysis process were as follows: 1 dried palm oil husks at a certain weight were put into the pyrolysis reactor and heated up to a certain temperafure; 2 the product leaving the reactor was cooled down to room temperature; and 3 the liquid product was collected in a flask while the gas product was put into a big bottle. The best temperature obtained for producing liquid product was 400 oC for lignin from palm oil fruit fibers and 350 oC for lignin from palm oil fruit stems. The surfactant developed was in the range between 34 and 38% from the pyrolysis product. In this experiment, the reaction rate was assumed to be in first order. The result showed that the surfactant obtained from the experiment could form emulsion

  20. 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.

  1. Determinação da concentração de beta-glucano em cogumelo Agaricus blazei Murill por método enzimático Determination of beta-glucan concentration in Agaricus blazei Murill mushroom by enzymatic method

    Directory of Open Access Journals (Sweden)

    Yong K. Park

    2003-12-01

    Full Text Available Cogumelos comestíveis contêm importantes propriedades funcionais. Em particular, beta-glucanos, homo- e hetero-glucanos com ligações glicosídicas beta(1->3, beta(1->4 e beta(1->6, supostamente responsáveis por algumas propriedades benéficas à saúde humana, como atividade imunomodulatória, antioxidante, antiinflamatória e anticancerígena. Neste trabalho, a quantidade de beta-glucano presente em cogumelo Agaricus blazei Murill, coletados de três diferentes locais, foi analisada utilizando-se método enzimático. As amostras (em base seca foram tratadas com alfa-amilase, protease bacteriana e com glicoamilase fúngica. beta-glucano foi quantificado após hidrólise ácida e determinação da glicose liberada. Foi verificado que amostras de A. blazei Murill cultivadas em estufas apresentaram menor concentração de b-glucano (8,4±0,9 e 7,6±2,8g/100g quando comparado com amostras cultivadas em campo aberto (10,1±2,1g/100g. Observou-se ainda que, mesmo sendo cultivado em condições semelhantes, porém em locais diferentes, as amostras apresentaram diferenças significativas (7,6±2,8 e 8,4±0,9g/100g.Edible mushrooms contains a very interesting functional properties. Among them, the beta-glucans, polysaccharides with beta-1,3; b-1,4 and beta-1,6glucosidic linkages, they are responsible to a series of properties to human health, such as immunomodulatory, antioxidant, antiinflammatory and, antitumoral activities. In the present work, the Agaricus blazei Murill beta-glucan concentrations from three locations, were determined through the enzymatic method. Samples were treated with alpha-amylase, bacterial protease and fungal glucoamylase. beta-glucans were quantified after acid hydrolysis and, the glucose determined for spectrophotometric method. It was verified that samples cultivated inside stoves presented smaller beta-glucan concentration (8.4±0.9 and 7.6±2.8g/100g, when compared with samples cultivated in open field (10.1±2.1g/100

  2. Overexpression of artificially fused bifunctional enzyme 4CL1?CCR: a method for production of secreted 4-hydroxycinnamaldehydes in Escherichia coli

    OpenAIRE

    Liu, Shuxin; Qi, Qi; Chao, Nan; Hou, Jiayin; Rao, Guodong; Xie, Jin; Lu, Hai; Jiang, Xiangning; Gai, Ying

    2015-01-01

    Background 4-Hydroxycinnamaldehydes are important intermediates in several secondary metabolism pathways, including those involved in the biosynthesis of phenolic acids, flavonoids, terpenoids and monolignols. They are also involved in the biosynthesis and degradation of lignins, which are important limiting factors during the processes of papermaking and biofuel production. Access to these aromatic polymers is necessary to explore the secondary biometabolic pathways they are involved in. Con...

  3. VUV/UV light inducing accelerated phenol degradation with a low electric input.

    Science.gov (United States)

    Li, Mengkai; Wen, Dong; Qiang, Zhimin; Kiwi, John

    2017-01-23

    This study presents the first evidence for the accelerated degradation of phenol by Fenton's reagent in a mini-fluidic VUV/UV photoreaction system (MVPS). A low-pressure mercury lamp used in the MVPS led to a complete degradation of phenol within 4-6 min. The HO˙ and HO 2 ˙ originating from both Fenton's reagent and VUV photolysis of water were identified with suitable radical scavengers. The effects of initial concentrations of phenol, H 2 O 2 and Fe 3+ as well as solution pH on phenol degradation kinetics were examined. Increasing the initial phenol concentration slowed down the phenol degradation, whereas increasing the initial H 2 O 2 or Fe 3+ concentration accelerated the phenol degradation. The optimal solution pH was 3.7. At both 254 and 185 nm, increasing phenol concentration enhanced its absorption for the incident photons. The reaction mechanism for the degradation of phenol was suggested consistent with the results obtained. This study indicates that the VUV/UV photo-Fenton process has potential applications in the treatment of industrial wastewater containing phenol and related aromatic pollutants.

  4. Immobilized acclimated biomass-powdered activated carbon for the bioregeneration of granular activated carbon loaded with phenol and o-cresol.

    Science.gov (United States)

    Toh, Run-Hong; Lim, Poh-Eng; Seng, Chye-Eng; Adnan, Rohana

    2013-09-01

    The objectives of the study are to use immobilized acclimated biomass and immobilized biomass-powdered activated carbon (PAC) as a novel approach in the bioregeneration of granular activated carbon (GAC) loaded with phenol and o-cresol, respectively, and to compare the efficiency and rate of the bioregeneration of the phenolic compound-loaded GAC using immobilized and suspended biomasses under varying GAC dosages. Bioregeneration of GAC loaded with phenol and o-cresol, respectively, was conducted in batch system using the sequential adsorption and biodegradation approach. The results showed that the bioregeneration efficiency of GAC loaded with phenol or o-cresol was basically the same irrespective of whether the immobilized or suspended biomass was used. Nonetheless, the duration for bioregeneration was longer under immobilized biomass. The beneficial effect of immobilized PAC-biomass for bioregeneration is the enhancement of the removal rate of the phenolic compounds via adsorption and the shortening of the bioregeneration duration. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. 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...

  6. 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

  7. Plant hormone interaction and phenolic metabolism in the regulation of russet spotting in iceberg lettuce.

    Science.gov (United States)

    Ke, D; Saltveit, M E

    1988-12-01

    Russet spotting (RS) is a physiological disorder induced in iceberg lettuce (Lactuca sativa L.) by exposure to parts per million levels of ethylene at 5 +/- 2 degrees C. Ethylene induced phenylalanine ammonia-lyase and ionically bound peroxidase activities that correlated with development of RS symptoms. The ethylene-treated tissue had significantly higher lignin content than air control tissue with lignification localized in walls of RS-affected cells. Ethylene also caused the accumulation of the flavonoids (+)catechin and (-)epicatechin and the chlorogenic acid derivatives 3-caffeoyl-quinic acid, 3,5-dicaffeoylquinic acid, and 4,5-dicaffeoylquinic acid. These soluble phenolic compounds were readily oxidized to brown substances by polyphenol oxidase isolated from RS tissue. Ethylene substantially increased ionically bound indole-3-acetic acid (IAA) oxidase activity, while IAA application greatly reduced ethylene-induced phenylalanine ammonia-lyase, peroxidase, and IAA oxidase activities, soluble phenolic content, and RS development.

  8. 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.

  9. Influence of foliar nutrients on phenol levels in leaves of Eugenia uniflora

    Directory of Open Access Journals (Sweden)

    Rosa M. Santos

    2011-08-01

    Full Text Available Eugenia uniflora L., Myrtaceae, leaves contain high amounts of phenolic compounds which are responsible for several pharmacological activities. In order to evaluate the phenolics seasonal variation leaves were analysed on a monthly basis during the period of two years for the contents of hydrolysable tannins, total phenols, flavonoids, and nutrients (N, P, K, S, Ca, Mg, Mn, Zn, Cu, and Fe. Results were correlated with climate conditions (rainfall, humidity, and mean temperature by Principal Component and ClusterAnalysis which allowed four groups to be distinguished with respect to the age of the leaves and the content of some metals. Young leaves were characterised by high levels of Zn and nitrogen whereas old leaves contained high levels of Fe and calcium, and both groups had moderate amounts of phenolics. Adult leaves were divided in two groups and results revealed that while one group had the highest levels of all phenols and lowest amounts of Mn and Cu, the other showed opposite quantities. The Canonical Correlation Analysis confirmed a highly significant negative correlation between phenol contents and Mn and Cu. These facts suggested that flavonoids and tannins production depends of the amounts of foliar nutrients, Cu and Mn in particular, which are cofactors of enzymes involved in phenol degradation and lignin biosynthesis. This knowledge can improve this specie cultivation in order to enhance the phenolic compounds concentration.

  10. Production of renewable phenolic resins by thermochemical conversion of biomass: A review

    Energy Technology Data Exchange (ETDEWEB)

    Effendi, A.; Gerhauser, H.; Bridgwater, A.V. [Bio-Energy Research Group, Aston University, Birmingham B4 7ET (United Kingdom)

    2008-10-15

    This review covers the production and utilisation of liquids from the thermal processing of biomass and related materials to substitute for synthetic phenol and formaldehyde in phenol formaldehyde resins. These resins are primarily employed in the manufacture of wood panels such as plywood, MDF, particle-board and OSB. The most important thermal conversion methods for this purpose are fast pyrolysis and vacuum pyrolysis, pressure liquefaction and phenolysis. Many feedstocks have been tested for their suitability as sources of phenolics including hard and softwoods, bark and residual lignins. Resins have been prepared utilising either the whole liquid product, or a phenolics enriched fraction obtained after fractional condensation or further processing, such as solvent extraction. None of the phenolics production and fractionation techniques covered in this review are believed to allow substitution of 100% of the phenol content of the resin without impacting its effectiveness compared to commercial formulations based on petroleum derived phenol. This survey shows that considerable progress has been made towards reaching the goal of a price competitive renewable resin, but that further research is required to meet the twin challenges of low renewable resin cost and satisfactory quality requirements. Particular areas of concern are wood panel press times, variability of renewable resin properties, odour, lack of reactive sites compared to phenol and potential for increased emissions of volatile organic compounds. (author)

  11. Wine phenolics.

    Science.gov (United States)

    Waterhouse, Andrew L

    2002-05-01

    Wine contains many phenolic substances, most of which originate in the grape berry. The phenolics have a number of important functions in wine, affecting the tastes of bitterness and astringency, especially in red wine. Second, the color of red wine is caused by phenolics. Third, the phenolics are the key wine preservative and the basis of long aging. Lastly, since phenolics oxidize readily, they are the component that suffers owing to oxidation and the substance that turns brown in wine (and other foods) when exposed to air. Wine phenolics include the non-flavonoids: hydroxycinnamates, hydroxybenzoates and the stilbenes; plus the flavonoids: flavan-3-ols, the flavonols, and the anthocyanins. While polymeric condensed tannins and pigmented tannins constitute the majority of wine phenolics, their large size precludes absorption and thus they are not likely to have many health effects (except, perhaps, in the gut). The total amount of phenols found in a glass of red wine is on the order of 200 mg versus about 40 mg in a glass of white wine.

  12. Labelling of. beta. -endorphin (. beta. -END) and. beta. -lipotropin (. beta. -LPH) by /sup 125/I

    Energy Technology Data Exchange (ETDEWEB)

    Deby-Dupont, G.; Joris, J.; Franchimont, P. (Universite de Liege (Belgique)); Reuter, A.M.; Vrindts-Gevaert, Y. (Institut des Radioelements, Fleurus (Belgique))

    1983-01-01

    5 ..mu..g of human ..beta..-endorphin were labelled with 2 mCi /sup 125/I by the chloramine T technique. After two gel filtrations on Sephadex G-15 and on Sephadex G-50 in phosphate buffer with EDTA, Trasylol and mercapto-ethanol, a pure tracer was obtained with a specific activity about 150 ..mu..Ci/..mu..g.Kept at + 4/sup 0/C, the tracer remained utilizable for 30 days without loss of immunoreactivity. The labelling with lactoperoxydase and the use of another gel filtration method (filtration on Aca 202) gave a /sup 125/I ..beta..-END tracer with the same immunoreactivity. The binding of this tracer to the antibody of an anti-..beta..-END antiserum diluted at 1/8000 was 32% with a non specific binding of 2%. 5 ..mu..g of human ..beta..-lipotropin were labelled with 0.5 mCi /sup 125/I by the lactoperoxydase method. After two gel filtrations on Sephadex G-25 and on Sephadex G-75 in phosphate buffer with EDTA, Trasylol and mercapto-ethanol, a pure tracer with a specific activity of 140 ..mu..Ci/..mu..g was obtained. It remained utilizable for 30 days when kept at + 4/sup 0/C. Gel filtration on Aca 202 did not give good purification, while gel filtration on Aca 54 was good but slower than on Sephadex G-75. The binding to antibody in absence of unlabelled ..beta..-LPH was 32% for an anti-..beta..-LPH antiserum diluted at 1/4000. The non specific binding was 2.5%.

  13. Silicon Promotes Exodermal Casparian Band Formation in Si-Accumulating and Si-Excluding Species by Forming Phenol Complexes.

    Directory of Open Access Journals (Sweden)

    Alexander T Fleck

    Full Text Available We studied the effect of Silicon (Si on Casparian band (CB development, chemical composition of the exodermal CB and Si deposition across the root in the Si accumulators rice and maize and the Si non-accumulator onion. Plants were cultivated in nutrient solution with and without Si supply. The CB development was determined in stained root cross-sections. The outer part of the roots containing the exodermis was isolated after enzymatic treatment. The exodermal suberin was transesterified with MeOH/BF3 and the chemical composition was measured using gas chromatography-mass spectroscopy (GC-MS and flame ionization detector (GC-FID. Laser ablation-inductively coupled plasma-mass spectroscopy (LA-ICP-MS was used to determine the Si deposition across root cross sections. Si promoted CB formation in the roots of Si-accumulator and Si non-accumulator species. The exodermal suberin was decreased in rice and maize due to decreased amounts of aromatic suberin fractions. Si did not affect the concentration of lignin and lignin-like polymers in the outer part of rice, maize and onion roots. The highest Si depositions were found in the tissues containing CB. These data along with literature were used to suggest a mechanism how Si promotes the CB development by forming complexes with phenols.

  14. The influence of TiO2 and aeration on the kinetics of electrochemical oxidation of phenol in packed bed reactor

    International Nuclear Information System (INIS)

    Wang Lizhang; Zhao Yuemin; Fu Jianfeng

    2008-01-01

    The electrochemical oxidation of phenolic wastewater in a lab-scale reactor, packed into granular activated carbon (GAC) with Ti/SnO 2 anodes and stainless steel cathodes, was interpreted in this study. GAC saturated rapidly if it was only used as sorbent, but application of suitable electric energy for the system simultaneously could recover the adsorption ability of GAC and maintain the continuous running effectively. The titanium dioxide (TiO 2 ) as catalyst and airflow were also applied to the electrochemical reactor to examine the enhancement for phenol oxidation process. Results revealed that the electrochemical degradation of phenol could be reasonably described by first-order kinetics. In addition, it was illustrated that acid region, increased voltage, more dosage of TiO 2 and higher aeration intensity were all beneficial parameters for phenol oxidation rates. By inspecting the relationship between the rate constants (k) and influencing factors, respectively, an overall kinetic model for phenol oxidation was proposed. The kinetics obtained from the experiments under corresponding electrochemical conditions could provide an accurate estimation of phenol concentration effluent and better design of the packed bed reactor

  15. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    International Nuclear Information System (INIS)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

    2017-01-01

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

  16. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-11-14

    Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

  17. Chemical modification of straw by alkaline treatment. [Trolmen process

    Energy Technology Data Exchange (ETDEWEB)

    1977-01-01

    In straw from 9 Swedish cereal cultivars of barley, oats, wheat, and rye, low molecular weight carbohydrates constituted only 0.3-1.4% of the straw with sucrose, glucose, fructose, and the sugar alcohols arabinitol and mannitol as main constituents. Hemicellulose (18-24%), cellulose (27-37%) and Klason-lignin (19-24%) were the main constituents. The ash (3-12%) and silica (0.5-3%) values showed rather high variations. After the Trolmen process, a wet closed NaOH treatment method, there was a slight enrichment of carbohydrates and ash and a decrease of Klason-lignin in the treated straw. About 1% of phenolic acids, mainly alpha ..beta.. -dihydro-p-coumatic, trans-p-coumaric, alpha ..beta.. -dihydroferulic and trans-ferulic acids, were quantified in the black liquid from the Trolmen process. These acids were probably ester-linked to the hemicellulose in the native straw and released during alkali treatment.HOAc, probably from Ac groups in xylan, and some of the silica were also released during the process. Although the amount of dissolved lignin was small, linkages between lignin and hemicellulosic polymers, perhaps also to cellulose, may be broken during the treatment. Linkages of these types may block the carbohydrates from enzymic action and reduce the digestibility. The higher digestibility of alkali-treated straw is probably due both to breaking of such linkages and to swelling of the polysaccharides rather than removal of any large amounts of undigestible components as lignin and silica.

  18. Structural insights into the {beta}-xylosidase from Trichoderma reesei

    Energy Technology Data Exchange (ETDEWEB)

    Rojas, Adriana L.; Fischer, Hannes; Polikarpov, Igor [Sao Paulo Univ. (USP), Sao Carlos, SP (Brazil). Inst. de Fisica; Eneiskaya, Elena V.; Kulminskaya, Anna A.; Shabalin, Konstantin A.; Neustroev, Kirill N.; Golubev, Alexander M. [Petersburg Nuclear Physics Inst., Moskow (Russian Federation); Craievich, Aldo Felix [Sao Paulo Univ. (USP), SP (Brazil). Inst. de Fisica

    2005-07-01

    Xylan is a major structural polysaccharide in plant cells, and is the second most abundant polysaccharide in nature, accounting for approximately one-third of all renewable organic carbon on earth. Xylan together with cellulose (1,4-{beta}-glucan) and lignin (a complex polyphenolic compound) make up the major polymeric constituents of plant cell walls, recently, there was a significant industrial interest in Xylan and its hydrolytic enzymatic complex, as a supplement in animal feed, for the manufacture of bread, food and drinks, textiles, bleaching of cellulose pulp, ethanol and xylitol production. (author)

  19. Substituent Effects on the Hydrogen Bonding Between Phenolate and HF, H2O and NH3

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    B3LYP/6-31+g(d) calculations were performed on the hydrogen bonded complexes between substituted phenolates and HF, H2O as well as NH3. It was found that some properties of the non-covalent complexes, including the interaction energies, donor-acceptor (host-guest) distances, bond lengths, and vibration frequencies, could show well-defined substituent effects. Thus, from the substituent studies we can not only understand the mechanism of a particular non-covalent interaction better, but also easily predict the interaction energies and structures of a particular non-covalent complex, which might otherwise be very hard or resource-consuming to be known. This means that substituent effect is indeed a useful tool to be used in supramolecular chemistry and therefore, many valuable studies remain to be carried out.

  20. Fungicidal values of bio-oils and their lignin-rich fractions obtained from wood/bark fast pyrolysis.

    Science.gov (United States)

    Mohan, Dinesh; Shi, Jenny; Nicholas, Darrel D; Pittman, Charles U; Steele, Philip H; Cooper, Jerome E

    2008-03-01

    Pine wood, pine bark, oak wood and oak bark were pyrolyzed in an auger reactor. A total of 16 bio-oils or pyrolytic oils were generated at different temperatures and residence times. Two additional pine bio-oils were produced at the National Renewable Energy Laboratory in a fluidized-bed reactor at different temperatures. All these bio-oils were fractionated to obtain lignin-rich fractions which consist mainly of phenols and neutrals. The pyrolytic lignin-rich fractions were obtained by liquid-liquid extraction. Whole bio-oils and their lignin-rich fractions were studied as potential environmentally benign wood preservatives to replace metal-based CCA and copper systems that have raised environmental concerns. Each bio-oil and several lignin-rich fractions were tested for antifungal properties. Soil block tests were conducted using one brown-rot fungus (Gloeophyllum trabeum) and one white-rot fungus (Trametes versicolor). The lignin-rich fractions showed greater fungal inhibition than whole bio-oils for a impregnation solution 10% concentration level. Water repellence tests were also performed to study wood wafer swelling behavior before and after bio-oil and lignin-rich fraction treatments. In this case, bio-oil fractions did not exhibit higher water repellency than whole bio-oils. Comparison of raw bio-oils in soil block tests, with unleached wafers, at 10% and 25% bio-oil impregnation solution concentration levels showed excellent wood preservation properties at the 25% level. The good performance of raw bio-oils at higher loading levels suggests that fractionation to generate lignin-rich fractions is unnecessary. At this more effective 25% loading level in general, the raw bio-oils performed similarly. Prevention of leaching is critically important for both raw bio-oils and their fractions to provide decay resistance. Initial tests of a polymerization chemical to prevent leaching showed some success.