Raman imaging to investigate ultrastructure and composition of plant cell walls: distribution of lignin and cellulose in black spruce wood (Picea mariana).

PubMed

Agarwal, Umesh P

2006-10-01

A detailed understanding of the structural organization of the cell wall of vascular plants is important from both the perspectives of plant biology and chemistry and of commercial utilization. A state-of-the-art 633-nm laser-based confocal Raman microscope was used to determine the distribution of cell wall components in the cross section of black spruce wood in situ. Chemical information from morphologically distinct cell wall regions was obtained and Raman images of lignin and cellulose spatial distribution were generated. While cell corner (CC) lignin concentration was the highest on average, lignin concentration in compound middle lamella (CmL) was not significantly different from that in secondary wall (S2 and S2-S3). Images generated using the 1,650 cm(-1) band showed that coniferaldehyde and coniferyl alcohol distribution followed that of lignin and no particular cell wall layer/region was therefore enriched in the ethylenic residue. In contrast, cellulose distribution showed the opposite pattern-low concentration in CC and CmL and high in S2 regions. Nevertheless, cellulose concentration varied significantly in some areas, and concentrations of both lignin and cellulose were high in other areas. Though intensity maps of lignin and cellulose distributions are currently interpreted solely in terms of concentration differences, the effect of orientation needs to be carefully considered to reveal the organization of the wood cell wall.

Enzymatic synthesis of lignin-siloxane hybrid functional polymers.

PubMed

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

2012-02-01

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

Base-Catalyzed Depolymerization of Solid Lignin-Rich Streams Enables Microbial Conversion

DOE PAGES

Rodriguez, Alberto; Salvachúa, Davinia; Katahira, Rui; ...

2017-08-01

Lignin valorization offers significant potential to enhance the economic viability of lignocellulosic biorefineries. However, because of its heterogeneous and recalcitrant nature, conversion of lignin to value-added coproducts remains a considerable technical challenge. Here, we employ base-catalyzed depolymerization (BCD) using a process-relevant solid lignin stream produced via deacetylation, mechanical refining, and enzymatic hydrolysis to enable biological lignin conversion. BCD was conducted with the solid lignin substrate over a range of temperatures at two NaOH concentrations, and the results demonstrate that the lignin can be partially extracted and saponified at temperatures as low as 60 degrees C. At 120 °C and 2%more » NaOH, the high extent of lignin solubility was accompanied by a considerable decrease in the lignin average molecular weight and the release of lignin-derived monomers including hydroxycinnamic acids. BCD liquors were tested for microbial growth using seven aromatic-catabolizing bacteria and two yeasts. Three organisms (Pseudomonas putida KT2440, Rhodotorula mucilaginosa, and Corynebacterium glutamicum) tolerate high BCD liquor concentrations (up to 90% v/v) and rapidly consume the main lignin-derived monomers, resulting in lignin conversion of up to 15%. Furthermore, as a proof of concept, muconic acid production from a representative lignin BCD liquor was demonstrated with an engineered P. putida KT2440 strain. Our results highlight the potential for a mild lignin depolymerization process to enhance the microbial conversion of solid lignin-rich biorefinery streams.« less

Base-Catalyzed Depolymerization of Solid Lignin-Rich Streams Enables Microbial Conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez, Alberto; Salvachúa, Davinia; Katahira, Rui

Lignin valorization offers significant potential to enhance the economic viability of lignocellulosic biorefineries. However, because of its heterogeneous and recalcitrant nature, conversion of lignin to value-added coproducts remains a considerable technical challenge. Here, we employ base-catalyzed depolymerization (BCD) using a process-relevant solid lignin stream produced via deacetylation, mechanical refining, and enzymatic hydrolysis to enable biological lignin conversion. BCD was conducted with the solid lignin substrate over a range of temperatures at two NaOH concentrations, and the results demonstrate that the lignin can be partially extracted and saponified at temperatures as low as 60 degrees C. At 120 °C and 2%more » NaOH, the high extent of lignin solubility was accompanied by a considerable decrease in the lignin average molecular weight and the release of lignin-derived monomers including hydroxycinnamic acids. BCD liquors were tested for microbial growth using seven aromatic-catabolizing bacteria and two yeasts. Three organisms (Pseudomonas putida KT2440, Rhodotorula mucilaginosa, and Corynebacterium glutamicum) tolerate high BCD liquor concentrations (up to 90% v/v) and rapidly consume the main lignin-derived monomers, resulting in lignin conversion of up to 15%. Furthermore, as a proof of concept, muconic acid production from a representative lignin BCD liquor was demonstrated with an engineered P. putida KT2440 strain. Our results highlight the potential for a mild lignin depolymerization process to enhance the microbial conversion of solid lignin-rich biorefinery streams.« less

Host lignin composition affects haustorium induction in the parasitic plants Phtheirospermum japonicum and Striga hermonthica.

PubMed

Cui, Songkui; Wada, Syogo; Tobimatsu, Yuki; Takeda, Yuri; Saucet, Simon B; Takano, Toshiyuki; Umezawa, Toshiaki; Shirasu, Ken; Yoshida, Satoko

2018-04-01

Parasitic plants in the family Orobanchaceae are destructive weeds of agriculture worldwide. The haustorium, an essential parasitic organ used by these plants to penetrate host tissues, is induced by host-derived phenolic compounds called haustorium-inducing factors (HIFs). The origin of HIFs remains unknown, although the structures of lignin monomers resemble that of HIFs. Lignin is a natural phenylpropanoid polymer, commonly found in secondary cell walls of vascular plants. We therefore investigated the possibility that HIFs are derived from host lignin. Various lignin-related phenolics, quinones and lignin polymers, together with nonhost and host plants that have different lignin compositions, were tested for their haustorium-inducing activity in two Orobanchaceae species, a facultative parasite, Phtheirospermum japonicum, and an obligate parasite, Striga hermonthica. Lignin-related compounds induced haustoria in P. japonicum and S. hermonthica with different specificities. High concentrations of lignin polymers induced haustorium formation. Treatment with laccase, a lignin degradation enzyme, promoted haustorium formation at low concentrations. The distinct lignin compositions of the host and nonhost plants affected haustorium induction, correlating with the response of the different parasitic plants to specific types of lignin-related compounds. Our study provides valuable insights into the important roles of lignin biosynthesis and degradation in the production of HIFs. © 2018 The Authors. New Phytologist © 2018 New Phytologist Trust.

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

PubMed

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.

UV-Vis as quantification tool for solubilized lignin following a single-shot steam process.

PubMed

Lee, Roland A; Bédard, Charles; Berberi, Véronique; Beauchet, Romain; Lavoie, Jean-Michel

2013-09-01

In this short communication, UV/Vis was used as an analytical tool for the quantification of lignin concentrations in aqueous mediums. A significant correlation was determined between absorbance and concentration of lignin in solution. For this study, lignin was produced from different types of biomasses (willow, aspen, softwood, canary grass and hemp) using steam processes. Quantification was performed at 212, 225, 237, 270, 280 and 287 nm. UV-Vis quantification of lignin was found suitable for different types of biomass making this a timesaving analytical system that could lead to uses as Process Analytical Tool (PAT) in biorefineries utilizing steam processes or comparable approaches. Copyright © 2013 Elsevier Ltd. All rights reserved.

Lignin geochemistry of sediments from the Narragansett Bay Estuary

NASA Astrophysics Data System (ADS)

Requejo, A. G.; Brown, John S.; Boehm, Paul D.

1986-12-01

Cupric oxide oxidation has been employed to characterize the lignin geochemistry of Narragansett Bay sediments. Lignin concentrations throughout the estuary are low when expressed on a carbon-normalized basis, but can be characterized as enriched when expressed on a mass-normalized basis. This implies substantial dilution of the sedimentary lignin by inputs of lignin-poor carbon. Lignin concentrations do not correlate with the 13C isotopic composition of the sedimentary organic matter. These results are consistent with a sediment lignin component consisting of varying amounts of vascular plant debris and lignin-depleted organic matter, the latter originating from both marine (planktonic) and terrestrial (uncharacterized) sources. Compositional plots of lignin-derived phenols show that sediments in the upper estuary are influenced to a greater extent by gymnosperm lignin sources than those in the mid-and lower estuary. Given the extent to which the upper estuary is affected by pollution sources, inputs from anthropogenic discharges are the most likely cause of these compositional differences. However, an evaluation of processed paper products as an "anthropogenic" lignin source indicates that the lignin content of these materials is insufficient to account for the levels found in the sediments. Subsurface lignin compositions at an upper estuary site reveal that lignin originating from the inferred anthropogenic sources disappears at a depth shallower than that which would be expected based on the distribution of other trace organic pollutants (hydrocarbons and several synthetic organic compounds). We speculate that differences in either the depositional history or the degree of preservation of these two compound classes are responsible for the observed trends.

Interference of condensed tannin in lignin analyses of dry bean and forage crops.

PubMed

Marles, M A Susan; Coulman, Bruce E; Bett, Kirstin E

2008-11-12

Legumes with high concentrations of condensed tannin (pinto bean [Phaseolus vulgaris L.], sainfoin [Onobrychis viciifolia Scop.], and big trefoil [Lotus uliginosus Hoff.]), were compared to a selection of forages, with low or zero condensed tannin (smooth bromegrass [ Bromus inermis Leyss], Lotus japonicus [Regel] K. Larsen, and alfalfa [Medicago sativa L.]), using four methods to estimate fiber or lignin. Protocols were validated by using semipurified condensed tannin polymers in adulteration assays that tested low-lignin tissue with polyphenolic-enriched samples. The effect on lignin assay methods by condensed tannin concentration was interpreted using a multivariate analysis. There was an overestimation of fiber or lignin in the presence of condensed tannin in the acid detergent fiber (ADF) and Klason lignin (KL) assays compared to that in the thioglycolic acid (TGA) and acid detergent lignin (ADL) methods. Sulfite reagents (present in TGA lignin method) or sequential acidic digests at high temperatures (ADF followed by ADL) were required to eliminate condensed tannin. The ADF (alone) and KL protocols are not recommended to screen nonwoody plants, such as forages, where condensed tannin has accumulated in the tissue.

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

PubMed

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.

Improved lignin polyurethane properties with Lewis acid treatment.

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

Torrefied biomass-polypropylene composites

USDA-ARS?s Scientific Manuscript database

Torrefied almond shells and wood chips were incorporated into polypropylene as fillers to produce torrefied biomass-polymer composites. Response surface methodology was used to examine the effects of filler concentration, filler size, and lignin factor (relative lignin to cellulose concentration) on...

Aliphatic and aromatic plant biopolymer dynamics in soil particles isolated from sequential density fractionation

NASA Astrophysics Data System (ADS)

Caldwell, B.; Filley, T.; Sollins, P.; Lajtha, K.; Swanston, C.; Kleber, M.; Kramer, M.

2007-12-01

A recent multi-layer-based soil organic matter-mineral interaction mechanistic model to describe the nature of soil organic matter-mineral surface mechanism for soil organic matter stabilization predicts that proteinaceous and aliphatic materials establish the core of strong binding-interactions upon which other organic matter is layered. A key methodology providing data underpinning this hypothesis is sequential density fractionation where soil is partitioned into particles of increasing density with the assumption that a partial control on organic matter distribution through density series is the thickness of its layering. Four soils of varying mineralogy and texture were investigated for their biopolymer, isotopic, and mineralogical properties. Light fractions (<1.8 g/cm3), although dominanted by organic detritus, did not always contain the highest concentration of lignin and substituted fatty acids from cutin and suberin while heavier fractions, 1.8-2.6 g/cm3, exhibited a progressive decrease in concentration in plant derived biopolymers with density. Extractable lignin phenols exhibited a progressive oxidation state with density. The concentration of biopolymers roughly mirrored the C:N ratio of soil particles which dropped consistently with increasing particle density. Although, in all soils, both lignin phenols and SFA concentration generally decreased with increasing density the ratio SFA/lignin varied with density and depending upon the soil. All soils, except the oxisol, exhibited an increase in SFA with respect to lignin suggesting a selective stabilization of those material with respect to lignin. In the oxisol, which showed little variation in its hematite dominated mineralogy across density, SFA/lignin remained constant, potentially indicating a greater capacity to stabilize lignin in that system. Interestingly, the lignin oxidation state increased with density in the oxisol. Given the variation in soil character, the consistency in these trends it suggests a general phenomenon of progressive decay in plant derived material with thinness of mineral coating but an overall relative increase in aliphatic character-all consistent with the multi-layer model.

Connecting tropical river DOM and POM to the landscape with lignin

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Remote sensing of canopy chemistry and nitrogen cycling in temperate forest ecosystems

NASA Technical Reports Server (NTRS)

Wessman, Carol A.; Aber, John D.; Peterson, David L.; Melillo, Jerry M.

1988-01-01

The use of images acquired by the Airborne Imaging Spectrometer, an experimental high-spectral resolution imaging sensor developed by NASA, to estimate the lignin concentration of whole forest canopies in Wisconsin is reported. The observed strong relationship between canopy lignin concentration and nitrogen availability in seven undisturbed forest ecosystems on Blackhawk Island, Wisconsin, suggests that canopy lignin may serve as an index for site nitrogen status. This predictive relationship presents the opportunity to estimate nitrogen-cycling rates across forested landscapes through remote sensing.

Concentration of extracellular superoxide radical as a function of time during lignin degradation by the fungus Coriolus versicolor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amer, G.I.; Drew, S.W.

1981-01-01

During a 9 day fermentation of lignin by C. versicolor, the concentration of superoxide radical in the extracellular medium of the submerged culture rose and fell, reaching a maximum after 2 and 6 days of incubation, and a minimum at 3 and 8 days. The results indicate that the extracellular superoxide radical is involved in lignin degradation, but there was no evidence that it is an initial attacking agent. (Refs. 9).

Compositional dynamics of dissolved lignin in watersheds: small temperate streams to large tropical rivers

NASA Astrophysics Data System (ADS)

Ward, N. D.; Keil, R. G.; Medeiros, P. M.; Brito, D.; Krusche, A. V.; Richey, J. E.

2012-12-01

The most abundant biochemicals on land are cellulose, hemicellulose, and lignin. Lignin, alone, composes roughly 30% of the organic carbon (OC) in the terrestrial biosphere (Boerjan et al., 2003) and a significant portion of the OC mobilized into stream and river networks worldwide. Here we present a synthesis of several studies examining (i) the mobilization dynamics/compositional changes in dissolved lignin during rapid storm events in small temperate streams (Hood Canal, WA, USA), and (ii) the respiration dynamics/biological overturning of dissolved (and particulate) lignin in the Amazon River mainstem. Rapid sampling (3 hour intervals) during short-term rainfall events has revealed that the concentration of dissolved lignin phenols (as well as DOC) in small temperate streams is strongly correlated with river discharge (Ward et al., 2012). Additionally, rapid discharge increases resulted in an increase in Ad/Al and C/V ratios and decrease in the S/V ratio of dissolved lignin phenols, indicating a mobilization of relatively degraded non-woody/gymnosperm-derived material in the dissolved phase during storms occurring after a long dry period. We hypothesize that sorption to soil surfaces imparts an additional control on lignin mobilization: degraded phenols are relatively more soluble than their non-degraded counterparts and are easily mobilized by rapid flow, whereas non-degraded phenols are slowly mobilized by base flow and continuously degraded in soils. Once lignin is mobilized into the aquatic setting it is often assumed to be refractory. However, evidence in the Amazon River mainstem suggests the contrary. We have assessed the biodegradability of dissolved (and particulate) lignin, as well as a vast suite (~120) of similar phenolic compounds with a series of incubation experiments performed on four Amazon River cruises. We estimate that on average the degradation of lignin and similar phenolic compounds supports 30-50% of bulk respiration rates in the river, implying that lignin may be a highly important organic matter fuel for CO2 outgassing from the world's inland waters. Contrary to bulk respiration rates, which poorly correlate with bulk OC concentrations, the respiration of lignin appears to be almost entirely controlled by substrate composition. Lignin (and OC) concentrations and lignin degradation rates both correlate well with the seasonal hydrograph in the Amazon (Ward et al., submitted). Based on the measurements made here, and by others (Hedges et al., 1988; Field et al., 1998; Houghton et al., 2001; Malhi et al., 2008; Bose et al., 2009) we estimate that roughly 80 Tg C of lignin is sequestered in Amazonian soils annually, roughly 40% of this lignin is respired in soils, 55% is respired within the river continuum, and less than 5% is delivered to the ocean.

Quantitative investigation of free radicals in bio-oil and their potential role in condensed-phase polymerization.

PubMed

Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah; Gable, Preston; Brown, Robert C

2015-03-01

We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20)  spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of oxidized leachate on degradation of lignin by sulfate-reducing bacteria.

PubMed

Kim, Jong-Ho; Kim, Moonil; Bae, Wooken

2009-08-01

Municipal solid waste materials (MSWs) in landfills need a long period of stabilization because lignin compounds in MSWs and leachate are not readily biodegraded, but inhibit methanogenic metabolism. Recirculation of leachate into the landfill offers the potential advantage of increasing the rate of decomposition of organic matter. However, the degradation of lignin by leachate recirculation alone is quite difficult. Several recent studies have demonstrated that sulfate-reducing bacteria (SRB) were able to degrade lignin compounds. In this study, batch tests were conducted to investigate the impacts of SRB enrichment on lignin decomposition rates as well as the decomposition of other biodegradable organics. Further, the effects of nitrite and nitrate on lignin degradation rates were also studied. A 16S rRNA assay showed that the SRB used herein, which were obtained by enriching solid waste collected from a closed MSW landfill, were Thaurea sp. and Desulfovibrio sp. Lignin was found to be biodegraded by the SRB and the rate of lignin removal per unit of waste volatile suspended solid was 2.9 mg lignin g(-1) VSS day(- 1). It was found that the initial degradation rate increased under higher initial lignin concentrations. However, the degradation rate during days 6-19 became slower than that during the initial 9 days because lignin consisted of complexly bonded aromatic compounds that were not readily biodegradable. Adding other organics such as lactate seemed to improve the rate and amount of lignin degradation, probably due to the increase in SRB associated with consumption of the additional organics. The lignin removal percentage decreased with increases in oxidized nitrogen (nitrite or nitrate) concentrations, indicating that oxidized nitrogen could inhibit SRB activity. Conclusively, the study verified the existence of SRB in the landfill and showed that the SRB could be activated for the degradation of lignin by the recirculation of the leachate, which is consistent with other studies showing that leachate recirculation could shorten the stabilization period of the landfill.

Impact assessment of bisphenol A on lignin-modifying enzymes by basidiomycete Trametes versicolor.

PubMed

Takamiya, Minako; Magan, Naresh; Warner, Philip J

2008-06-15

The impact of different concentrations of bisphenol A (BPA) was evaluated on growth of the white-rot basidiomycete, Trametes versicolor, and on the expression of genes encoding lignin-modifying enzyme (LME) activities. Effective doses (EDs) were obtained from fungal growth rate to monitor LME activities and the expression levels of their encoding genes. The fungus showed mycelial growth at concentrations of up to 300 microg ml(-1) of BPA with an ED50 value of 185 microg ml(-1). The LME activities were stimulated by BPA concentrations up to 300 microg ml(-1). The lignin peroxidase (LIP) encoding gene may be sensitive to BPA stress.

Selective Cleavage of the Aryl Ether Bonds in Lignin for Depolymerization by Acidic Lithium Bromide Molten Salt Hydrate under Mild Conditions.

PubMed

Yang, Xiaohui; Li, Ning; Lin, Xuliang; Pan, Xuejun; Zhou, Yonghong

2016-11-09

The present study demonstrates that the concentrated lithium bromide (LiBr) solution with acid as catalyst was able to selectively cleave the β-O-4 aryl ether bond and lead to lignin depolymerization under mild conditions (e.g., in 60% LiBr with 0.3 M HCl at 110 °C for 2 h). Four industrial lignins from different pulping and biorefining processes, including softwood kraft lignin (SKL), hardwood kraft lignin (HKL), softwood ethanol organosolv lignin (EOL), and acid corncob lignin (ACL), were treated in the LiBr solution. The molecular weight, functional group, and interunit linkages of the lignins were characterized using GPC, FTIR, and NMR. The results indicated that the β-O-4 aryl ether bonds of the lignins were selectively cleaved, and both LiBr and HCl played crucial roles in catalyzing the cleavage of the ether bonds.

On the relationships between leaf-litter lignin and net primary productivity in tropical rain forests.

PubMed

Kitayama, Kanehiro; Suzuki, Shizuo; Hori, Masato; Takyu, Masaaki; Aiba, Shin-Ichiro; Majalap-Lee, Noreen; Kikuzawa, Kihachiro

2004-07-01

We investigated if tropical rainforest trees produced more-lignified leaves in less productive environments using forests on Mount Kinabalu, Borneo. Our investigation was based on two earlier suggestions that slower litter decomposition occurs under less productive forests and that trees under resource limitation invest a large amount of carbon as lignin as a defense substance to minimize the loss from herbivores. When nine forests at different altitudes (700-3100 m) and soil conditions (derived from sedimentary or ultrabasic rocks) but with the same gentle relief position were compared, the concentrations of leaf-litter lignin were positively correlated with litterfall rates and leaf-litter nitrogen concentrations. These patterns would be reinforced in intact leaves if the effects of resorption at the time of leaf shedding were taken into account, because greater magnitude of resorption of mobile elements but not of lignin would occur in less productive environments (i.e. dilution of lignin in intact leaves). These results did not support earlier suggestions to explain the variation of leaf-litter lignin. Instead, we suggest that lower lignin contents are adaptive to recycle minerals without retarding decomposition in less productive environments.

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

PubMed

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

2015-11-01

Biodegradable composite films were prepared using two renewable resources based biopolymers, agar and lignin alkali. The lignin was used as a reinforcing material and agar as a biopolymer matrix. The effect of lignin concentration (1, 3, 5, and 10wt%) on the performance of the composite films was studied. In addition, the mechanical, water vapor barrier, UV light barrier properties, FE-SEM, and TGA of the films were analyzed. The agar/lignin films exhibited higher mechanical and UV barrier properties along with lower water vapor permeability compared to the neat agar film. The FTIR and SEM results showed the compatibility of lignin with agar polymer. The swelling ratio and moisture content of agar/lignin composite films were decreased with increase in lignin content. The thermostability and char content of agar/lignin composite films increased with increased lignin content. The results suggested that agar/lignin films have a potential to be used as a UV barrier food packaging material for maintaining food safety and extending the shelf-life of the packaged food. Copyright © 2015 Elsevier B.V. All rights reserved.

New perspective on glycoside hydrolase binding to lignin from pretreated corn stover

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yarbrough, John M.; Mittal, Ashutosh; Mansfield, Elisabeth

Background: Non-specific binding of cellulases to lignin has been implicated as a major factor in the loss of cellulase activity during biomass conversion to sugars. It is believed that this binding may strongly impact process economics through loss of enzyme activities during hydrolysis and enzyme recycling scenarios. The current model suggests glycoside hydrolase activities are lost though non-specific/non-productive binding of carbohydrate-binding domains to lignin, limiting catalytic site access to the carbohydrate components of the cell wall. Results: In this study, we compared component enzyme affinities of a commercial Trichoderma reesei cellulase formulation, Cellic CTec2, towards extracted corn stover lignin usingmore » sodium dodecyl sulfate-polyacrylamide gel electrophoresis and p-nitrophenyl substrate activities to monitor component binding, activity loss, and total protein binding. Protein binding was strongly affected by pH and ionic strength. β-D-glucosidases and xylanases, which do not have carbohydrate-binding modules (CBMs) and are basic proteins, demonstrated the strongest binding at low ionic strength, suggesting that CBMs are not the dominant factor in enzyme adsorption to lignin. Despite strong adsorption to insoluble lignin, β-D-glucosidase and xylanase activities remained high, with process yields decreasing only 4–15 % depending on lignin concentration. Conclusion: We propose that specific enzyme adsorption to lignin from a mixture of biomass-hydrolyzing enzymes is a competitive affinity where β-D-glucosidases and xylanases can displace CBM interactions with lignin. Process parameters, such as temperature, pH, and salt concentration influence the individual enzymes’ affinity for lignin, and both hydrophobic and electrostatic interactions are responsible for this binding phenomenon. Moreover, our results suggest that concern regarding loss of critical cell wall degrading enzymes to lignin adsorption may be unwarranted when complex enzyme mixtures are used to digest biomass.« less

New perspective on glycoside hydrolase binding to lignin from pretreated corn stover

DOE PAGES

Yarbrough, John M.; Mittal, Ashutosh; Mansfield, Elisabeth; ...

2015-12-18

Background: Non-specific binding of cellulases to lignin has been implicated as a major factor in the loss of cellulase activity during biomass conversion to sugars. It is believed that this binding may strongly impact process economics through loss of enzyme activities during hydrolysis and enzyme recycling scenarios. The current model suggests glycoside hydrolase activities are lost though non-specific/non-productive binding of carbohydrate-binding domains to lignin, limiting catalytic site access to the carbohydrate components of the cell wall. Results: In this study, we compared component enzyme affinities of a commercial Trichoderma reesei cellulase formulation, Cellic CTec2, towards extracted corn stover lignin usingmore » sodium dodecyl sulfate-polyacrylamide gel electrophoresis and p-nitrophenyl substrate activities to monitor component binding, activity loss, and total protein binding. Protein binding was strongly affected by pH and ionic strength. β-D-glucosidases and xylanases, which do not have carbohydrate-binding modules (CBMs) and are basic proteins, demonstrated the strongest binding at low ionic strength, suggesting that CBMs are not the dominant factor in enzyme adsorption to lignin. Despite strong adsorption to insoluble lignin, β-D-glucosidase and xylanase activities remained high, with process yields decreasing only 4–15 % depending on lignin concentration. Conclusion: We propose that specific enzyme adsorption to lignin from a mixture of biomass-hydrolyzing enzymes is a competitive affinity where β-D-glucosidases and xylanases can displace CBM interactions with lignin. Process parameters, such as temperature, pH, and salt concentration influence the individual enzymes’ affinity for lignin, and both hydrophobic and electrostatic interactions are responsible for this binding phenomenon. Moreover, our results suggest that concern regarding loss of critical cell wall degrading enzymes to lignin adsorption may be unwarranted when complex enzyme mixtures are used to digest biomass.« less

Biodegradation of high molecular weight lignin under sulfate reducing conditions: lignin degradability and degradation by-products.

PubMed

Ko, Jae-Jung; Shimizu, Yoshihisa; Ikeda, Kazuhiro; Kim, Seog-Ku; Park, Chul-Hwi; Matsui, Saburo

2009-02-01

This study is designed to investigate the biodegradation of high molecular weight (HMW) lignin under sulfate reducing conditions. With a continuously mesophilic operated reactor in the presence of co-substrates of cellulose, the changes in HMW lignin concentration and chemical structure were analyzed. The acid precipitable polymeric lignin (APPL) and lignin monomers, which are known as degradation by-products, were isolated and detected. The results showed that HMW lignin decreased and showed a maximum degradation capacity of 3.49 mg/l/day. APPL was confirmed as a polymeric degradation by-product and was accumulated in accordance with HMW lignin reduction. We also observed non-linear accumulation of aromatic lignin monomers such as hydrocinnamic acid. Through our experimental results, it was determined that HMW lignin, when provided with a co-substrate of cellulose, is biodegraded through production of APPL and aromatic monomers under anaerobic sulfate reducing conditions with a co-substrate of cellulose.

Effects of lignin-metal complexation on enzymatic hydrolysis of cellulose

Treesearch

H. Liu; Junyong Zhu; S.Y. Fu

2010-01-01

This study investigated the inhibition of enzymatic hydrolysis by unbound lignin (soluble and insoluble) with or without the addition of metal compounds. Sulfonated, Organosolv, and Kraft lignin were added in aqueous enzyme-cellulose systems at different concentrations before hydrolysis. The measured substrate enzymatic digestibility (SED) of cellulose was decreased by...

Fractionation of Organosolv Lignin Using Acetone:Water and Properties of the Obtained Fractions

DOE PAGES

Sadeghifar, Hasan; Wells, Tyrone; Le, Rosemary Khuu; ...

2016-11-07

In this study, lignin fractions with different molecular weight were prepared using a simple and almost green method from switchgrass and pine organosolv lignin. Different proportions of acetone in water, ranging from 30 to 60%, were used for lignin fractionation. A higher concentration of acetone dissolved higher molecular weight fractions of the lignin. Fractionated organosolv lignin showed different molecular weight and functional groups. Higher molecular weight fractions exhibited more aliphatic and less phenolic OH than lower molecular weight fractions. Lower molecular weight fractions lead to more homogeneous structure compared to samples with a higher molecular weight. In conclusion, all fractionsmore » showed strong antioxidant activity.« less

Flocculation of high purity wheat straw soda lignin.

PubMed

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

2014-01-01

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

Plant growth, biomass partitioning and soil carbon formation in response to altered lignin biosynthesis in Populus tremuloides

Treesearch

Jessica E. Hancock; Wendy M. Loya; Christian P. Giardina; Laigeng Li; Vincent L. Chiang; Kurt S. Pregitzer

2007-01-01

We conducted a glasshouse mesocosm study that combined 13C isotope techniques with wild-type and transgenic aspen (Populus tremuloides) in order to examine how altered lignin biosynthesis affects plant production and soil carbon formation. Our transgenic aspen lines expressed low stem lignin concentration but normal cellulose...

Expression of brown-midrib in a spontaneous sorghum mutant is linked to a 5'-UTR deletion in lignin biosynthesis gene SbCAD2

USDA-ARS?s Scientific Manuscript database

Brown midrib (bmr) mutants in sorghum (Sorghum bicolor (L.) Moench) and several other C4 grasses are associated with reduced lignin concentration, altered lignin composition and improved cell wall digestibility, which are desirable properties in biomass development for the emerging lignocellulosic b...

Belowground impacts of perennial grass cultivation for sustainable biofuel feedstock production in the tropics

DOE PAGES

Sumiyoshi, Yudai; Crow, Susan E.; Litton, Creighton M.; ...

2016-07-08

Perennial grasses can sequester soil organic carbon (SOC) in sustainably managed biofuel systems, directly mitigating atmospheric CO 2 concentrations while simultaneously generating biomass for renewable energy. Our objective was to quantify SOC accumulation and identify the primary drivers of belowground C dynamics in a zero-tillage production system of tropical perennial C4 grasses grown for biofuel feedstock in Hawaii. Specifically, the quantity, quality, and fate of soil C inputs were determined for eight grass accessions – four varieties each of napier grass and guinea grass. Carbon fluxes (soil CO 2 efflux, aboveground net primary productivity, litterfall, total belowground carbon flux, rootmore » decay constant), C pools (SOC pool and root biomass), and C quality (root chemistry, C and nitrogen concentrations, and ratios) were measured through three harvest cycles following conversion of a fallow field to cultivated perennial grasses. A wide range of SOC accumulation occurred, with both significant species and accession effects. Aboveground biomass yield was greater, and root lignin concentration was lower for napier grass than guinea grass. Structural equation modeling revealed that root lignin concentration was the most important driver of SOC pool: varieties with low root lignin concentration, which was significantly related to rapid root decomposition, accumulated the greatest amount of SOC. Roots with low lignin concentration decomposed rapidly, but the residue and associated microbial biomass/by-products accumulated as SOC. In general, napier grass was better suited for promoting soil C sequestration in this system. Further, high-yielding varieties with low root lignin concentration provided the greatest climate change mitigation potential in a ratoon system. By understanding the factors affecting SOC accumulation and the net greenhouse gas trade-offs within a biofuel production system will aid in crop selection to meet multiple goals toward environmental and economic sustainability.« less

Diagenetic changes of lignin compounds in a more than 0.6 million-year-old lacustrine sediment (Lake Biwa, Japan)

NASA Astrophysics Data System (ADS)

Ishiwatari, Ryoshi; Uzaki, Minoru

1987-02-01

A vertical profile of lignin in the upper 700 m layer of a 1400 m sediment core of Lake Biwa, an oligotrophic freshwater lake in Japan, was determined using a CuO oxidative degradation method. The results indicated that lignin is found throughout the core, demonstrating lignin to be very stable for over 0.6 million years. Moreover, the upper 250 m (approximately 0.6 million years old) segment of the sediment core was investigated to determine the apparent long term degradation rate of lignin. A downward lignin concentration decrease is observed over the upper 250 m of the core which corresponds to a calculated half life of at least approximately 40 × 10 4 years, assuming that lignin decrease is due to its in situ degradation (diagenesis).

Lignin nanotubes as vehicles for gene delivery into human cells.

PubMed

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

2014-01-13

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

Growth, metabolism of Phanerochaete chrysosporium and route of lignin degradation in response to cadmium stress in solid-state fermentation.

PubMed

Zhao, Meihua; Zhang, Chaosheng; Zeng, Guangming; Huang, Danlian; Xu, Piao; Cheng, Min

2015-11-01

This study examines the growth, metabolism of Phanerochaete chrysosporium (P. chrysosporium) and route of lignin degradation in response to cadmium (Cd) stress in solid-state fermentation of rice straw. Less living fungi biomass was found under Cd exposure, suggesting that Cd had strong toxicity to P. chrysosporium. The maximum values of lignin peroxidase and manganese peroxidase were 0.34 and 5.21 U g(-1) at the Cd concentration of 32 mg kg(-1), respectively, lower than that in control, which indicated Cd stress would inhibit ligninolytic enzymes. The production of reactive oxygen species (ROS) including hydroxyl radicals (OH), superoxide anion radical (O2(-)) and hydrogen peroxide (H2O2) increased after Cd exposure. Higher concentration of oxalate was detected at high Cd concentrations. Cd stress also had influence on the rates of lignocelluloses degradation and the route of lignin degradation. Partial Cd could be removed by P. chrysosporium. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fluorescence analyzer for lignin

DOEpatents

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

1993-01-01

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

Characterization and enzymatic hydrolysis of wood from transgenic Pinus taeda engineered with syringyl lignin or reduced lignin content

DOE Office of Scientific and Technical Information (OSTI.GOV)

Edmunds, Charles W.; Peralta, Perry; Kelley, Stephen S.

Softwood is an abundant resource; however, currently its utilization for bioconversion to obtain platform sugars is limited. Pinus taeda trees which were genetically modified to either produce S lignin or to decrease lignin content were characterized with a suite of analytic techniques. Syringyl lignin was visualized in the secondary xylem of one genetic line with Maule staining. Solid-state nuclear magnetic resonance identified the S lignin units were coupled into the lignin through β-O-4 linkages, and thioacidolysis measured approximately 13% S lignin content in the same sample. Reductions of the lignin of as much as 33% were observed in the transgenics.more » To better understand how these modifications affect bioconversion, their amenability to hot water and dilute acid pretreatments and enzymatic hydrolysis was evaluated. Lignin reductions resulted in 1.9-3.2-fold increases in glucose release compared to the control. However, no apparent benefit was observed by S lignin incorporation at the concentrations reported in this study. Finally, these results highlight the potential for softwood cell wall properties to be improved for bioenergy/biochemical applications.« less

Characterization and enzymatic hydrolysis of wood from transgenic Pinus taeda engineered with syringyl lignin or reduced lignin content

DOE PAGES

Edmunds, Charles W.; Peralta, Perry; Kelley, Stephen S.; ...

2017-02-22

Softwood is an abundant resource; however, currently its utilization for bioconversion to obtain platform sugars is limited. Pinus taeda trees which were genetically modified to either produce S lignin or to decrease lignin content were characterized with a suite of analytic techniques. Syringyl lignin was visualized in the secondary xylem of one genetic line with Maule staining. Solid-state nuclear magnetic resonance identified the S lignin units were coupled into the lignin through β-O-4 linkages, and thioacidolysis measured approximately 13% S lignin content in the same sample. Reductions of the lignin of as much as 33% were observed in the transgenics.more » To better understand how these modifications affect bioconversion, their amenability to hot water and dilute acid pretreatments and enzymatic hydrolysis was evaluated. Lignin reductions resulted in 1.9-3.2-fold increases in glucose release compared to the control. However, no apparent benefit was observed by S lignin incorporation at the concentrations reported in this study. Finally, these results highlight the potential for softwood cell wall properties to be improved for bioenergy/biochemical applications.« less

Determination of ethylenic residues in wood and TMP of spruce by FT-Raman spectroscopy

Treesearch

Umesh P. Agarwal; Sally A. Ralph

2008-01-01

A method based on FT-Raman spectroscopy is proposed for determining in situ concentrations of ethylenic residues in softwood lignin. Raman contributions at 1133 and 1654 cm-1, representing coniferaldehyde and coniferyl alcohol structures, respectively, were used in quantifying these units in spruce wood with subsequent conversion to concentrations in lignin. For...

Rapid and near-complete dissolution of wood lignin at ≤80°C by a recyclable acid hydrotrope

PubMed Central

Chen, Liheng; Dou, Jinze; Ma, Qianli; Li, Ning; Wu, Ruchun; Bian, Huiyang; Yelle, Daniel J.; Vuorinen, Tapani; Fu, Shiyu; Pan, Xuejun; Zhu, Junyong (J.Y.)

2017-01-01

We report the discovery of the hydrotropic properties of a recyclable aromatic acid, p-toluenesulfonic acid (p-TsOH), for potentially low-cost and efficient fractionation of wood through rapid and near-complete dissolution of lignin. Approximately 90% of poplar wood (NE222) lignin can be dissolved at 80°C in 20 min. Equivalent delignification using known hydrotropes, such as aromatic salts, can be achieved only at 150°C or higher for more than 10 hours or at 150°C for 2 hours with alkaline pulping. p-TsOH fractionated wood into two fractions: (i) a primarily cellulose-rich water-insoluble solid fraction that can be used for the production of high-value building blocks, such as dissolving pulp fibers, lignocellulosic nanomaterials, and/or sugars through subsequent enzymatic hydrolysis; and (ii) a spent acid liquor stream containing mainly dissolved lignin that can be easily precipitated as lignin nanoparticles by diluting the spent acid liquor to below the minimal hydrotrope concentration. Our nuclear magnetic resonance analyses of the dissolved lignin revealed that p-TsOH can depolymerize lignin via ether bond cleavage and can separate carbohydrate-free lignin from the wood. p-TsOH has a relatively low water solubility, which can facilitate efficient recovery using commercially proven crystallization technology by cooling the concentrated spent acid solution to ambient temperatures to achieve environmental sustainability through recycling of p-TsOH. PMID:28929139

EFFECTS OF COFIRING LIGNIN AND BIOSOLIDS WITH COAL ON FIRESIDE PERFORMANCE AND COMBUSTION PRODUCTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kevin C. Galbreath

2002-08-01

Lignin, derived from municipal solid waste and biosolid feedstocks using Masada Resource Group's patented CES OxyNol{trademark} process, and acidified biosolids were evaluated as supplemental fuels with coal for producing steam and electricity. Tests were conducted in a pilot-scale (550,000-Btu/hr [580-MJ/hr]) combustion system to evaluate the effects of coal characteristics, blend mixture (on a dry wt% basis) and furnace exit gas temperature (FEGT) on boiler heat-exchange surface slagging and fouling, NO{sub x} and SO{sub x} production, fly ash characteristics, and combustion efficiency. The effects of blending lignin and acidified biosolids with coal on fuel handling and pulverization characteristics were also addressed.more » An 80 wt% Colorado--20 wt% subbituminous Powder River Basin coal blend from the Tennessee Valley Authority Colbert Steam Plant, hereafter referred to as the Colbert coal, and a bituminous Pittsburgh No. 8 coal were tested. The lignin and acidified biosolids were characterized by possessing higher moisture content and lower carbon, hydrogen, and heating values relative to the coals. Ash contents of the fuels were similar. The lignin also possessed higher concentrations of TiO{sub 2}, CaO, and SO{sub 3} and lower concentrations of SiO{sub 2}, Al{sub 2}O{sub 3}, Fe{sub 2}O{sub 3}, K{sub 2}O, and N relative to the coals. The sulfur content of lignin could be reduced through a more thorough washing and drying of the lignin in an efficient commercial-scale dewatering device. Acidified biosolids were distinguished by higher concentrations of P{sub 2}O{sub 5} and MgO and lower SiO{sub 2} and Al{sub 2}O{sub 3} relative to the other fuels. Trace element concentrations, especially for Cr, Pb, Hg, and Ni, were generally greater in the lignin and acidified biosolid fuels relative to the Colbert coal. Maximum trace element emission factors were calculated for 95:5 Colbert coal--lignin and 90:5:5 Colbert coal--lignin--acidified biosolid blends and compared to U.S. Environmental Protection Agency emission factors for pulverized coal-fired units that are unequipped with pollution control devices. Calculated maximum trace element emission factors for the fuel blends were generally less than or within the range of those for the uncontrolled coal-fired units, except for Cr and Pb which were greater.« less

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

PubMed

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

2014-09-24

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

Interactions between Cellulolytic Enzymes with Native, Autohydrolysis, and Technical Lignins and the Effect of a Polysorbate Amphiphile in Reducing Nonproductive Binding.

PubMed

Fritz, Consuelo; Ferrer, Ana; Salas, Carlos; Jameel, Hasan; Rojas, Orlando J

2015-12-14

Understanding enzyme-substrate interactions is critical in designing strategies for bioconversion of lignocellulosic biomass. In this study we monitored molecular events, in situ and in real time, including the adsorption and desorption of cellulolytic enzymes on lignins and cellulose, by using quartz crystal microgravimetry and surface plasmon resonance. The effect of a nonionic surface active molecule was also elucidated. Three lignin substrates relevant to the sugar platform in biorefinery efforts were considered, namely, hardwood autohydrolysis cellulolytic (HWAH), hardwood native cellulolytic (MPCEL), and nonwood native cellulolytic (WSCEL) lignin. In addition, Kraft lignins derived from softwoods (SWK) and hardwoods (HWK) were used as references. The results indicated a high affinity between the lignins with both, monocomponent and multicomponent enzymes. More importantly, the addition of nonionic surfactants at concentrations above their critical micelle concentration reduced remarkably (by over 90%) the nonproductive interactions between the cellulolytic enzymes and the lignins. This effect was hypothesized to be a consequence of the balance of hydrophobic and hydrogen bonding interactions. Moreover, the reduction of surface roughness and increased wettability of lignin surfaces upon surfactant treatment contributed to a lower affinity with the enzymes. Conformational changes of cellulases were observed upon their adsorption on lignin carrying preadsorbed surfactant. Weak electrostatic interactions were determined in aqueous media at pH between 4.8 and 5.5 for the native cellulolytic lignins (MPCEL and WSCEL), whereby a ∼20% reduction in the enzyme affinity was observed. This was mainly explained by electrostatic interactions (osmotic pressure effects) between charged lignins and cellulases. Noteworthy, adsorption of nonionic surfactants onto cellulose, in the form cellulose nanofibrils, did not affect its hydrolytic conversion. Overall, our results highlight the benefit of nonionic surfactant pretreatment to reduce nonproductive enzyme binding while maintaining the reactivity of the cellulosic substrate.

Export of Dissolved Lignin from Coastal Wetlands to the Louisiana Shelf

NASA Astrophysics Data System (ADS)

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.

Geochemistry and Flux of Terrigenous Dissolved Organic Matter to the Arctic Ocean

NASA Astrophysics Data System (ADS)

Spencer, R. G.; Mann, P. J.; Hernes, P. J.; Tank, S. E.; Striegl, R. G.; Dyda, R. Y.; Peterson, B. J.; McClelland, J. W.; Holmes, R. M.

2011-12-01

Rivers draining into the Arctic Ocean exhibit high concentrations of terrigenous dissolved organic carbon (DOC) and recent studies indicate that DOC export is changing due to climatic warming and alteration in permafrost condition. The fate of exported DOC in the Arctic Ocean is of key importance for understanding the regional carbon cycle and remains a point of discussion in the literature. As part of the Arctic Great Rivers Observatory (Arctic-GRO) project, samples were collected for DOC, chromophoric dissolved organic matter (CDOM) and lignin phenols from the Ob', Yenisey, Lena, Kolyma, Mackenzie and Yukon rivers in 2009 - 2010. DOC and lignin concentrations were elevated during the spring freshet and measurements related to DOC composition indicated an increasing contribution from terrestrial vascular plant sources at this time of year (e.g. lignin carbon-normalized yield, CDOM spectral slope, SUVA254, humic-like fluorescence). CDOM absorption was found to correlate strongly with both DOC (r2=0.83) and lignin concentration (r2=0.92) across the major arctic rivers. Utilizing these relationships we modeled loads for DOC and lignin export from high-resolution CDOM measurements (daily across the freshet) to derive improved flux estimates, particularly from the dynamic spring discharge maxima period when the majority of DOC and lignin export occurs. The new load estimates for DOC and lignin are higher than previous evaluations, emphasizing that if these are more representative of current arctic riverine export, terrigenous DOC is transiting through the Arctic Ocean at a faster rate than previously thought. It is apparent that higher resolution sampling of arctic rivers is exceptionally valuable with respect to deriving accurate fluxes and we highlight the potential of CDOM in this role for future studies and the applicability of in-situ CDOM sensors.

Degradation of Lignin in Agricultural Residues by locally Isolated Fungus Neurospora discreta.

PubMed

Pamidipati, Sirisha; Ahmed, Asma

2017-04-01

Locally isolated fungus, Neurospora discreta, was evaluated for its ability to degrade lignin in two agricultural residues: cocopeat and sugarcane bagasse with varying lignin concentrations and structures. Using Klason's lignin estimation, high-performance liquid chromatography, and UV-visible spectroscopy, we found that N. discreta was able to degrade up to twice as much lignin in sugarcane bagasse as the well-known white rot fungus Phanerochaete chrysosporium and produced nearly 1.5 times the amount of lignin degradation products in submerged culture. Based on this data, N. discreta is a promising alternative to white rot fungi for faster microbial pre-treatment of agricultural residues. This paper presents the lignin degrading capability of N. discreta for the first time and also discusses the difference in biodegradability of cocopeat and sugarcane bagasse as seen from the analysis carried out using Fourier transform infrared spectroscopy.

Dissolved Organic Matter Land-Ocean Linkages in the Arctic

NASA Astrophysics Data System (ADS)

Mann, P. J.; Spencer, R. M.; Hernes, P. J.; Tank, S. E.; Striegl, R.; Dyda, R. Y.; Peterson, B. J.; McClelland, J. W.; Holmes, R. M.

2012-04-01

Rivers draining into the Arctic Ocean exhibit high concentrations of terrigenous dissolved organic carbon (DOC), and recent studies indicate that DOC export is changing due to climatic warming and alteration in permafrost condition. The fate of exported DOC in the Arctic Ocean is important for understanding the regional carbon cycle and remains a point of discussion in the literature. As part of the NSF funded Arctic Great Rivers Observatory (Arctic-GRO) project, samples were collected for DOC, chromophoric and fluorescent dissolved organic matter (CDOM & FDOM) and lignin phenols from the Ob', Yenisey, Lena, Kolyma, Mackenzie and Yukon rivers in 2009 - 2010. DOC and lignin concentrations were elevated during the spring freshet and measurements related to DOC composition indicated an increasing contribution from terrestrial vascular plant sources at this time of year (e.g. lignin carbon-normalized yield, CDOM spectral slope, SUVA254, humic-like fluorescence). CDOM absorption was found to correlate strongly with both DOC (r2=0.83) and lignin concentration (r2=0.92) across the major arctic rivers. Lignin composition was also successfully modeled using FDOM measurements decomposed using PARAFAC analysis. Utilizing these relationships we modeled loads for DOC and lignin export from high-resolution CDOM measurements (daily across the freshet) to derive improved flux estimates, particularly from the dynamic spring discharge maxima period when the majority of DOC and lignin export occurs. The new load estimates for DOC and lignin are higher than previous evaluations, emphasizing that if these are more representative of current arctic riverine export, terrigenous DOC is transiting through the Arctic Ocean at a faster rate than previously thought. It is apparent that higher resolution sampling of arctic rivers is exceptionally valuable with respect to deriving accurate fluxes and we highlight the potential of CDOM in this role for future studies and the applicability of in-situ CDOM sensors.

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

PubMed

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

2015-06-19

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

Transcript Profiling of Two Alfalfa Genotypes with Contrasting Cell Wall Composition in Stems Using a Cross-Species Platform: Optimizing Analysis by Masking Biased Probes

USDA-ARS?s Scientific Manuscript database

The stem cell walls of alfalfa [Medicago sativa (L.) ssp. sativa] genotype 252 have high cellulose and lignin concentrations, while stem cell walls of genotype 1283 have low cellulose and lignin concentrations. The GeneChip® Medicago Genome Array, developed for Medicago truncatula, is a suitable pla...

Higher acid-chlorite reactivity of cell corner middle lamella lignin in black spruce

Treesearch

Umesh P. Agarwal

2007-01-01

To determine if there was a delignification behavior difference between secondary wall (S2) and middle lamella (cell corner or CC) lignin, black spruce cross-sections were acid-chlorite delignified and the tissue was evaluated in-situ by Raman imaging. Lignin concentration in S2 and CC was determined in numerous latewood cell areas in the two hour delignified cross...

Molecular-Level Transformations of Lignin During Photo-Oxidation and Biodegradation

NASA Astrophysics Data System (ADS)

Feng, X.; Hills, K.; Simpson, A. J.; Simpson, M. J.

2009-05-01

As the second most abundant component of terrestrial plant residues, lignin plays a key role in regulating plant litter decomposition, humic substance formation, and dissolved organic matter (OM) production from terrestrial sources. Biodegradation is the primary decomposition process of lignin on land. However, photo- oxidation of lignin-derived compounds has been reported in aquatic systems and is considered to play a vital role in arid and semiarid regions. With increasing ultraviolet (UV) radiation due to ozone depletion, it is important to understand the biogeochemical fate of lignin exposed to photo-oxidation in terrestrial environments. This study examines and compares the transformation of lignin in a three-month laboratory simulation of biodegradation and photo-oxidation using molecular-level techniques. Lignin-derived monomers extracted by copper oxidation were analyzed by gas chromatography/mass spectrometry (GC/MS) from the water-soluble and insoluble OM of 13C-labeled corn leaves. Biodegradation increased the solubility of lignin monomers in comparison to the control samples, and the acid-to-aldehyde (Ad/Al) ratios increased in both the water-soluble and insoluble OM, indicating a higher degree of side-chain lignin oxidation. Photo-oxidation did not produce a significant change on the solubility or Ad/Al ratios of lignin from corn leaves. However, the ratios of trans-to-cis isomers of both cinnamyl units (p-coumaric acid and ferulic acid) increased with photo-oxidation and decreased with biodegradation in the insoluble OM. We also investigated the role of photo-oxidation in lignin transformation in soils cropped with 13C-labeled corn. Interestingly, the organic carbon content increased significantly with time in the water-soluble OM from soil/corn residues under UV radiation. An increase in the concentration of lignin monomers and dimers and the Ad/Al ratios was also observed with photo-oxidation. Iso-branched fatty acids of microbial origin remained in a similar concentration in the water-soluble OM from the UV-radiated and control soils, indicating little microbial contribution to the observed increase in water-soluble carbon. These observations suggest that photo-oxidation may increase the solubility of soil organic matter (SOM) through the oxidation of lignin-derived compounds. Mechanisms of lignin oxidation (demethylation or side-chain oxidation) and molecular size distribution changes of the water-soluble and NaOH-soluble OM during photo-oxidation and biodegradation will also be examined using solution-state nuclear magnetic resonance (NMR) spectroscopy. Collectively, our experiment demonstrates that while biodegradation predominates in the decomposition of lignin in plant litter, photo- oxidation may play an important part in destabilizing lignin-derived compounds in the soil.

Molecular-level transformations of lignin during photo-oxidation and biodegradation

NASA Astrophysics Data System (ADS)

Feng, X.; Hills, K.; Simpson, A. J.; Simpson, M. J.

2009-04-01

As the second most abundant component of terrestrial plant residues, lignin plays a key role in regulating plant litter decomposition, humic substance formation, and dissolved organic matter (OM) production from terrestrial sources. Biodegradation is the primary decomposition process of lignin on land. However, photo-oxidation of lignin-derived compounds has been reported in aquatic systems and is considered to play a vital role in arid and semiarid regions. With increasing ultraviolet (UV) radiation due to ozone depletion, it is important to understand the biogeochemical fate of lignin exposed to photo-oxidation in terrestrial environments. This study examines and compares the transformation of lignin in a three-month laboratory simulation of biodegradation and photo-oxidation using molecular-level techniques. Lignin-derived monomers extracted by copper oxidation were analyzed by gas chromatography/mass spectrometry (GC/MS) from the water-soluble and insoluble OM of 13C-labeled corn leaves. Biodegradation increased the solubility of lignin monomers in comparison to the control samples, and the acid-to-aldehyde (Ad/Al) ratios increased in both the water-soluble and insoluble OM, indicating a higher degree of side-chain lignin oxidation. Photo-oxidation did not produce a significant change on the solubility or Ad/Al ratios of lignin from corn leaves. However, the ratios of trans-to-cis isomers of both cinnamyl units (p-coumaric acid and ferulic acid) increased with photo-oxidation and decreased with biodegradation in the insoluble OM. We also investigated the role of photo-oxidation in lignin transformation in soils cropped with 13C-labeled corn. Interestingly, the organic carbon content increased significantly with time in the water-soluble OM from soil/corn residues under UV radiation. An increase in the concentration of lignin monomers and dimers and the Ad/Al ratios was also observed with photo-oxidation. Iso-branched fatty acids of microbial origin remained in a similar concentration in the water-soluble OM from the UV-radiated and control soils, indicating little microbial contribution to the observed increase in water-soluble carbon. These observations suggest that photo-oxidation may increase the solubility of soil organic matter (SOM) through the oxidation of lignin-derived compounds. Mechanisms of lignin oxidation (demethylation or side-chain oxidation) and molecular size distribution changes of the water-soluble and NaOH-soluble OM during photo-oxidation and biodegradation will also be examined using solution-state nuclear magnetic resonance (NMR) spectroscopy. Collectively, our experiment demonstrates that while biodegradation predominates in the decomposition of lignin in plant litter, photo-oxidation may play an important part in destabilizing lignin-derived compounds in the soil.

Membrane Technology for the Recovery of Lignin: A Review

PubMed Central

Humpert, Daniel; Ebrahimi, Mehrdad; Czermak, Peter

2016-01-01

Utilization of renewable resources is becoming increasingly important, and only sustainable processes that convert such resources into useful products can achieve environmentally beneficial economic growth. Wastewater from the pulp and paper industry is an unutilized resource offering the potential to recover valuable products such as lignin, pigments, and water [1]. The recovery of lignin is particularly important because it has many applications, and membrane technology has been investigated as the basis of innovative recovery solutions. The concentration of lignin can be increased from 62 to 285 g∙L−1 using membranes and the recovered lignin is extremely pure. Membrane technology is also scalable and adaptable to different waste liquors from the pulp and paper industry. PMID:27608047

Source to sink: Evolution of lignin composition in the Madre de Dios River system with connection to the Amazon basin and offshore

NASA Astrophysics Data System (ADS)

Feng, Xiaojuan; Feakins, Sarah J.; Liu, Zongguang; Ponton, Camilo; Wang, Renée. Z.; Karkabi, Elias; Galy, Valier; Berelson, William M.; Nottingham, Andrew T.; Meir, Patrick; West, A. Joshua

2016-05-01

While lignin geochemistry has been extensively investigated in the Amazon River, little is known about lignin distribution and dynamics within deep, stratified river channels or its transformations within soils prior to delivery to rivers. We characterized lignin phenols in soils, river particulate organic matter (POM), and dissolved organic matter (DOM) across a 4 km elevation gradient in the Madre de Dios River system, Peru, as well as in marine sediments to investigate the source-to-sink evolution of lignin. In soils, we found more oxidized lignin in organic horizons relative to mineral horizons. The oxidized lignin signature was maintained during transfer into rivers, and lignin was a relatively constant fraction of bulk organic carbon in soils and riverine POM. Lignin in DOM became increasingly oxidized downstream, indicating active transformation of dissolved lignin during transport, especially in the dry season. In contrast, POM accumulated undegraded lignin downstream during the wet season, suggesting that terrestrial input exceeded in-river degradation. We discovered high concentrations of relatively undegraded lignin in POM at depth in the lower Madre de Dios River in both seasons, revealing a woody undercurrent for its transfer within these deep rivers. Our study of lignin evolution in the soil-river-ocean continuum highlights important seasonal and depth variations of river carbon components and their connection to soil carbon pools, providing new insights into fluvial carbon dynamics associated with the transfer of lignin biomarkers from source to sink.

Stable carbon isotope ratios and intrinsic water-use efficiency of Miocene fossil leaves compared to modern congeners

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, J.D.; Zhang, J.; Rember, W.C.

Miocene fossil leaves of forest trees were extracted from the Clarkia, Idaho fossil beds and their stable carbon isotope ratios were analyzed. Fossils had higher lignin concentrations and lower cellulose concentrations that modern leaves due to diagenesis and the HF used to extract the fossils. Therefore, [delta][sup 13]C of extracted fossil lignin was compared to that of modern lignin. Fossil lignin [delta][sup 13]C was significantly different from that of congeneric modern leaves (paired t-test, P<0.0001), but was 1.9% less negative. Gymnosperms (Metasequoia, Taxodium) were less negative than angiosperms (e.g., Magnolia, Quercus, Acer, Persea), but no difference between evergreen and deciduousmore » species was detected. Using published estimates of the concentration and [delta][sup 13]C of atmospheric CO[sub 2] during the Miocene was estimated the CO[sub 2] partial pressure gradient across the stomata (intrinsic water-use efficiency). Intrinsic water-use efficiency was at least 70% higher during this past [open quotes]greenhouse[close quotes] period than at present.« less

Integrated production of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) using an easily recyclable di-carboxylic acid

Treesearch

Huiyang Bian; Liheng Chen; Hongqi Dai; J.Y. Zhu

2017-01-01

Here we demonstrate di-carboxylic acid hydrolysis for the integrated production of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) using two unbleached hardwood chemical pulps of lignin contents of 3.9 and 17.2%. Acid hydrolysis experiments used maleic acid solution of 60 wt% concentration at 120°C for 120 min under ambient pressure. Yields of...

Density functional theory study of spirodienone stereoisomers in lignin

Treesearch

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

2017-01-01

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

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

PubMed

Woo, Hannah L; Hazen, Terry C

2018-01-01

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

Enzymatic tranformations of lignin. Annual report 1 July 1980-30 June 1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glasser, W.G.; Hall, P.L.

1981-06-01

Research is summarized on biological approaches to the utilization of lignin degradation to raw material for the manufacture of chemicals and materials. This investigation studied the possible involvement of reduced oxygen species produced by the white-rot fungus, C. versicolor, in the initial breakdown of the lignin macromolecule during its biodegradation. This fungus was shown to be capable of exporting superoxide radical. While the degree to which this organism was responsible for actual lignin degradation is not clear, there were indications that a correlation may exist between the concentration of extracellular superoxide radical in the medium and the extent of ligninmore » degradation. Two different fermentation schemes were compared and several control fermentation experiments were made. Research dealing with improvements in lignin structure analysis, liquefaction of lignin preparations by reaction with propylene oxide, and solidification of liquified kraft lignin by crosslinking with diisocyanate compounds was explored. The use of scanning electron microscopy for revealing interaction between fiber and binder is noted.« less

Synergetic Effects of Alcohol/Water Mixing on the Catalytic Reductive Fractionation of Poplar Wood

DOE Office of Scientific and Technical Information (OSTI.GOV)

Renders, Tom; Van den Bosch, Sander; Vangeel, Thijs

One of the foremost challenges in lignocellulose conversion encompasses the integration of effective lignin valorization in current carbohydrate-oriented biorefinery schemes. Catalytic reductive fractionation (CRF) of lignocellulose offers a technology to simultaneously produce lignin-derived platform chemicals and a carbohydrate-enriched pulp via the combined action of lignin solvolysis and metal-catalyzed hydrogenolysis. Herein, the solvent (composition) plays a crucial role. In this contribution, we study the influence of alcohol/water mixtures by processing poplar sawdust in varying MeOH/water and EtOH/water blends. The results show particular effects that strongly depend on the applied water concentration. Low water concentrations enhance the removal of lignin from themore » biomass, while the majority of the carbohydrates are left untouched (scenario A). Contrarily, high water concentrations favor the solubilization of both hemicellulose and lignin, resulting in a more pure cellulosic residue (scenario B). For both scenarios, an evaluation was made to determine the most optimal solvent composition, based on two earlier introduced empirical efficiency descriptors (denoted LFDE and LFFE). According to these measures, 30 (A) and 70 vol % water (B) showed to be the optimal balance for both MeOH/water and EtOH/water mixtures. This successful implementation of alcohol/water mixtures allows operation under milder processing conditions in comparison to pure alcohol solvents, which is advantageous from an industrial point of view.« less

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers.

PubMed

Harman-Ware, Anne E; Happs, Renee M; Davison, Brian H; Davis, Mark F

2017-01-01

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H), and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10, and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid-state NMR spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.

Synthesis of sodium lignosulphonate from oil palm empty fruit bunches's lignin

NASA Astrophysics Data System (ADS)

Prakoso, Nurcahyo Iman; Purwono, Suryo; Rochmadi

2017-03-01

Synthesis of sodium lignosulphonate have been done by using batch method. Optimation of synthesis method was achieved through this study. The study was conducted on the optimation of mass ratio of lignin to the NaHSO3 solution, the concentration of NaHSO3 solution, reaction temperature, and reaction time. Of all the treatments, it was found that the optimum mass ratio of lignin to the NaHSO3 solution, concentration of NaHSO3 solution, reaction temperature, and reaction time respectively, 0.3 M, 0.1 M 97 °C, and the reaction was carried out for 4 hours. Excellent yields and selective products were obtained (90-92%)

Investigating Biochemical and Developmental Dependencies of Lignification with a Click-Compatible Monolignol Analog in Arabidopsis thaliana Stems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pandey, Jyotsna L.; Kiemle, Sarah N.; Richard, Tom L.

Lignin is a key structural component of plant cell walls that provides rigidity, strength, and resistance against microbial attacks. This hydrophobic polymer also serves a crucial role in water transport. Despite its abundance and essential functions, several aspects of lignin biosynthesis and deposition remain cryptic. Lignin precursors are known to be synthesized in the cytoplasm by complex biosynthetic pathways, after which they are transported to the apoplastic space, where they are polymerized via free radical coupling reactions into polymeric lignin. However, the lignin deposition process and the factors controlling it are unclear. In this study, the biochemical and developmental dependenciesmore » of lignification were investigated using a click-compatible monolignol analog, 3-O-propargylcaffeyl alcohol (3-OPC), which can incorporate into both in vitro polymerized lignin and Arabidopsis thaliana tissues. Fluorescence labeling of 3-OPC using click chemistry followed by confocal fluorescence microscopy enabled the detection and imaging of 3-OPC incorporation patterns. These patterns were consistent with endogenous lignification observed in different developmental stages of Arabidopsis stems. However, the concentration of supplied monolignols influenced where lignification occurred at the subcellular level, with low concentrations being deposited in cell corners and middle lamellae and high concentrations also being deposited in secondary walls. Experimental inhibition of multiple lignification factors confirmed that 3-OPC incorporation proceeds via a free radical coupling mechanism involving peroxidases/laccases and reactive oxygen species (ROS). Finally, the presence of peroxide-producing enzymes determined which cell walls lignified: adding exogenous peroxide and peroxidase caused cells that do not naturally lignify in Arabidopsis stems to lignify. In conclusion, 3-OPC accurately mimics natural lignification patterns in different developmental stages of Arabidopsis stems and allows for the dissection of key biochemical and enzymatic factors controlling lignification.« less

Investigating Biochemical and Developmental Dependencies of Lignification with a Click-Compatible Monolignol Analog in Arabidopsis thaliana Stems

PubMed Central

Pandey, Jyotsna L.; Kiemle, Sarah N.; Richard, Tom L.; Zhu, Yimin; Cosgrove, Daniel J.; Anderson, Charles T.

2016-01-01

Lignin is a key structural component of plant cell walls that provides rigidity, strength, and resistance against microbial attacks. This hydrophobic polymer also serves a crucial role in water transport. Despite its abundance and essential functions, several aspects of lignin biosynthesis and deposition remain cryptic. Lignin precursors are known to be synthesized in the cytoplasm by complex biosynthetic pathways, after which they are transported to the apoplastic space, where they are polymerized via free radical coupling reactions into polymeric lignin. However, the lignin deposition process and the factors controlling it are unclear. In this study, the biochemical and developmental dependencies of lignification were investigated using a click-compatible monolignol analog, 3-O-propargylcaffeyl alcohol (3-OPC), which can incorporate into both in vitro polymerized lignin and Arabidopsis thaliana tissues. Fluorescence labeling of 3-OPC using click chemistry followed by confocal fluorescence microscopy enabled the detection and imaging of 3-OPC incorporation patterns. These patterns were consistent with endogenous lignification observed in different developmental stages of Arabidopsis stems. However, the concentration of supplied monolignols influenced where lignification occurred at the subcellular level, with low concentrations being deposited in cell corners and middle lamellae and high concentrations also being deposited in secondary walls. Experimental inhibition of multiple lignification factors confirmed that 3-OPC incorporation proceeds via a free radical coupling mechanism involving peroxidases/laccases and reactive oxygen species (ROS). Finally, the presence of peroxide-producing enzymes determined which cell walls lignified: adding exogenous peroxide and peroxidase caused cells that do not naturally lignify in Arabidopsis stems to lignify. In summary, 3-OPC accurately mimics natural lignification patterns in different developmental stages of Arabidopsis stems and allows for the dissection of key biochemical and enzymatic factors controlling lignification. PMID:27630649

Investigating Biochemical and Developmental Dependencies of Lignification with a Click-Compatible Monolignol Analog in Arabidopsis thaliana Stems

DOE PAGES

Pandey, Jyotsna L.; Kiemle, Sarah N.; Richard, Tom L.; ...

2016-08-31

Lignin is a key structural component of plant cell walls that provides rigidity, strength, and resistance against microbial attacks. This hydrophobic polymer also serves a crucial role in water transport. Despite its abundance and essential functions, several aspects of lignin biosynthesis and deposition remain cryptic. Lignin precursors are known to be synthesized in the cytoplasm by complex biosynthetic pathways, after which they are transported to the apoplastic space, where they are polymerized via free radical coupling reactions into polymeric lignin. However, the lignin deposition process and the factors controlling it are unclear. In this study, the biochemical and developmental dependenciesmore » of lignification were investigated using a click-compatible monolignol analog, 3-O-propargylcaffeyl alcohol (3-OPC), which can incorporate into both in vitro polymerized lignin and Arabidopsis thaliana tissues. Fluorescence labeling of 3-OPC using click chemistry followed by confocal fluorescence microscopy enabled the detection and imaging of 3-OPC incorporation patterns. These patterns were consistent with endogenous lignification observed in different developmental stages of Arabidopsis stems. However, the concentration of supplied monolignols influenced where lignification occurred at the subcellular level, with low concentrations being deposited in cell corners and middle lamellae and high concentrations also being deposited in secondary walls. Experimental inhibition of multiple lignification factors confirmed that 3-OPC incorporation proceeds via a free radical coupling mechanism involving peroxidases/laccases and reactive oxygen species (ROS). Finally, the presence of peroxide-producing enzymes determined which cell walls lignified: adding exogenous peroxide and peroxidase caused cells that do not naturally lignify in Arabidopsis stems to lignify. In conclusion, 3-OPC accurately mimics natural lignification patterns in different developmental stages of Arabidopsis stems and allows for the dissection of key biochemical and enzymatic factors controlling lignification.« less

Increased lodging resistance in long-culm, low-lignin gh2 rice for improved feed and bioenergy production

PubMed Central

Ookawa, Taiichiro; Inoue, Kazuya; Matsuoka, Makoto; Ebitani, Takeshi; Takarada, Takeshi; Yamamoto, Toshio; Ueda, Tadamasa; Yokoyama, Tadashi; Sugiyama, Chisato; Nakaba, Satoshi; Funada, Ryo; Kato, Hiroshi; Kanekatsu, Motoki; Toyota, Koki; Motobayashi, Takashi; Vazirzanjani, Mehran; Tojo, Seishu; Hirasawa, Tadashi

2014-01-01

Lignin modification has been a breeding target for the improvements of forage digestibility and energy yields in forage and bioenergy crops, but decreased lignin levels are often accompanied by reduced lodging resistance. The rice mutant gold hull and internode2 (gh2) has been identified to be lignin deficient. GH2 has been mapped to the short arm of chromosome 2 and encodes cinnamyl-alcohol dehydrogenase (CAD). We developed a long-culm variety, ‘Leaf Star’, with superior lodging resistance and a gh phenotype similar to one of its parents, ‘Chugoku 117’. The gh loci in Leaf Star and Chugoku 117 were localized to the same region of chromosome 2 as the gh2 mutant. Leaf Star had culms with low lignin concentrations due to a natural mutation in OsCAD2 that was not present in Chugoku 117. However, this variety had high culm strength due to its strong, thick culms. Additionally, this variety had a thick layer of cortical fiber tissue with well-developed secondary cell walls. Our results suggest that rice can be improved for forage and bioenergy production by combining superior lodging resistance, which can be obtained by introducing thick and stiff culm traits, with low lignin concentrations, which can be obtained using the gh2 variety. PMID:25298209

Polyphenol oxidase activity and differential accumulation of polyphenolics in seed coats of pinto bean (Phaseolus vulgaris L.) characterize postharvest color changes.

PubMed

Marles, M A Susan; Vandenberg, Albert; Bett, Kirstin E

2008-08-27

Postharvest darkening of pinto bean (Phaseolus vulgaris L.) was evaluated in a population of recombinant inbred lines derived from a cross between CDC Pintium (a regular-darkening line) and 1533-15 (a slow-darkening line). Flavonoid metabolite concentrations, polyphenol oxidase activity, lignin concentration, and seed coat anatomy characteristics were assessed for cosegregation with the darkening phenotype. Significantly lower kaempferol concentrations (p = 0.00001) together with differences in polyphenol oxidase activity (p = 0.0045) were two of the key findings associated with these recombinant inbred lines. In addition, two different assays (thioglycolic acid and Klason lignin) to quantify lignin together with an assessment of extractable condensed tannin were used to estimate the contribution of these polymers to changes in the seed coat tissue. This is the first report of precise biochemical characterization of polyphenolics that associate with postharvest darkening in legumes.

Poly(ethylene oxide)-Assisted Macromolecular Self-Assembly of Lignin in ABS Matrix for Sustainable Composite Applications

DOE PAGES

Akato, Kokouvi M.; Tran, Chau D.; Chen, Jihua; ...

2015-11-05

Here we report the compatibilization of biomass-derived lignin polymer in acrylonitrile butadiene styrene (ABS) thermoplastic matrix without loss of mechanical properties via poly(ethylene oxide) (PEO)-mediated macromolecular self-assembly. ABS was blended with lignin in different concentrations, and blends with 10 wt % PEO (relative to lignin) were prepared. The relative tensile strength improved slightly at low lignin content but diminished rapidly as the lignin content was increased. However, the inclusion of PEO as an interfacial adhesion promoter helped avoid deleterious effects. Dynamic mechanical analysis showed that PEO plasticized the hard phase and thus lowered the activation energy (E a) for itsmore » relaxation but caused stiffening of the soft phase and increased its E a. Microscopy revealed that incorporating lignin in ABS led to the statistical dispersion of discrete lignin domains (300–1000 nm) which, after PEO addition, were reduced to smaller interconnected particles (200–500 nm). The lignin-extended partially renewable ABS resins showed shear-thinning behavior and reduced viscosity compared to neat ABS. The preferred lignin-loaded compositions reinforced with 20 vol % chopped carbon fibers exhibited mechanical performances (77–80 MPa) equivalent to those of reinforced ABS materials reportedly used in 3D printing applications. In conclusion, this approach could lower the cost of ABS while reducing its carbon footprint.« less

Lignin phenols in sediments of Lake Baikal, Siberia: Application to paleoenvironmental studies

USGS Publications Warehouse

Orem, W.H.; Colman, Steven M.; Lerch, H.E.

1997-01-01

Sediments from three cores obtained from distinct depositional environments in Lake Baikal, Siberia were analyzed for organic carbon, total nitrogen and lignin phenol concentration and composition. Results were used to examine changes in paleoenvironmental conditions during climatic cycles of the late Quaternary (< 125 ka). Average organic carbon, and total nitrogen concentrations, atomic C/N ratios and organic carbon accumulation rates were significantly higher in the Holocene compared with the late Pleistocene, reflecting overall warmer temperatures and increased runoff during the Holocene. A Holocene maximum in organic carbon was observed at about 6 ka, and may represent the warmest wettest period of the Holocene. At one site (Academician Ridge) pronounced late Pleistocene maxima in organic carbon and biogenic silica were observed at about 80-85 ka, probably indicative of an interstadial period with enhanced aquatic productivity. Total sedimentary lignin phenol contents were generally lower in the late Pleistocene compared to the Holocene, but with several peaks in concentration during the late Pleistocene. These late Pleistocene peaks in total sedimentary lignin content (dated at about 80, 50 and 30 ka) directly precede or occur during peaks in sedimentary biogenic silica contents. These periods likely represent relatively warm interstadial times, with increased precipitation producing the observed increase in terrestrial runoff and aquatic productivity. Lignin phenol ratios (S/V, C/V and P/V) were used to examine changes in terrestrial vegetation type resulting from changes in paleoenvironmental conditions during the late Pleistocene. A degree of caution must be used in the interpretation of these ratios with regard to vegetation sources and paleoenvironmental conditions, because of potential compositional changes in lignin resulting from biodegradation. Nevertheless, results show that long glacial periods were characterized by terrestrial vegetation composed of a mix of non-woody angiosperm vegetation and minor gymnosperm forest. Shorter interstadial periods are defined by a change to dominant gymnosperm forest and were observed at about 80, 75, 63, 50 and 30 ka, ranging from about 2-6 kyr in duration. These interstadial periods of the late Pleistocene defined by lignin phenol ratios generally occur during longer periods of enhanced sedimentary biogenic silica content (about 10-15 ka in duration), providing corroborative evidence of these warm interstadial periods.Sediments obtained in Lake Baikal were analyzed for organic carbon, total nitrogen and lignin phenol composition and used to study changes in paleoenvironmental conditions during climatic cycles of the late Quaternary. The organic carbon, total nitrogen concentrations, atomic C/N ratios and organic carbon accumulation rates were higher in the Holocene showing overall warmer temperatures and increased runoff. Total lignin phenol contents were lower in the Pleistocene representing relatively warm interstadial times with increased precipitation, runoff and aquatic productivity. Lignin phenol was used to examine vegetation changes due to paleoenvironmental conditions and showed that long glacial periods were characterized by terrestrial vegetation.

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harman-Ware, Anne E.; Happs, Renee M.; Davison, Brian H.

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H) and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10 and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid state NMRmore » spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.« less

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers

DOE PAGES

Harman-Ware, Anne E.; Happs, Renee M.; Davison, Brian H.; ...

2017-11-30

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H) and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10 and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid state NMRmore » spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.« less

Improving the enzymatic hydrolysis of dilute acid pretreated wheat straw by metal ion blocking of non-productive cellulase adsorption on lignin.

PubMed

Akimkulova, Ardak; Zhou, Yan; Zhao, Xuebing; Liu, Dehua

2016-05-01

Eleven salts were selected to screen the possible metal ions for blocking the non-productive adsorption of cellulase onto the lignin of dilute acid pretreated wheat straw. Mg(2+) was screened finally as the promising candidate. The optimal concentration of MgCl2 was 1 mM, but the beneficial action was also dependent on pH, hydrolysis time and cellulase loading. Significant improvement of glucan conversion (19.3%) was observed at low cellulase loading (5 FPU/g solid). Addition of isolated lignins, tannic acid and lignin model compounds to pure cellulose hydrolysis demonstrated that phenolic hydroxyl group (Ph-OH) was the main active site blocked by Mg(2+). The interaction between Mg(2+) and Ph-OH of lignin monomeric moieties followed an order of p-hydroxyphenyl (H)>guaiacyl (G)>syringyl (S). Mg(2+) blocking made the lignin surface less negatively charged, which might weaken the hydrogen bonding and electrostatically attractive interaction between lignin and cellulase enzymes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Organosolv extraction of lignin from hydrolyzed almond shells and application of the delta-value theory.

PubMed

Quesada-Medina, Joaquín; López-Cremades, Francisco Javier; Olivares-Carrillo, Pilar

2010-11-01

The solubility of lignin from hydrolyzed almond (Prunus amygdalus) shells in different acetone, ethanol and dioxane-water mixtures and conditions (extraction time and temperature) was studied. The concept of the solubility parameter (delta-value) was applied to explain the effect of organic solvent concentration on lignin solubility. The organic solvent-water mixture that led to the highest lignin extraction was composed of a 75% vol. of organic solvent for all the solvent series investigated (acetone, ethanol and dioxane). Moreover, the best lignin extraction conditions were a temperature of 210 degrees C and an extraction time of 40 min for the acetone and ethanol series, and 25 min for the dioxane series. The delta-value of the hydrolyzed almond shell lignin [14.60 (cal/cm(3))(1/2)] and that of the organic solvent-water mixtures was calculated. The experimental delignification capacity of the aqueous organic solvents clearly reflected the proximity of their delta-value to that of lignin. The hydrogen-bonding capacity of the solvent-water mixtures was also taken into account. Copyright 2010 Elsevier Ltd. All rights reserved.

Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

USGS Publications Warehouse

Eckard, Robert S.; Hernes, Peter J.; Bergamaschi, Brian A.; Stepanauskas, Ramunas; Kendall, Carol

2007-01-01

Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L-1 within the Sacramento River to 39.9 mg L-1 at the outfall from an island drain (median 3.0 mg L-1), while lignin concentrations ranged from 3.0 μL-1 within the Sacramento River to 111 μL-1 at the outfall from an island drain (median 11.6 μL-1). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC)-1 at an island drain to 0.84 mg (100 mg OC)-1 for a wetland (median 0.36 mg (100 mg OC)-1), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of localized landscape features, and is also the first to indicate a significant negative correlation between lignin and DOC bioavailability within environmental samples. Based upon observed trends: (1) Delta features exhibit significant spatial variability in organic chemical composition, and (2) localized Delta features appear to exert strong controls on terrigenous DOC as it passes through the Delta and is exported into the Pacific Ocean.

Response of oxidative enzyme activities to nitrogen deposition affects soil concentrations of dissolved organic carbon

USGS Publications Warehouse

Waldrop, M.P.; Zak, D.R.

2006-01-01

Recent evidence suggests that atmospheric nitrate (NO3- ) deposition can alter soil carbon (C) storage by directly affecting the activity of lignin-degrading soil fungi. In a laboratory experiment, we studied the direct influence of increasing soil NO 3- concentration on microbial C cycling in three different ecosystems: black oak-white oak (BOWO), sugar maple-red oak (SMRO), and sugar maple-basswood (SMBW). These ecosystems span a broad range of litter biochemistry and recalcitrance; the BOWO ecosystem contains the highest litter lignin content, SMRO had intermediate lignin content, and SMBW leaf litter has the lowest lignin content. We hypothesized that increasing soil solution NO 3- would reduce lignolytic activity in the BOWO ecosystem, due to a high abundance of white-rot fungi and lignin-rich leaf litter. Due to the low lignin content of litter in the SMBW, we further reasoned that the NO3- repression of lignolytic activity would be less dramatic due to a lower relative abundance of white-rot basidiomycetes; the response in the SMRO ecosystem should be intermediate. We increased soil solution NO3- concentrations in a 73-day laboratory incubation and measured microbial respiration and soil solution dissolved organic carbon (DOC) and phenolics concentrations. At the end of the incubation, we measured the activity of ??-glucosidase, N-acetyl-glucosaminidase, phenol oxidase, and peroxidase, which are extracellular enzymes involved with cellulose and lignin degradation. We quantified the fungal biomass, and we also used fungal ribosomal intergenic spacer analysis (RISA) to gain insight into fungal community composition. In the BOWO ecosystem, increasing NO 3- significantly decreased oxidative enzyme activities (-30% to -54%) and increased DOC (+32% upper limit) and phenolic (+77% upper limit) concentrations. In the SMRO ecosystem, we observed a significant decrease in phenol oxidase activity (-73% lower limit) and an increase in soluble phenolic concentrations (+57% upper limit) in response to increasing NO 3- in soil solution, but there was no significant change in DOC concentration. In contrast to these patterns, increasing soil solution NO3- in the SMBW soil resulted in significantly greater phenol oxidase activity (+700% upper limit) and a trend toward lower DOC production (-52% lower limit). Nitrate concentration had no effect on microbial respiration or ??-glucosidase or N-acetyl-glucosaminidase activities. Fungal abundance and basidiomycete diversity tended to be highest in the BOWO soil and lowest in the SMBW, but neither displayed a consistent response to NO 3- additions. Taken together, our results demonstrate that oxidative enzyme production by microbial communities responds directly to NO3- deposition, controlling extracellular enzyme activity and DOC flux. The regulation of oxidative enzymes by different microbial communities in response to NO3- deposition highlights the fact that the composition and function of soil microbial communities directly control ecosystem-level responses to environmental change. ?? 2006 Springer Science+Business Media, Inc.

Litter dynamics in two Sierran mixed conifer forests. II. Nutrient release in decomposing leaf litter

USGS Publications Warehouse

Stohlgren, Thomas J.

1988-01-01

The factors influencing leaf litter decomposition and nutrient release patterns were investigated for 3.6 years in two mixed conifer forests in the southern Sierra Nevada of California. The giant sequoia–fir forest was dominated by giant sequoia (Sequoiadendrongiganteum (Lindl.) Buchh.), white fir (Abiesconcolor Lindl. & Gord.), and sugar pine (Pinuslambertiana Dougl.). The fir–pine forest was dominated by white fir, sugar pine, and incense cedar (Calocedrusdecurrens (Torr.) Florin). Initial concentrations of nutrients and percent lignin, cellulose, and acid detergent fiber vary considerably in freshly abscised leaf litter of the studied species. Giant sequoia had the highest concentration of lignin (20.3%) and the lowest concentration of nitrogen (0.52%), while incense cedar had the lowest concentration of lignin (9.6%) and second lowest concentration of nitrogen (0.63%). Long-term (3.6 years) foliage decomposition rates were best correlated with initial lignin/N (r2 = 0.94, p r2 = 0.92, p r2 = 0.80, p < 0.05). Patterns of nutrient release were highly variable. Giant sequoia immobilized N and P, incense cedar immobilized N and to a lesser extent P, while sugar pine immobilized Ca. Strong linear or negative exponential relationships existed between initial concentrations of N, P, K, and Ca and percent original mass remaining of those nutrients after 3.6 years. This suggests efficient retention of these nutrients in the litter layer of these ecosystems. Nitrogen concentrations steadily increase in decomposing leaf litter, effectively reducing the C/N ratios from an initial range of 68–96 to 27–45 after 3.6 years.

Micro-Spectroscopic Imaging of Lignin-Carbohydrate Complexes in Plant Cell Walls and Their Migration During Biomass Pretreatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Yining; Zhao, Shuai; Wei, Hui

2015-04-27

In lignocellulosic biomass, lignin is the second most abundant biopolymer. In plant cell walls, lignin is associated with polysaccharides to form lignin-carbohydrate complexes (LCC). LCC have been considered to be a major factor that negatively affects the process of deconstructing biomass to simple sugars by cellulosic enzymes. Here, we report a micro-spectroscopic approach that combines fluorescence lifetime imaging microscopy and Stimulated Raman Scattering microscopy to probe in situ lignin concentration and conformation at each cell wall layer. This technique does not require extensive sample preparation or any external labels. Using poplar as a feedstock, for example, we observe variation ofmore » LCC in untreated tracheid poplar cell walls. The redistribution of LCC at tracheid poplar cell wall layers is also investigated when the chemical linkages between lignin and hemicellulose are cleaved during pretreatment. Our study would provide new insights into further improvement of the biomass pretreatment process.« less

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

PubMed

Lamminpää, Kaisa; Ahola, Juha; Tanskanen, Juha

2015-02-01

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

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

PubMed

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

2017-04-01

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

TREATMENT OF A PENTACHLOROPHENOL AND CREOSOTE-CONTAMINATED SOIL USING THE LIGNIN-DEGRADING FUNGUS PHANERO- CHAETE SORDIDA: A FIELD DEMONSTRATION

EPA Science Inventory

The feasibility of large-scale fungal bioaugmentation was evaluated by assessing the ability of the lignin-degrading fungus Phanerochaete sordida to decrease the soil concentrations of pentachlorophenol (PCP) and 13 priority pollutant polynuclear aromatic (PNA) creosote component...

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

PubMed

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

2007-03-27

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

Changes in Lignin and Polysaccharide Components in 13 Cultivars of Rice Straw following Dilute Acid Pretreatment as Studied by Solution-State 2D 1H-13C NMR

PubMed Central

Teramura, Hiroshi; Sasaki, Kengo; Oshima, Tomoko; Aikawa, Shimpei; Matsuda, Fumio; Okamoto, Mami; Shirai, Tomokazu; Kawaguchi, Hideo; Ogino, Chiaki; Yamasaki, Masanori; Kikuchi, Jun; Kondo, Akihiko

2015-01-01

A renewable raw material, rice straw is pretreated for biorefinery usage. Solution-state two-dimensional (2D) 1H-13 C hetero-nuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy, was used to analyze 13 cultivars of rice straw before and after dilute acid pretreatment, to characterize general changes in the lignin and polysaccharide components. Intensities of most (15 of 16) peaks related to lignin aromatic regions, such as p-coumarate, guaiacyl, syringyl, p-hydroxyphenyl, and cinnamyl alcohol, and methoxyl, increased or remained unchanged after pretreatment. In contrast, intensities of most (11 of 13) peaks related to lignin aliphatic linkages or ferulate decreased. Decreased heterogeneity in the intensities of three peaks related to cellulose components in acid-insoluble residues resulted in similar glucose yield (0.45–0.59 g/g-dry biomass). Starch-derived components showed positive correlations (r = 0.71 to 0.96) with glucose, 5-hydroxymethylfurfural (5-HMF), and formate concentrations in the liquid hydrolysates, and negative correlations (r = –0.95 to –0.97) with xylose concentration and acid-insoluble residue yield. These results showed the fate of lignin and polysaccharide components by pretreatment, suggesting that lignin aromatic regions and cellulose components were retained in the acid insoluble residues and starch-derived components were transformed into glucose, 5-HMF, and formate in the liquid hydrolysate. PMID:26083431

Screening of Bacillus coagulans strains in lignin supplemented minimal medium with high throughput turbidity measurements.

PubMed

Glaser, Robert; Venus, Joachim

2014-12-01

The aim of this study was to extend the options for screening and characterization of microorganism through kinetic growth parameters. In order to obtain data, automated turbidimetric measurements were accomplished to observe the response of strains of Bacillus coagulans . For the characterization, it was decided to examine the influence of varying concentrations of lignin with respect to bacterial growth. Different mathematical models are used for comparison: logistic, Gompertz, Baranyi and Richards and Stannard. The growth response was characterized by parameters like maximum growth rate, maximum population, and the lag time. In this short analysis we present a mathematical approach towards a comparison of different microorganisms. Furthermore, it can be demonstrated that lignin in low concentrations can have a positive influence on the growth of B. coagulans .

Lignin geochemistry of a Late Quaternary sediment core from Lake Washington

NASA Astrophysics Data System (ADS)

Hedges, John I.; Ertel, John R.; Leopold, Estella B.

1982-10-01

Long-term lignin stability and paleovegetation patterns were investigated using CuO oxidation products of sediments from an 11 m core of Late Quaternary sediment collected from the mid-basin of Lake Washington, Washington State. Relatively constant yields of lignin-derived phenols (normalized to organic carbon) from the entire core indicate minimal in situ lignin degradation over the last 13,000 years. Compositional patterns within the phenolic suite and increased corresponding yields from baseextracted sediments indicate that sedimentary lignins are present predominantly as well preserved plant tissue fragments. Abundance patterns of vanillyl, syringyl, and cinnamyl phenols record four distinct sequences within the core characterized by: (a) high concentrations of gymnosperm wood in a basal horizon of glacial flour, 11-10 m; (b) an essentially pure mixture of nonwoody angiosperm tissues in late Pleistocene sediments, 10-8 m; (c) relatively high concentrations of angiosperm woods in the bottom half of a limnic peat sequence deposited approximately 10,000-7,000 years B.P., 8-4 m; and (d) a progressive enrichment in gymnosperm woods at the expense of angiosperm woods over the last 7,000 years in the upper limnic peat, 4-0 m. Vascular plant tissues account for less than half the total sedimentary organic carbon throughout the core.

Application of a two-stream radiative transfer model for leaf lignin and cellulose concentrations from spectral reflectance measurements, part 2

NASA Technical Reports Server (NTRS)

Conel, James E.; Vandenbosch, Jeannette; Grove, Cindy I.

1993-01-01

We used the Kubelka-Munk theory of diffuse spectral reflectance in layers to analyze influences of multiple chemical components in leaves. As opposed to empirical approaches to estimation of plant chemistry, the full spectral resolution of laboratory reflectance data was retained in an attempt to estimate lignin or other constituent concentrations from spectral band positions. A leaf water reflectance spectrum was derived from theoretical mixing rules, reflectance observations, and calculations from theory of intrinsic k- and s-functions. Residual reflectance bands were then isolated from spectra of fresh green leaves. These proved hard to interpret for composition in terms of simple two component mixtures such as lignin and cellulose. We next investigated spectral and dilution influences of other possible components (starch, protein). These components, among others, added to cellulose in hypothetical mixtures, produce band displacements similar to lignin, but will disguise by dilution the actual abundance of lignin present in a multicomponent system. This renders interpretation of band positions problematical. Knowledge of end-members and their spectra, and a more elaborate mixture analysis procedure may be called for. Good observational atmospheric and instrumental conditions and knowledge thereof are required for retrieval of expected subtle reflectance variations present in spectra of green vegetation.

Early diagenesis of lignin-associated phenolics in the salt marsh grass Spartina alterniflora

NASA Astrophysics Data System (ADS)

Haddad, R. I.; Newell, S. Y.; Martens, C. S.; Fallon, R. D.

1992-10-01

The predepositional stability of lignin in the salt marsh cordgrass Spartina alterniflora was examined in two different degradation studies: one was a traditional litterbag study carried out using post-senescent brown leaves in a North Carolina marsh creek, and the other was a study in which senescing, standing plants were tagged and allowed to undergo in situ degradation in a Sapelo Island, Georgia, salt marsh. Based on results from lignin oxidation product (LOP) analysis of leaves, lignin in the S. alterniflora was shown to be significantly degraded in both studies, with 13 ± 2% and 25 ± 12% of the total lignin mass loss occurring over the 496-day litterbag and 146-day tagged studies, respectively. A comparison of the results from both studies suggests that most of the calculated lignin loss (> 90%) occurs early in the degradation history of the plant, with a significant portion occurring while the plant is still standing in the salt marsh. Further detailed evaluation of this loss demonstrates that selective lignin degradation occurs in S. alterniflora, deriving from the preferential loss of labile lignin moieties. The most labile component, trans-ferulic acid, accounted for 57% and 82% of the total lignin loss in the litterbag and tagged studies, respectively, based on normalization to syringyl-phenol concentrations. Comparison of these two data sets supports the following approximate lignin stability sequence for S. alterniflora:S ≅ Ca ≅ V > P > Fa. Based on measured changes in both the lignin mass loss and the LOP acid/aldehyde ratio, as well as evidence suggesting that degradation occurred under oxic conditions, it is proposed that aromatic ring cleavage was the predominant mechanism of lignin degradation in both studies. In light of these results and those from other recent lignin degradation studies, we discuss the geochemical consequences regarding the usefulness of lignin oxidation products as quantitative tracers of vascular plant-derived organic matter being transported, deposited, and buried in aquatic environments.

Development of a genetically programed vanillin-sensing bacterium for high-throughput screening of lignin-degrading enzyme libraries.

PubMed

Sana, Barindra; Chia, Kuan Hui Burton; Raghavan, Sarada S; Ramalingam, Balamurugan; Nagarajan, Niranjan; Seayad, Jayasree; Ghadessy, Farid J

2017-01-01

Lignin is a potential biorefinery feedstock for the production of value-added chemicals including vanillin. A huge amount of lignin is produced as a by-product of the paper industry, while cellulosic components of plant biomass are utilized for the production of paper pulp. In spite of vast potential, lignin remains the least exploited component of plant biomass due to its extremely complex and heterogenous structure. Several enzymes have been reported to have lignin-degrading properties and could be potentially used in lignin biorefining if their catalytic properties could be improved by enzyme engineering. The much needed improvement of lignin-degrading enzymes by high-throughput selection techniques such as directed evolution is currently limited, as robust methods for detecting the conversion of lignin to desired small molecules are not available. We identified a vanillin-inducible promoter by RNAseq analysis of Escherichia coli cells treated with a sublethal dose of vanillin and developed a genetically programmed vanillin-sensing cell by placing the 'very green fluorescent protein' gene under the control of this promoter. Fluorescence of the biosensing cell is enhanced significantly when grown in the presence of vanillin and is readily visualized by fluorescence microscopy. The use of fluorescence-activated cell sorting analysis further enhances the sensitivity, enabling dose-dependent detection of as low as 200 µM vanillin. The biosensor is highly specific to vanillin and no major response is elicited by the presence of lignin, lignin model compound, DMSO, vanillin analogues or non-specific toxic chemicals. We developed an engineered E. coli cell that can detect vanillin at a concentration as low as 200 µM. The vanillin-sensing cell did not show cross-reactivity towards lignin or major lignin degradation products including vanillin analogues. This engineered E. coli cell could potentially be used as a host cell for screening lignin-degrading enzymes that can convert lignin to vanillin.

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

PubMed

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

2007-06-05

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

Fungicidal values of bio-oils and their lignin-rich fractions obtained from wood/bark fast pyrolysis.

PubMed

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.

Azo Dye Biodecolorization Enhanced by Echinodontium taxodii Cultured with Lignin

PubMed Central

Meng, Jing; Yu, Hongbo; Zhang, Xiaoyu

2014-01-01

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

Elevated CO2 induces alteration in lignin accumulation in celery (Apium graveolens L.).

PubMed

Liu, Jie-Xia; Feng, Kai; Wang, Guang-Long; Xu, Zhi-Sheng; Wang, Feng; Xiong, Ai-Sheng

2018-06-01

Carbon dioxide (CO 2 ) is an important regulator of plant growth and development, and its proportion in the atmosphere continues to rise now. Lignin is one of the major secondary products in plants with vital biological functions. However, the relationship between CO 2 level and xylogenesis in celery is still unknown. In order to investigate the effects of increasing CO 2 concentration on lignin accumulation in celery, 'Jinnanshiqin' were exposed to two CO 2 applications, 400 (e 0 ) and 1000 μmol mol -1 (e 1 ), respectively. Plant morphology and lignin distribution in celery plants treated with elevated CO 2 did not change significantly. There was an upward trend on lignin content in celery leaves, and the transcript abundance of 12 genes involved in lignin metabolism has altered in response to elevated CO 2 . The effects of high level of CO 2 on different tissues were different. Our works confirmed that CO 2 may play an important role in lignin accumulation in celery leaves. The current study will offer new evidence to understand the regulation mechanism of lignin biosynthesis under elevated CO 2 and provide a reference to improve celery quality by adjusting the growth environment. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Transmission electron microscopy, fluorescence microscopy, and confocal raman microscopic analysis of ultrastructural and compositional heterogeneity of Cornus alba L. wood cell wall.

PubMed

Ma, Jianfeng; Ji, Zhe; Zhou, Xia; Zhang, Zhiheng; Xu, Feng

2013-02-01

Transmission electron microscopy (TEM), fluorescence microscopy, and confocal Raman microscopy can be used to characterize ultrastructural and compositional heterogeneity of plant cell walls. In this study, TEM observations revealed the ultrastructural characterization of Cornus alba L. fiber, vessel, axial parenchyma, ray parenchyma, and pit membrane between cells, notably with the ray parenchyma consisting of two well-defined layers. Fluorescence microscopy evidenced that cell corner middle lamella was more lignified than adjacent compound middle lamella and secondary wall with variation in lignification level from cell to cell. In situ Raman images showed that the inhomogeneity in cell wall components (cellulose and lignin) among different cells and within morphologically distinct cell wall layers. As the significant precursors of lignin biosynthesis, the pattern of coniferyl alcohol and aldehyde (joint abbreviation Lignin-CAA for both structures) distribution in fiber cell wall was also identified by Raman images, with higher concentration occurring in the fiber secondary wall where there was the highest cellulose concentration. Moreover, noteworthy was the observation that higher concentration of lignin and very minor amounts of cellulose were visualized in the pit membrane areas. These complementary microanalytical methods provide more accurate and complete information with regard to ultrastructural and compositional characterization of plant cell walls.

Lignin Peroxidase from Streptomyces viridosporus T7A: Enzyme Concentration Using Ultrafiltration

NASA Astrophysics Data System (ADS)

Gottschalk, Leda M. F.; Bon, Elba P. S.; Nobrega, Ronaldo

It is well known that lignin degradation is a key step in the natural process of biomass decay whereby oxidative enzymes such as laccases and high redox potential ligninolytic peroxidases and oxidases play a central role. More recently, the importance of these enzymes has increased because of their prospective industrial use for the degradation of the biomass lignin to increase the accessibility of the cellulose and hemicellulose moieties to be used as renewable material for the production of fuels and chemicals. These biocatalysts also present potential application on environmental biocatalysis for the degradation of xenobiotics and recalcitrant pollutants. However, the cost for these enzymes production, separation, and concentration must be low to permit its industrial use. This work studied the concentration of lignin peroxidase (LiP), produced by Streptomyces viridosporus T7A, by ultrafiltration, in a laboratory-stirred cell, loaded with polysulfone (PS) or cellulose acetate (CA) membranes with molecular weight cutoffs (MWCO) of 10, 20, and 50 KDa. Experiments were carried out at 25 °C and pH 7.0 in accordance to the enzyme stability profile. The best process conditions and enzyme yield were obtained using a PS membrane with 10 KDa MWCO, whereby it was observed a tenfold LiP activity increase, reaching 1,000 U/L and 90% enzyme activity upholding.

Organic matter compositions of rivers draining into Hudson Bay: Present-day trends and potential as recorders of future climate change

NASA Astrophysics Data System (ADS)

Godin, Pamela; Macdonald, Robie W.; Kuzyk, Zou Zou A.; Goñi, Miguel A.; Stern, Gary A.

2017-07-01

Concentrations and compositions of particulate and dissolved organic carbon (POC and DOC, respectively) and aromatic compounds including lignin were analyzed in water samples from 17 rivers flowing into Hudson Bay, northern Canada. These rivers incorporate basins to the south with no permafrost to basins in the north with continuous permafrost, and dominant vegetation systems that include Boreal Forest, the Hudson Plains, Taiga Shield, and Tundra. Major latitudinal trends in organic carbon and lignin concentrations and compositions were evident, with both DOC and dissolved lignin concentrations dominating over their particulate counterparts and exhibiting significant correlations with total dissolved and suspended solids, respectively. The composition of lignin reaction products in terms of the syringyl, cinnamyl, and vanillyl compositions indicate mixed sources of vascular land plant-derived organic carbon, with woody gymnosperms contributions dominating in the southern river basins whereas nonwoody angiosperm sources were more important in the most northerly rivers. The composition of nonlignin aromatic compounds, which provides a tracer for nonvascular plant contributions, suggests stronger contributions from Sphagnum mosses to dissolved organic matter in rivers below the tree line, including those with large peat bogs in their basins. Acid/aldehyde ratios of the lignin products together with Δ14C data for DOC in selected rivers indicate that DOC has generally undergone greater alteration than POC. Interestingly, several northern rivers exhibited relatively old DOC according to the Δ14C data suggesting that either old DOC is being released from permafrost or old DOC survives river transport in these rivers.

Pyrolysis of sunflower seed hulls for obtaining bio-oils.

PubMed

Casoni, Andrés I; Bidegain, Maximiliano; Cubitto, María A; Curvetto, Nestor; Volpe, María A

2015-02-01

Bio-oils from pyrolysis of as received sunflower seed hulls (SSH), hulls previously washed with acid (SSHA) and hulls submitted to a mushroom enzymatic attack (BSSH) were analyzed. The concentration of lignin, hemicellulose and cellulose varied with the pre-treatment. The liquid corresponding to SSH presented a relatively high concentration of acetic acid and a high instability to storage. The bio-oil from SSHA showed a high concentration of furfural and an appreciable amount of levoglucosenone. Lignin was degraded upon enzymatic activity, for this reason BSSH led to the highest yield of bio-oil, with relative high concentration of acetic acid and stability to storage. Copyright © 2014 Elsevier Ltd. All rights reserved.

 The application of computational chemistry to lignin

Treesearch

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

2017-01-01

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

Effective depolymerization of concentrated acid hydrolysis lignin using a carbon-supported ruthenium catalyst in ethanol/formic acid media.

PubMed

Kristianto, Ivan; Limarta, Susan Olivia; Lee, Hyunjoo; Ha, Jeong-Myeong; Suh, Dong Jin; Jae, Jungho

2017-06-01

Lignin isolated by two-step concentrated acid hydrolysis of empty fruit bunch (EFB) was effectively depolymerized into a high-quality bio-oil using formic acid (FA) as an in-situ hydrogen source and Ru/C as a catalyst in supercritical ethanol. A bio-oil yield of 66.3wt% with an average molecular weight of 822g/mol and an aromatic monomer content of 6.1wt% was achieved at 350°C and a FA-to-lignin mass ratio of 3 after a reaction time of 60min. The combination of Ru/C and FA also resulted in a significant reduction in the oxygen content of the bio-oil by ∼60% and a corresponding increase in the higher heating value (HHV) to 32.7MJ/kg due to the enhanced hydrodeoxygenation activity. An examination of the FA decomposition characteristics revealed that Ru/C provides a greater increase in the rate of hydrogen production from FA, explaining the efficient depolymerization of lignin in a combined system. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evidence supporting dissimilatory and assimilatory lignin degradation in Enterobacter lignolyticus SCF1

PubMed Central

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

2013-01-01

Lignocellulosic biofuels are promising as sustainable alternative fuels, but lignin inhibits access of enzymes to cellulose, and by-products of lignin degradation can be toxic to cells. The fast growth, high efficiency and specificity of enzymes employed in the anaerobic litter deconstruction carried out by tropical soil bacteria make these organisms useful templates for improving biofuel production. The facultative anaerobe Enterobacter lignolyticus SCF1 was initially cultivated from Cloud Forest soils in the Luquillo Experimental Forest in Puerto Rico, based on anaerobic growth on lignin as sole carbon source. The source of the isolate was tropical forest soils that decompose litter rapidly with low and fluctuating redox potentials, where bacteria using oxygen-independent enzymes likely play an important role in decomposition. We have used transcriptomics and proteomics to examine the observed increased growth of SCF1 grown on media amended with lignin compared to unamended growth. Proteomics suggested accelerated xylose uptake and metabolism under lignin-amended growth, with up-regulation of proteins involved in lignin degradation via the 4-hydroxyphenylacetate degradation pathway, catalase/peroxidase enzymes, and the glutathione biosynthesis and glutathione S-transferase (GST) proteins. We also observed increased production of NADH-quinone oxidoreductase, other electron transport chain proteins, and ATP synthase and ATP-binding cassette (ABC) transporters. This suggested the use of lignin as terminal electron acceptor. We detected significant lignin degradation over time by absorbance, and also used metabolomics to demonstrate moderately significant decreased xylose concentrations as well as increased metabolic products acetate and formate in stationary phase in lignin-amended compared to unamended growth conditions. Our data show the advantages of a multi-omics approach toward providing insights as to how lignin may be used in nature by microorganisms coping with poor carbon availability. PMID:24065962

Evidence supporting dissimilatory and assimilatory lignin degradation in Enterobacter lignolyticus SCF1.

PubMed

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

2013-01-01

Lignocellulosic biofuels are promising as sustainable alternative fuels, but lignin inhibits access of enzymes to cellulose, and by-products of lignin degradation can be toxic to cells. The fast growth, high efficiency and specificity of enzymes employed in the anaerobic litter deconstruction carried out by tropical soil bacteria make these organisms useful templates for improving biofuel production. The facultative anaerobe Enterobacter lignolyticus SCF1 was initially cultivated from Cloud Forest soils in the Luquillo Experimental Forest in Puerto Rico, based on anaerobic growth on lignin as sole carbon source. The source of the isolate was tropical forest soils that decompose litter rapidly with low and fluctuating redox potentials, where bacteria using oxygen-independent enzymes likely play an important role in decomposition. We have used transcriptomics and proteomics to examine the observed increased growth of SCF1 grown on media amended with lignin compared to unamended growth. Proteomics suggested accelerated xylose uptake and metabolism under lignin-amended growth, with up-regulation of proteins involved in lignin degradation via the 4-hydroxyphenylacetate degradation pathway, catalase/peroxidase enzymes, and the glutathione biosynthesis and glutathione S-transferase (GST) proteins. We also observed increased production of NADH-quinone oxidoreductase, other electron transport chain proteins, and ATP synthase and ATP-binding cassette (ABC) transporters. This suggested the use of lignin as terminal electron acceptor. We detected significant lignin degradation over time by absorbance, and also used metabolomics to demonstrate moderately significant decreased xylose concentrations as well as increased metabolic products acetate and formate in stationary phase in lignin-amended compared to unamended growth conditions. Our data show the advantages of a multi-omics approach toward providing insights as to how lignin may be used in nature by microorganisms coping with poor carbon availability.

Organic geochemistry of sediments from the continental margin off southern New England, U.S.A.--Part I. Amino acids, carbohydrates and lignin

NASA Technical Reports Server (NTRS)

Steinberg, S. M.; Venkatesan, M. I.; Kaplan, I. R.

1987-01-01

Total organic carbon (TOC), lignin, amino acids, sugars and amino sugars were measured in recent sediments for the continental margin off southern New England. The various organic carbon fractions decreased in concentration with increasing distance from shore. The fraction of the TOC that was accounted for by these major components also decreased with increasing distance from shore. The concentration of lignin indicated that only about 3-5% of the organic carbon in the nearshore sediment was of terrestrial origin. The various fractions were highly correlated, which was consistent with a simple linear mixing model of shelf organic matter with material form the slope and rise and indicated a significant transport of sediment from the continental shelf to the continental slope and rise.

A polymer of caffeyl alcohol in plant seeds

PubMed Central

Chen, Fang; Tobimatsu, Yuki; Havkin-Frenkel, Daphna; Dixon, Richard A.; Ralph, John

2012-01-01

Lignins are complex phenylpropanoid polymers mostly associated with plant secondary cell walls. Lignins arise primarily via oxidative polymerization of the three monolignols, p-coumaryl, coniferyl, and sinapyl alcohols. Of the two hydroxycinnamyl alcohols that represent incompletely methylated biosynthetic products (and are not usually considered to be monolignols), 5-hydroxyconiferyl alcohol is now well established as incorporating into angiosperm lignins, but incorporation of caffeyl alcohol has not been shown. We report here the presence of a homopolymer of caffeyl alcohol in the seed coats of both monocot and dicot plants. This polymer (C-lignin) is deposited to high concentrations in the seed coat during the early stages of seed development in the vanilla orchid (Vanilla planifolia), and in several members of the Cactaceae. The lignin in other parts of the Vanilla plant is conventionally biosynthesized from coniferyl and sinapyl alcohols. Some species of cacti contain only C-lignin in their seeds, whereas others contain only classical guaiacyl/syringyl lignin (derived from coniferyl and sinapyl alcohols). NMR spectroscopic analysis revealed that the Vanilla seed-coat polymer was massively comprised of benzodioxane units and was structurally similar to the polymer synthesized in vitro by peroxidase-catalyzed polymerization of caffeyl alcohol. CD spectroscopy did not detect any optical activity in the seed polymer. These data support the contention that the C-lignin polymer is produced in vivo via combinatorial oxidative radical coupling that is under simple chemical control, a mechanism analogous to that theorized for classical lignin biosynthesis. PMID:22307645

Decomposition behavior of hemicellulose and lignin in the step-change flow rate liquid hot water.

PubMed

Zhuang, Xinshu; Yu, Qiang; Wang, Wen; Qi, Wei; Wang, Qiong; Tan, Xuesong; Yuan, Zhenhong

2012-09-01

Hemicellulose and lignin are the main factors limiting accessibility of hydrolytic enzymes besides the crystallinity of cellulose. The decomposition behavior of hemicellulose and lignin in the step-change flow rate hot water system was investigated. Xylan removal increased from 64.53% for batch system (solid concentration 4.25% w/v, 18 min, 184°C) to 83.78% at high flow rates of 30 ml/min for 8 min, and then 10 ml/min for 10 min. Most of them (80-90%) were recovered as oligosaccharide. It was hypothesized that the flowing water could enhance the mass transfer to improve the sugars recovery. In addition, the solubilization mechanism of lignin in the liquid hot water was proposed according to the results of Fourier transform-infrared spectroscopy and scanning electron microscopy of the water-insoluble fraction and gas chromatography-mass spectrometry of the water-soluble fraction. It was proposed that lignin in the liquid hot water first migrated out of the cell wall in the form of molten bodies, and then flushed out of the reactor. A small quantity of them was further degraded into monomeric products such as vanillin, syringe aldehyde, coniferyl aldehyde, ferulic acid, and p-hydroxy-cinnamic acid. All of these observations would provide important information for the downstream processing, such as purification and concentration of sugars and the enzymatic digestion of residual solid.

The use of natural abundance stable isotopic ratios to indicate the presence of oxygen-containing chemical linkages between cellulose and lignin in plant cell walls.

PubMed

Zhou, Youping; Stuart-Williams, Hilary; Farquhar, Graham D; Hocart, Charles H

2010-06-01

Qualitative and quantitative understanding of the chemical linkages between the three major biochemical components (cellulose, hemicellulose and lignin) of plant cell walls is crucial to the understanding of cell wall structure. Although there is convincing evidence for chemical bonds between hemicellulose and lignin and the absence of chemical bonds between hemicellulose and cellulose, there is no conclusive evidence for the presence of covalent bonds between cellulose and lignin. This is caused by the lack of selectivity of current GC/MS-, NMR- and IR-based methods for lignin characterisation as none of these techniques directly targets the possible ester and ether linkages between lignin and cellulose. We modified the widely-accepted "standard" three-step extraction method for isolating cellulose from plants by changing the order of the steps for hemicellulose and lignin removal (solubilisation with concentrated NaOH and oxidation with acetic acid-containing NaClO(2), respectively) so that cellulose and lignin could be isolated with the possible chemical bonds between them intact. These linkages were then cleaved with NaClO(2) reagent in aqueous media of contrasting (18)O/(16)O ratios. We produced cellulose with higher purity (a lower level of residual hemicellulose and no detectable lignin) than that produced by the "standard" method. Oxidative artefacts may potentially be introduced at the lignin removal stage; but testing showed this to be minimal. Cellulose samples isolated from processing plant-derived cellulose-lignin mixtures in media of contrasting (18)O/(16)O ratios were compared to provide the first quantitative evidence for the presence of oxygen-containing ester and ether bonds between cellulose and lignin in Zea mays leaves. However, no conclusive evidence for the presence or lack of similar bonds in Araucaria cunninghamii wood was obtained. Copyright 2010 Elsevier Ltd. All rights reserved.

Release and retention patterns of organic compounds and nutrients after the cold period in foliar litterfall of pure European larch, common beech and red oak plantations in Lithuania

NASA Astrophysics Data System (ADS)

Čiuldienė, D.; Aleinikovienė, J.; Muraškienė, M.; Marozas, V.; Armolaitis, K.

2017-01-01

This study was carried out in alien warmth-tolerant forest plantations of red oak ( Quercus rubra), common beech ( Fagus sylvatica) and European larch ( Larix decidua). We compared the changes in foliar litterfall mass and biochemical composition after five months of cold period. The mean mass of fresh foliar litterfall collected in late autumn was 30% higher in red oak compared to the larch and beech plantations. After the cold period, the reduction of foliar litterfall mass did not exceed 10% in any of the studied plantations. The fresh foliar litterfall of red oak was the richest in cellular fibre and easily decomposable glucose and nutrients such as P and Mg, larch was distinguished by the highest lignin, N, K and Ca concentrations, while beech fresh foliar litterfall was the poorest in the aforementioned nutrients. After the cold period, the changes in the biochemical composition of foliar litterfall revealed different patterns. In the spring, the beech and red oak foliar litterfall was the richest in N, P and Ca, meanwhile the larch foliar litterfall still had the highest concentration of lignin but, in contrast to the autumn, was the poorest in nutrients. After the cold period Lignin: N, C: N and C: P ratios reached critical values indicating that the foliar litterfall of beech and red oak had started to decompose. The highest lignin concentration and the highest and most stable Lignin: N, C: N, C: P and N: P ratios after the cold period indicated that the slowest foliar litterfall decomposition took place in the larch plantation.

Methylenetetrahydrofolate Reductase Modulates Methyl Metabolism and Lignin Monomer Methylation in Maize.

PubMed

Wu, Zhenying; Ren, Hao; Xiong, Wangdan; Roje, Sanja; Liu, Yuchen; Su, Kunlong; Fu, Chunxiang

2018-05-30

The brown midrib2 (bm2) mutant of maize, with a modified lignin composition, contains a mutation in the methylenetetrahydrofolate reductase (MTHFR) gene. We here show that a MITE transposon insertion caused downregulation of MTHFR with accompanying decrease in 5-methyl-THF and increase in 5, 10-methylene-THF and THF in the bm2 mutant. Furthermore, MTHFR mutation did not change the content of SAM, the methyl group donor involved in the biosynthesis of guaiacyl (G) and syringyl (S) lignins, but increased the level of S-adenosyl homocysteine (SAH), the de-methylation product of SAM. Moreover, competitive inhibition of the maize caffeoyl CoA O-methyltransferase (CCoAOMT) and caffeic acid O-methyltransferase (COMT) enzyme activities by SAH was found, suggesting that SAH/SAM ratio rather than SAM concentration regulates the transmethylation reactions of lignin intermediates. Phenolic profiling revealed that caffeoyl alcohol glucose derivatives accumulated in the mutant, indicating impaired 3-O-methylation of monolignols. A remarkable increase in the unusual catechyl (C) lignin determined in the mutant demonstrates that MTHFR downregulation mainly affects G lignin biosynthesis, consistent with the observation that CCoAOMT is more sensitive to SAH inhibition than COMT. This study which uncovered a novel regulatory mechanism in lignin biosynthesis and may offer an effective approach to utilize lignocellulosic feedstocks in future.

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

NASA Astrophysics Data System (ADS)

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.

Influence of pectins on the solubility and the molar mass distribution of dehydrogenative polymers (DHPs, lignin model compounds).

PubMed

Cathala, B; Monties, B

2001-07-19

Dehydrogenation polymers (DHPs, lignin model compounds) were synthesized in the presence of increasing pectin concentrations using two different methods. The first method ('Zutropfverfahren', ZT) consists in the slow adding of monomers whereas in the second method ('Zulaufverfahren', ZL) all the reactants are added simultaneously. DHPs solubility increases with the pectin concentration in the ZT experiments and remains stable in the ZL experiments. Covalent bonds between pectin and DHP are formed during ZT polymerization resulting in lignin carbohydrate complex (LCC) which keeps the unbound DHPs in solution by the formation of aggregate or micelle-like structures. In contrast LCC are not formed during the ZL process which behave like the DHP reference. The ZT DHP molar masses increase observed is attributed to the reactivity of the high molar mass polymer solubilized by the LCC whereas ZL higher molar mass polymers are precipitated out of the solution and cannot react further.

Improving wood properties for wood utilization through multi-omics integration in lignin biosynthesis

DOE PAGES

Wang, Jack P.; Matthews, Megan L.; Williams, Cranos M.; ...

2018-04-20

A multi-omics quantitative integrative analysis of lignin biosynthesis can advance the strategic engineering of wood for timber, pulp, and biofuels. Lignin is polymerized from three monomers (monolignols) produced by a grid-like pathway. The pathway in wood formation of Populus trichocarpa has at least 21 genes, encoding enzymes that mediate 37 reactions on 24 metabolites, leading to lignin and affecting wood properties. We perturb these 21 pathway genes and integrate transcriptomic, proteomic, fluxomic and phenomic data from 221 lines selected from ~2000 transgenics (6-month-old). The integrative analysis estimates how changing expression of pathway gene or gene combination affects protein abundance, metabolic-flux,more » metabolite concentrations, and 25 wood traits, including lignin, tree-growth, density, strength, and saccharification. The analysis then predicts improvements in any of these 25 traits individually or in combinations, through engineering expression of specific monolignol genes. The analysis may lead to greater understanding of other pathways for improved growth and adaptation.« less

Density Functional Theory Study of Spirodienone Stereoisomers in Lignin

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Improving wood properties for wood utilization through multi-omics integration in lignin biosynthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jack P.; Matthews, Megan L.; Williams, Cranos M.

A multi-omics quantitative integrative analysis of lignin biosynthesis can advance the strategic engineering of wood for timber, pulp, and biofuels. Lignin is polymerized from three monomers (monolignols) produced by a grid-like pathway. The pathway in wood formation of Populus trichocarpa has at least 21 genes, encoding enzymes that mediate 37 reactions on 24 metabolites, leading to lignin and affecting wood properties. We perturb these 21 pathway genes and integrate transcriptomic, proteomic, fluxomic and phenomic data from 221 lines selected from ~2000 transgenics (6-month-old). The integrative analysis estimates how changing expression of pathway gene or gene combination affects protein abundance, metabolic-flux,more » metabolite concentrations, and 25 wood traits, including lignin, tree-growth, density, strength, and saccharification. The analysis then predicts improvements in any of these 25 traits individually or in combinations, through engineering expression of specific monolignol genes. The analysis may lead to greater understanding of other pathways for improved growth and adaptation.« less

Density Functional Theory Study of Spirodienone Stereoisomers in Lignin

DOE PAGES

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

2017-06-28

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

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

PubMed

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

2018-07-01

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

Simulation of the ozone pretreatment of wheat straw.

PubMed

Bhattarai, Sujala; Bottenus, Danny; Ivory, Cornelius F; Gao, Allan Haiming; Bule, Mahesh; Garcia-Perez, Manuel; Chen, Shulin

2015-11-01

Wheat straw is a potential feedstock in biorefinery for sugar production. However, the cellulose, which is the major source of sugar, is protected by lignin. Ozonolysis deconstructs the lignin and makes cellulose accessible to enzymatic digestion. In this study, the change in lignin concentration with different ozonolysis times (0, 1, 2, 3, 5, 7, 10, 15, 20, 30, 60min) was fit to two different kinetic models: one using the model developed by Garcia-Cubero et al. (2012) and another including an outer mass transfer barrier or "cuticle" region where ozone mass transport is reduced in proportion to the mass of unreacted insoluble lignin in the cuticle. The kinetic parameters of two mathematical models for predicting the soluble and insoluble lignin at different pretreatment time were determined. The results showed that parameters derived from the cuticle-based model provided a better fit to experimental results compared to a model without a cuticle layer. Copyright © 2015 Elsevier Ltd. All rights reserved.

Release kinetics of esterified p-coumaric acid and ferulic acid from rice straw in mild alkaline solution.

PubMed

Linh, Tran Ngoc; Fujita, Hirokata; Sakoda, Akiyoshi

2017-05-01

The release kinetics of esterified p-coumaric acid (PCA) and ferulic acid (FA) from rice straw under a mild alkaline condition were investigated to collect fundamental data for the design of a recovery process. The results showed that the straw size, NaOH concentration, and temperature were the key parameters governing release kinetics. The analysis demonstrated that FA is released considerably faster than PCA. The close relationship between lignin and the PCA dissolution indicates a reciprocal and/or simultaneous release. Moreover, PCA is broadly distributed in the lignin network but tends to be located more densely in the lignin fraction which is not easily solubilized by alkaline treatment. In contrast, the release of FA is strongly affected by removal of lignin fraction which is easily solubilized. These results suggest that the release kinetics are controlled by the accessibility of NaOH to their ester sites in the lignin/hemicellulose network, and by their localization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Improving wood properties for wood utilization through multi-omics integration in lignin biosynthesis.

PubMed

Wang, Jack P; Matthews, Megan L; Williams, Cranos M; Shi, Rui; Yang, Chenmin; Tunlaya-Anukit, Sermsawat; Chen, Hsi-Chuan; Li, Quanzi; Liu, Jie; Lin, Chien-Yuan; Naik, Punith; Sun, Ying-Hsuan; Loziuk, Philip L; Yeh, Ting-Feng; Kim, Hoon; Gjersing, Erica; Shollenberger, Todd; Shuford, Christopher M; Song, Jina; Miller, Zachary; Huang, Yung-Yun; Edmunds, Charles W; Liu, Baoguang; Sun, Yi; Lin, Ying-Chung Jimmy; Li, Wei; Chen, Hao; Peszlen, Ilona; Ducoste, Joel J; Ralph, John; Chang, Hou-Min; Muddiman, David C; Davis, Mark F; Smith, Chris; Isik, Fikret; Sederoff, Ronald; Chiang, Vincent L

2018-04-20

A multi-omics quantitative integrative analysis of lignin biosynthesis can advance the strategic engineering of wood for timber, pulp, and biofuels. Lignin is polymerized from three monomers (monolignols) produced by a grid-like pathway. The pathway in wood formation of Populus trichocarpa has at least 21 genes, encoding enzymes that mediate 37 reactions on 24 metabolites, leading to lignin and affecting wood properties. We perturb these 21 pathway genes and integrate transcriptomic, proteomic, fluxomic and phenomic data from 221 lines selected from ~2000 transgenics (6-month-old). The integrative analysis estimates how changing expression of pathway gene or gene combination affects protein abundance, metabolic-flux, metabolite concentrations, and 25 wood traits, including lignin, tree-growth, density, strength, and saccharification. The analysis then predicts improvements in any of these 25 traits individually or in combinations, through engineering expression of specific monolignol genes. The analysis may lead to greater understanding of other pathways for improved growth and adaptation.

Reductive de-polymerization of kraft lignin for chemicals and fuels using formic acid as an in-situ hydrogen source.

PubMed

Huang, Shanhua; Mahmood, Nubla; Tymchyshyn, Matthew; Yuan, Zhongshun; Xu, Chunbao Charles

2014-11-01

In this study, formic acid (FA) was employed as an in-situ hydrogen donor for the reductive de-polymerization of kraft lignin (KL). Under the optimum operating conditions, i.e., 300 °C, 1 h, 18.6 wt.% substrate concentration, 50/50 (v/v) water-ethanol medium with FA at a FA-to-lignin mass ratio of 0.7, KL (Mw∼10,000 g/mol) was effectively de-polymerized, producing de-polymerized lignin (DL, Mw 1270 g/mol) at a yield of ∼90 wt.% and <1 wt.% yield of solid residue (SR). The MW of the DL products decreased with increasing reaction temperature, time and FA-to-lignin mass ratio. The sulfur contents of all DL products were remarkably lower than that in the original KL. It was also demonstrated that FA is a more reactive hydrogen source than external hydrogen for reductive de-polymerization of KL. Copyright © 2014 Elsevier Ltd. All rights reserved.

Single fiber lignin distributions based on the density gradient column method

Treesearch

Brian Boyer; Alan W. Rudie

2007-01-01

The density gradient column method was used to determine the effects of uniform and non-uniform pulping processes on variation in individual fiber lignin concentrations of the resulting pulps. A density gradient column uses solvents of different densities and a mixing process to produce a column of liquid with a smooth transition from higher density at the bottom to...

Eco-friendly processing in enzymatic xylooligosaccharides production from corncob: Influence of pretreatment with sonocatalytic-synergistic Fenton reaction and its antioxidant potentials.

PubMed

Kawee-Ai, Arthitaya; Srisuwun, Aungkana; Tantiwa, Nidtaya; Nontaman, Wimada; Boonchuay, Pinpanit; Kuntiya, Ampin; Chaiyaso, Thanongsak; Seesuriyachan, Phisit

2016-07-01

Delignification can be considered as a feasible process to pretreat lignocellulosic biomass in xylooligosaccharides production after the performance and efficiency has been improved through a few modifications. This study compared various pretreatment strategies such as Fenton, sonocatalytic, and sonocatalytic-synergistic Fenton employed on corncob in order to expose lignin content and saccharides to enhance the xylooligosaccharides yield by enzymatic hydrolysis. The dissolution of lignin and xylooligosaccharides production of corncob was enhanced by ultrasound assisted TiO2 and Fenton reaction. The corncob pretreated with a sonocatalytic-synergistic Fenton reaction gave the highest release of the lignin concentration level (1.03 g/L), dissolution level (80.25%), and xylooligosaccharides content (46.45 mg/g substrate). A two-step pretreatment processes consisting of the alkali treatment (pretreatment) and sonocatalytic-synergistic Fenton process (posttreatment) illustrated that subsequent enzymatic hydrolysis could be enhanced considerably. The release of the lignin concentration and xylooligosaccharides content were 33.20 g/L and 174.81 mg/g substrate, respectively. The antioxidant potential of xylooligosaccharides showed significant differences regarding the amount of xylooligosaccharides and the phenolic compounds produced. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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-steam-exploded corn stover, and consequently significantly improve the conversion of cellulose through enzymatic hydrolysis for biofuel production. The lignin fractions obtained as byproducts could be applied in high performance LPF resin preparation. The proposed model for the integral valorization of corn stover in this study is worth of popularization.

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

NASA Astrophysics Data System (ADS)

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 significantly higher VSC values compared to their parent soil types. However, the higher organic carbon concentrations in Andosol and Alisol (China)-derived paddy soils compared to their parent soil types, could not be explained by an enrichment of lignin-derived phenols. It seems that site specific incorporation of crop residues and properties of the parent soil types are likely more important for organic carbon contents and soil organic matter composition than the effect of paddy management itself.

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

PubMed

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 < 0.001) lower than in the CL. In alfalfa harvested at the 35-day CI, the RL alfalfa resulted in lower (P < 0.001) yield than CL. RL alfalfa lines had 24% and 22% lower (P < 0.001) ADL in Cut-1 and Cut-3 respectively than CL lines. The in vitro dry matter digestibility and aNDF digestibility (both as determined by the near-infrared reflectance method) were greater (P < 0.001) in RL than in CL lines harvested at the 35-day CI. In alfalfa harvested at the 35-day CI, extent of in vitro 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.

The maize brown midrib2 (bm2) gene encodes a methylenetetrahydrofolate reductase that contributes to lignin accumulation

PubMed Central

Tang, Ho Man; Liu, Sanzhen; Hill-Skinner, Sarah; Wu, Wei; Reed, Danielle; Yeh, Cheng-Ting; Nettleton, Dan; Schnable, Patrick S

2014-01-01

The midribs of maize brown midrib (bm) mutants exhibit a reddish-brown color associated with reductions in lignin concentration and alterations in lignin composition. Here, we report the mapping, cloning, and functional and biochemical analyses of the bm2 gene. The bm2 gene was mapped to a small region of chromosome 1 that contains a putative methylenetetrahydrofolate reductase (MTHFR) gene, which is down-regulated in bm2 mutant plants. Analyses of multiple Mu-induced bm2-Mu mutant alleles confirmed that this constitutively expressed gene is bm2. Yeast complementation experiments and a previously published biochemical characterization show that the bm2 gene encodes a functional MTHFR. Quantitative RT-PCR analyses demonstrated that the bm2 mutants accumulate substantially reduced levels of bm2 transcript. Alteration of MTHFR function is expected to influence accumulation of the methyl donor S-adenosyl-l-methionine (SAM). Because SAM is consumed by two methyltransferases in the lignin pathway (Ye et al., 1994), the finding that bm2 encodes a functional MTHFR is consistent with its lignin phenotype. Consistent with this functional assignment of bm2, the expression patterns of genes in a variety of SAM-dependent or -related pathways, including lignin biosynthesis, are altered in the bm2 mutant. Biochemical assays confirmed that bm2 mutants accumulate reduced levels of lignin with altered composition compared to wild-type. Hence, this study demonstrates a role for MTHFR in lignin biosynthesis. PMID:24286468

Molecular architecture requirements for polymer-grafted lignin superplasticizers.

PubMed

Gupta, Chetali; Sverdlove, Madeline J; Washburn, Newell R

2015-04-07

Superplasticizers are a class of anionic polymer dispersants used to inhibit aggregation in hydraulic cement, lowering the yield stress of cement pastes to improve workability and reduce water requirements. The plant-derived biopolymer lignin is commonly used as a low-cost/low-performance plasticizer, but attempts to improve its effects on cement rheology through copolymerization with synthetic monomers have not led to significant improvements. Here we demonstrate that kraft lignin can form the basis for high-performance superplasticizers in hydraulic cement, but the molecular architecture must be based on a lignin core with a synthetic-polymer corona that can be produced via controlled radical polymerization. Using slump tests of ordinary Portland cement pastes, we show that polyacrylamide-grafted lignin prepared via reversible addition-fragmentation chain transfer polymerization can reduce the yield stress of cement paste to similar levels as a leading commercial polycarboxylate ether superplasticizer at concentrations ten-fold lower, although the lignin material produced via controlled radical polymerization does not appear to reduce the dynamic viscosity of cement paste as effectively as the polycarboxylate superplasticizer, despite having a similar affinity for the individual mineral components of ordinary Portland cement. In contrast, polyacrylamide copolymerized with a methacrylated kraft lignin via conventional free radical polymerization having a similar overall composition did not reduce the yield stress or the viscosity of cement pastes. While further work is required to elucidate the mechanism of this effect, these results indicate that controlling the architecture of polymer-grafted lignin can significantly enhance its performance as a superplasticizer for cement.

Reactivity improvement of cellulolytic enzyme lignin via mild hydrothermal modification.

PubMed

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.

Efficient degradation of lignin in raw wood via pretreatment with heteropoly acids in γ-valerolactone/water.

PubMed

Zhang, Libo; Zheng, Wenxiu; Wang, Ziming; Ma, Yubo; Jiang, Ling; Wang, Tianfu

2018-08-01

The aim of this work was to study the degradation of lignin in raw wood via pretreatment with heteropoly acids as substitutes for traditional H 2 SO 4 in γ-valerolactone/water. By optimizing catalyst concentration, reaction time and temperature, the optimal lignin degradation conditions are obtained (130 °C, 3 h and 20 mM silicotungstic acid). SEM and FTIR measurements demonstrated the efficient lignin degradation ability of HPAs in the GVL/H 2 O solvent, with negligible damage to cellulose within the raw wood. Furthermore, an elaborated enzymatic hydrolysis study of the thus obtained cellulosic feedstock revealed its suitability for enzymatic digestion, with great potential as starting material for the production of fermentable sugar from biomass in future biorefinery applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Eco-friendly Fibre from Recycled Polypropylene of Bottle Cap Waste and Lignin

NASA Astrophysics Data System (ADS)

Soekoco, A. S.; Basuki, A.; Mardiyati

2016-01-01

Ecofriendly fibre is one of potential alternatives to fulfill the rising demand in textile material supply which is limited due to the decreasing reserve of oil. Large amount of polypropylene waste from bottle cap and lignin as a byproduct from pulp industry are potential solutions. Grinded polypropylene bottle cap was blended with lignin powder in concentration of 5 wt. % processed by melt spinning at 170° C temperature. The fibres produced have an average diameter 170 and 250 micrometres. In view of the mechanical properties. the tensile strength is 11.9 MPa for fibre with 170 micrometres diameter and 14.7 MPa for fibre with 250 micrometres diameter. Fibre surface morphology was further studied using micron microscope. and the result shows black flocks spread in the fibre. indicating that the lignin does not blend evenly.

Enhanced removal of hazardous dye form aqueous solutions and real textile wastewater using bifunctional chitin/lignin biosorbent.

PubMed

Wawrzkiewicz, Monika; Bartczak, Przemysław; Jesionowski, Teofil

2017-06-01

A new biomaterial based on chitin and lignin was prepared and applied for the removal of hazardous dye C.I. Direct Blue 71 (DB71) from aqueous solutions and wastewaters. The dye sorption on the chitin/lignin biosorbent (Ch/L) was examined depending on the initial dye concentration (50-200mg/L), phase contact time (1-1440min), kind of auxiliaries (NaCl, Na 2 SO 4 , anionic surfactant SDS) and their concentrations (1-20g/L salts, 0.1-0.75g/L SDS), initial solution pH as well as temperature (20-50°C). The equilibrium and kinetic characteristics of C.I. Direct Blue 71 uptake by chitin/lignin followed by the Freundlich isotherm model and the pseudo-second order model rather than the Langmuir, Tempkin models, and pseudo-first order model. C.I. Direct Blue 71 adsorption on chitin/lignin was spontaneous (-2.86 to -8.14kJ/mol) and endothermic (60.1kJ/mol). The possibilities of dye elution and reuse by means of the batch method were investigated and as follows the chemical reaction is an inseparable sorption mechanism. Purification of wastewaters containing direct dyes was made with 91% efficiency after 1h of phase contact time. For comparison, data obtained or obtained results in the DB71-chitin (Ch) system were also presented. Copyright © 2017 Elsevier B.V. All rights reserved.

Model-based characterisation of growth performance and l-lactic acid production with high optical purity by thermophilic Bacillus coagulans in a lignin-supplemented mixed substrate medium.

PubMed

Glaser, Robert; Venus, Joachim

2017-07-25

Three Bacillus coagulans strains were characterised in terms of their ability to grow in lignin-containing fermentation media and to consume the lignocellulose-related sugars glucose, xylose, and arabinose. An optical-density high-throughput screening was used for precharacterisation by means of different mathematical models for comparison (Logistic, Gompertz, Baranyi, Richards & Stannard, and Schnute). The growth response was characterised by the maximum growth rate and lag time. For a comparison of the screening and fermentation results, an unstructured mathematical model was proposed to characterise the lactate production, bacterial growth and substrate consumption. The growth model was then applied to fermentation procedures using wheat straw hydrolysates. The results indicated that the unstructured growth model can be used to evaluate lactate producing fermentation. Under the experimental fermentation conditions, one strain showed the ability to tolerate a high lignin concentration (2.5g/L) but lacked the capacity for sufficient pentose uptake. The lactate yield of the strains that were able to consume all sugar fractions of glucose, xylose and arabinose was ∼83.4%. A photometric measurement at 280nm revealed a dynamic change in alkali-lignin concentrations during lactate producing fermentation. A test of decolourisation of vanillin, ferulic acid, and alkali-lignin samples also showed the decolourisation performance of the B. coagulans strains under study. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

The influence of soil type and altered lignin biosynthesis on the physiology, growth and carbon allocation in Populus tremuloides

Treesearch

Jessica E. Hancock; Kate L. Bradley; Christian P. Giardina; Kurt S. Pregitzer

2008-01-01

Plants influence soil carbon (C) formation through the quality and quantity of C released to soil. Soil type, in turn can modify a plant's influence on soil through effects on plant production, tissue quality and regulation of soil C decomposition and stabilization. Wild-type aspen and three transgenic aspen lines expressing reduced stem lignin concentrations and/...

Bonding of wood fiber composites using a synthetic chelator-lignin activation system

Treesearch

D. Yelle; B. Goodell; D.J. Gardner; A. Amirbahman; P. Winistofer; S. Shaler

2004-01-01

Wood fibers, after thermo-mechanical pulping, have a high concentration of lignin on the outer surface of the fiber; the residual middle lamella of the woody cell wall. When wood fibers are oxidatively treated with a chelator produced by Gloeophyllum trabeum (a brown-rot fungus), in the presence of hydrogen peroxide (H2O2) and ferric iron (FeIII), free radicals are...

Increased saccharification yields from aspen biomass upon treatment with enzymatically generated peracetic acid.

PubMed

Duncan, Shona; Jing, Qing; Katona, Adrian; Kazlauskas, Romas J; Schilling, Jonathan; Tschirner, Ulrike; Aldajani, Waleed Wafa

2010-03-01

The recalcitrance of lignocellulosic biomass to enzymatic release of sugars (saccharification) currently limits its use as feedstock for biofuels. Enzymatic hydrolysis of untreated aspen wood releases only 21.8% of the available sugars due primarily to the lignin barrier. Nature uses oxidative enzymes to selectively degrade lignin in lignocellulosic biomass, but thus far, natural enzymes have been too slow for industrial use. In this study, oxidative pretreatment with commercial peracetic acid (470 mM) removed 40% of the lignin (from 19.9 to 12.0 wt.% lignin) from aspen and enhanced the sugar yields in subsequent enzymatic hydrolysis to about 90%. Increasing the amount of lignin removed correlated with increasing yields of sugar release. Unfortunately, peracetic acid is expensive, and concentrated forms can be hazardous. To reduce costs and hazards associated with using commercial peracetic acid, we used a hydrolase to catalyze the perhydrolysis of ethyl acetate generating 60-70 mM peracetic acid in situ as a pretreatment to remove lignin from aspen wood. A single pretreatment was insufficient, but multiple cycles (up to eight) removed up to 61.7% of the lignin enabling release of >90% of the sugars during saccharification. This value corresponds to a predicted 581 g of fermentable sugars from 1 kg of aspen wood. Improvements in the enzyme stability are needed before the enzymatically generated peracetic acid is a commercially viable alternative.

Cellulose and lignin biosynthesis is altered by ozone in wood of hybrid poplar (Populus tremula×alba)

PubMed Central

Richet, Nicolas; Afif, Dany; Huber, Françoise; Pollet, Brigitte; Banvoy, Jacques; El Zein, Rana; Lapierre, Catherine; Dizengremel, Pierre; Perré, Patrick; Cabané, Mireille

2011-01-01

Wood formation in trees is a dynamic process that is strongly affected by environmental factors. However, the impact of ozone on wood is poorly documented. The objective of this study was to assess the effects of ozone on wood formation by focusing on the two major wood components, cellulose and lignin, and analysing any anatomical modifications. Young hybrid poplars (Populus tremula×alba) were cultivated under different ozone concentrations (50, 100, 200, and 300 nl l−1). As upright poplars usually develop tension wood in a non-set pattern, the trees were bent in order to induce tension wood formation on the upper side of the stem and normal or opposite wood on the lower side. Biosynthesis of cellulose and lignin (enzymes and RNA levels), together with cambial growth, decreased in response to ozone exposure. The cellulose to lignin ratio was reduced, suggesting that cellulose biosynthesis was more affected than that of lignin. Tension wood was generally more altered than opposite wood, especially at the anatomical level. Tension wood may be more susceptible to reduced carbon allocation to the stems under ozone exposure. These results suggested a coordinated regulation of cellulose and lignin deposition to sustain mechanical strength under ozone. The modifications of the cellulose to lignin ratio and wood anatomy could allow the tree to maintain radial growth while minimizing carbon cost. PMID:21357770

Relationship between Fungal Biomass Production and the Brightening of Hardwood Kraft Pulp by Coriolus versicolor

PubMed Central

Kirkpatrick, Neil; Reid, Ian D.; Ziomek, Edmund; Ho, Christopher; Paice, Michael G.

1989-01-01

The white-rot fungus Coriolus versicolor increased the brightness of hardwood kraft pulp by two mechanisms depending on the concentration of available nitrogen. In low-nitrogen conditions, the brightening process was a chemical effect mediated by the fungus, associated with the removal of residual lignin in the pulp; kappa number was used as an indicator of lignin concentration. A five-day treatment in low-nitrogen conditions increased the brightness of hardwood kraft pulp from 36.2 to 54.5%, with a corresponding decrease in kappa number from 12.0 to 8.5, equivalent to a reduction in the lignin concentration from ca. 2.0% (wt/wt) to ca. 1.4% (wt/wt). Under these conditions, we concluded that the brightening of the pulp was a secondary metabolic event initiated after the depletion of available nitrogen. This method of brightening has been described as bleaching or biobleaching. By contrast, in high-nitrogen conditions, the brightening was a physical effect associated with the dilution of the dark pulp fibers by the relatively high levels of brighter fungal mycelium produced. Since this method of brightening was not evidently associated with lignin removal, it cannot be described as bleaching. In pulp samples brightened in high-nitrogen conditions, as brightness increased, there was a corresponding increase in kappa number. This observation was explained by the consumption of potassium permanganate by the fungal mycelium, which interfered with kappa number determinations at high fungal biomass levels. PMID:16347907

Intrapopulation Genotypic Variation of Foliar Secondary Chemistry during Leaf Senescence and Litter Decomposition in Silver Birch (Betula pendula)

PubMed Central

Paaso, Ulla; Keski-Saari, Sarita; Keinänen, Markku; Karvinen, Heini; Silfver, Tarja; Rousi, Matti; Mikola, Juha

2017-01-01

Abundant secondary metabolites, such as condensed tannins, and their interpopulation genotypic variation can remain through plant leaf senescence and affect litter decomposition. Whether the intrapopulation genotypic variation of a more diverse assortment of secondary metabolites equally persists through leaf senescence and litter decomposition is not well understood. We analyzed concentrations of intracellular phenolics, epicuticular flavonoid aglycones, epicuticular triterpenoids, condensed tannins, and lignin in green leaves, senescent leaves and partly decomposed litter of silver birch, Betula pendula. Broad-sense heritability (H2) and coefficient of genotypic variation (CVG) were estimated for metabolites in senescent leaves and litter using 19 genotypes selected from a B. pendula population in southern Finland. We found that most of the secondary metabolites remained through senescence and decomposition and that their persistence was related to their chemical properties. Intrapopulation H2 and CVG for intracellular phenolics, epicuticular flavonoid aglycones and condensed tannins were high and remarkably, increased from senescent leaves to decomposed litter. The rank of genotypes in metabolite concentrations was persistent through litter decomposition. Lignin was an exception, however, with a diminishing genotypic variation during decomposition, and the concentrations of lignin and condensed tannins had a negative genotypic correlation in the senescent leaves. Our results show that secondary metabolites and their intrapopulation genotypic variation can for the most part remain through leaf senescence and early decomposition, which is a prerequisite for initial litter quality to predict variation in litter decomposition rates. Persistent genotypic variation also opens an avenue for selection to impact litter decomposition in B. pendula populations through acting on their green foliage secondary chemistry. The negative genotypic correlations and diminishing heritability of lignin concentrations may, however, counteract this process. PMID:28694813

Carbon Structural Investigations of Concentric Layers Within Macro-aggregates From Forest and Agricultural Soils

NASA Astrophysics Data System (ADS)

Dria, K. J.; Gamblin, D. E.; Smucker, A. J.; Park, E.; Filley, T. R.

2004-12-01

Much of the current research on the potential of agricultural and forest soils to act as sinks for greenhouse gases focuses on the capacity of the systems to form long-term stabilized fractions of soil organic matter (SOM). One proposed mechanism is that carbon is sequestered within soil aggregate interiors during the aggregation process. Repeated wetting-drying cycles change internal pore geometries and associated microhabitats and create more stable macro-aggregates. Research by Smucker and coworkers (EGU Abstracts, 2004) suggest that the exterior portions of aggregates contain greater concentrations of C and N than their interiors, establishing gradients of \\ä13C values across these aggregates. We present the results of a study to test if there exists molecular evidence of such gradients. Soil samples from forest, conventional tillage (CT) and no tillage (NT) agriculture ecosystems in Hoytville and Wooster LTER sites were gently sieved into various size fractions. Soil macro-aggregates (6.3-9.5mm) were peeled, by mechanical erosion chambers, into concentric layers and separated into exterior, transitional and interior regions. Alkaline CuO oxidation was used to determine the composition of lignin, suberin, and cutin biopolymers to determine changes in source and degradative states of SOM. Preliminary results indicate that both soils show similar relative yields of lignin and hydroxyl fatty acids with a greater abundance of lignin than cutin and suberin acids. Greater abundances (per 100mg organic carbon) of CuO products were observed in the native forest than in either agricultural system. The lignin in the NT agricultural soil was least oxidized, followed by the forest soils, then the CT agricultural soils. For both soils, slight trends in biopolymer concentrations were observed between the exterior, transitional and interior regions of the aggregates from the forest and CT or NT ecosystems.

Intrapopulation Genotypic Variation of Foliar Secondary Chemistry during Leaf Senescence and Litter Decomposition in Silver Birch (Betula pendula).

PubMed

Paaso, Ulla; Keski-Saari, Sarita; Keinänen, Markku; Karvinen, Heini; Silfver, Tarja; Rousi, Matti; Mikola, Juha

2017-01-01

Abundant secondary metabolites, such as condensed tannins, and their interpopulation genotypic variation can remain through plant leaf senescence and affect litter decomposition. Whether the intrapopulation genotypic variation of a more diverse assortment of secondary metabolites equally persists through leaf senescence and litter decomposition is not well understood. We analyzed concentrations of intracellular phenolics, epicuticular flavonoid aglycones, epicuticular triterpenoids, condensed tannins, and lignin in green leaves, senescent leaves and partly decomposed litter of silver birch, Betula pendula . Broad-sense heritability ( H 2 ) and coefficient of genotypic variation ( CV G ) were estimated for metabolites in senescent leaves and litter using 19 genotypes selected from a B. pendula population in southern Finland. We found that most of the secondary metabolites remained through senescence and decomposition and that their persistence was related to their chemical properties. Intrapopulation H 2 and CV G for intracellular phenolics, epicuticular flavonoid aglycones and condensed tannins were high and remarkably, increased from senescent leaves to decomposed litter. The rank of genotypes in metabolite concentrations was persistent through litter decomposition. Lignin was an exception, however, with a diminishing genotypic variation during decomposition, and the concentrations of lignin and condensed tannins had a negative genotypic correlation in the senescent leaves. Our results show that secondary metabolites and their intrapopulation genotypic variation can for the most part remain through leaf senescence and early decomposition, which is a prerequisite for initial litter quality to predict variation in litter decomposition rates. Persistent genotypic variation also opens an avenue for selection to impact litter decomposition in B. pendula populations through acting on their green foliage secondary chemistry. The negative genotypic correlations and diminishing heritability of lignin concentrations may, however, counteract this process.

Microwave-assisted co-pyrolysis of pretreated lignin and soapstock for upgrading liquid oil: Effect of pretreatment parameters on pyrolysis behavior.

PubMed

Duan, Dengle; Ruan, Roger; Lei, Hanwu; Liu, Yuhuan; Wang, Yunpu; Zhang, Yayun; Zhao, Yunfeng; Dai, Leilei; Wu, Qiuhao; Zhang, Shumei

2018-06-01

The co-pyrolysis of pretreated lignin and soapstock was carried out to upgrade vapors under microwave irradiation. Results showed that the yield of 29.92-42.21 wt% of upgraded liquid oil was achieved under varied pretreatment conditions. Char yield decreased from 32.44 wt% for untreated control to 24.35 wt% for the 150 °C pretreated samples. The increased temperature, irradiation time and acid concentration were conducive to decrease the relative contents of phenols and oxygenates in liquid oils. The main components of the liquid oil were gasoline fraction (mono-aromatics and C5-C12 aliphatics), which ranged from 57.38 to 71.98% under various pretreatment conditions. Meanwhile, the diesel fraction (C12+ aliphatics) ranged from 13.16 to 22.62% from co-pyrolysis of pretreated lignin and soapstock, comparing with 10.18% of C12+ aliphatics from co-pyrolysis of non-pretreated lignin and soapstock. A possible mechanism was proposed for co-pyrolysis of pretreated lignin and soapstock for upgraded liquid oils. Copyright © 2018 Elsevier Ltd. All rights reserved.

The influence of lignin on steam pretreatment and mechanical pulping of poplar to achieve high sugar recovery and ease of enzymatic hydrolysis.

PubMed

Chandra, Richard P; Chu, QiuLu; Hu, Jinguang; Zhong, Na; Lin, Mandy; Lee, Jin-Suk; Saddler, Jack

2016-01-01

With the goal of enhancing overall carbohydrate recovery and reducing enzyme loading refiner mechanical pulping and steam pretreatment (210°C, 5 min) were used to pretreat poplar wood chips. Neutral sulphonation post-treatment indicated that, although the lignin present in the steam pretreated substrate was less reactive, the cellulose-rich, water insoluble component was more accessible to cellulases and Simons stain. This was likely due to lignin relocation as the relative surface lignin measured by X-ray photoelectron spectroscopy increased from 0.4 to 0.8. The integration of sulphite directly into steam pretreatment resulted in the solubilisation of 60% of the lignin while more than 80% of the carbohydrate present in the original substrate was recovered in the water insoluble fraction after Na2CO3 addition. More than 80% of the sugars present in the original cellulose and xylan could be recovered after 48 h using an enzyme loading of 20 mg protein/g cellulose at a 10% substrate concentration. Copyright © 2015 Elsevier Ltd. All rights reserved.

Delayed fungal evolution did not cause the Paleozoic peak in coal production.

PubMed

Nelsen, Matthew P; DiMichele, William A; Peters, Shanan E; Boyce, C Kevin

2016-03-01

Organic carbon burial plays a critical role in Earth systems, influencing atmospheric O2 and CO2 concentrations and, thereby, climate. The Carboniferous Period of the Paleozoic is so named for massive, widespread coal deposits. A widely accepted explanation for this peak in coal production is a temporal lag between the evolution of abundant lignin production in woody plants and the subsequent evolution of lignin-degrading Agaricomycetes fungi, resulting in a period when vast amounts of lignin-rich plant material accumulated. Here, we reject this evolutionary lag hypothesis, based on assessment of phylogenomic, geochemical, paleontological, and stratigraphic evidence. Lignin-degrading Agaricomycetes may have been present before the Carboniferous, and lignin degradation was likely never restricted to them and their class II peroxidases, because lignin modification is known to occur via other enzymatic mechanisms in other fungal and bacterial lineages. Furthermore, a large proportion of Carboniferous coal horizons are dominated by unlignified lycopsid periderm with equivalent coal accumulation rates continuing through several transitions between floral dominance by lignin-poor lycopsids and lignin-rich tree ferns and seed plants. Thus, biochemical composition had little relevance to coal accumulation. Throughout the fossil record, evidence of decay is pervasive in all organic matter exposed subaerially during deposition, and high coal accumulation rates have continued to the present wherever environmental conditions permit. Rather than a consequence of a temporal decoupling of evolutionary innovations between fungi and plants, Paleozoic coal abundance was likely the result of a unique combination of everwet tropical conditions and extensive depositional systems during the assembly of Pangea.

Delayed fungal evolution did not cause the Paleozoic peak in coal production

PubMed Central

Nelsen, Matthew P.; DiMichele, William A.; Peters, Shanan E.; Boyce, C. Kevin

2016-01-01

Organic carbon burial plays a critical role in Earth systems, influencing atmospheric O2 and CO2 concentrations and, thereby, climate. The Carboniferous Period of the Paleozoic is so named for massive, widespread coal deposits. A widely accepted explanation for this peak in coal production is a temporal lag between the evolution of abundant lignin production in woody plants and the subsequent evolution of lignin-degrading Agaricomycetes fungi, resulting in a period when vast amounts of lignin-rich plant material accumulated. Here, we reject this evolutionary lag hypothesis, based on assessment of phylogenomic, geochemical, paleontological, and stratigraphic evidence. Lignin-degrading Agaricomycetes may have been present before the Carboniferous, and lignin degradation was likely never restricted to them and their class II peroxidases, because lignin modification is known to occur via other enzymatic mechanisms in other fungal and bacterial lineages. Furthermore, a large proportion of Carboniferous coal horizons are dominated by unlignified lycopsid periderm with equivalent coal accumulation rates continuing through several transitions between floral dominance by lignin-poor lycopsids and lignin-rich tree ferns and seed plants. Thus, biochemical composition had little relevance to coal accumulation. Throughout the fossil record, evidence of decay is pervasive in all organic matter exposed subaerially during deposition, and high coal accumulation rates have continued to the present wherever environmental conditions permit. Rather than a consequence of a temporal decoupling of evolutionary innovations between fungi and plants, Paleozoic coal abundance was likely the result of a unique combination of everwet tropical conditions and extensive depositional systems during the assembly of Pangea. PMID:26787881

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

PubMed

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.

The maize brown midrib2 (bm2) gene encodes a methylenetetrahydrofolate reductase that contributes to lignin accumulation.

PubMed

Tang, Ho Man; Liu, Sanzhen; Hill-Skinner, Sarah; Wu, Wei; Reed, Danielle; Yeh, Cheng-Ting; Nettleton, Dan; Schnable, Patrick S

2014-02-01

The midribs of maize brown midrib (bm) mutants exhibit a reddish-brown color associated with reductions in lignin concentration and alterations in lignin composition. Here, we report the mapping, cloning, and functional and biochemical analyses of the bm2 gene. The bm2 gene was mapped to a small region of chromosome 1 that contains a putative methylenetetrahydrofolate reductase (MTHFR) gene, which is down-regulated in bm2 mutant plants. Analyses of multiple Mu-induced bm2-Mu mutant alleles confirmed that this constitutively expressed gene is bm2. Yeast complementation experiments and a previously published biochemical characterization show that the bm2 gene encodes a functional MTHFR. Quantitative RT-PCR analyses demonstrated that the bm2 mutants accumulate substantially reduced levels of bm2 transcript. Alteration of MTHFR function is expected to influence accumulation of the methyl donor S-adenosyl-L-methionine (SAM). Because SAM is consumed by two methyltransferases in the lignin pathway (Ye et al., ), the finding that bm2 encodes a functional MTHFR is consistent with its lignin phenotype. Consistent with this functional assignment of bm2, the expression patterns of genes in a variety of SAM-dependent or -related pathways, including lignin biosynthesis, are altered in the bm2 mutant. Biochemical assays confirmed that bm2 mutants accumulate reduced levels of lignin with altered composition compared to wild-type. Hence, this study demonstrates a role for MTHFR in lignin biosynthesis. © 2013 The Authors The Plant Journal © 2013 John Wiley & Sons Ltd.

Fuel Pellets from Wheat Straw: The Effect of Lignin Glass Transition and Surface Waxes on Pelletizing Properties

Treesearch

Wolfgang Stelte; Craig Clemons; Jens K. Holm; Jesper Ahrenfeldt; Ulrik B. Henriksen; Anand R. Sanadi

2012-01-01

The utilization of wheat straw as a renewable energy resource is limited due to its low bulk density. Pelletizing wheat straw into fuel pellets of high density increases its handling properties but is more challenging compared to pelletizing wood biomass. Straw has a lower lignin content and a high concentration of hydrophobic waxes on its outer surface that may limit...

Global estimate of net annual carbon flow to phenylpropanoid metabolism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walton, A.B.; Norman, E.G.; Turpin, D.H.

1993-05-01

The steady increase in the concentration of CO[sub 2] in the atmosphere is the focus of renewed interest in the global carbon cycle. Current research is centered upon modeling the effects of the increasing CO[sub 2] concentrations, and thus global warning, on global plant homeostasis. It has been estimated that the annual net primary production (NPP) values for terrestrial and oceanic biomes are 59.9 and 35 Pg C-yr[sup [minus]1], respectively (Melillo et al., 1990). Based on these NPP values, we have estimated the annual C flow to phenlpropanoid metabolism. In our calculation, lignin was used as a surrogate for phenylpropanoidmore » compounds, as lignin is the second most abundant plant polymer. This approach means that our estimate defines the lower limit of C flow to phenylpropanoid metabolism. Each biome was considered separately to determine the percent of the NPP which was directed to the biosynthesis of leaves, stems/branches, and roots. From published values of the lignin content of these organs, the total amount of C directed to the biosynthesis of lignin in each biome was determined. This was used to obtain a global value. Implications of these estimates will be discussed with reference to plant carbon and nitrogen metabolism.« less

Evaluation of monitoring indicators for the post-closure care of a landfill for MSW characterized with low lignin content.

PubMed

Zheng, Wei; Lü, Fan; Bolyard, Stephanie C; Shao, Liming; Reinhart, Debra R; He, Pinjing

2015-02-01

To understand the applicability of the termination indicators for landfill municipal solid waste (MSW) with low initial lignin content, four different accelerated landfill stabilization techniques were applied to anaerobic landfilled waste, including anaerobic flushing with water, anaerobic flushing with Fenton-treated leachate, and aerobic flushing with Fenton-treated and UV/H2O2-treated leachate. Termination indicators, including total organic carbon (TOC), ammonia-N (NH4(+)-N), the ratio of UV absorbance at 254 nm to TOC concentration (SUVA254), fluorescence spectra of leachate, methane production, oxygen consumption, lignocellulose content, and humus-like content were evaluated. Results suggest that oxygen consumption related indicators used as a termination indicator for low-lignin-content MSW were more sensitive than methane consumption related indicators. Aeration increased humic acid (HA) and (HA+FA)/HyI content by 2.9 and 1.7 times compared to the anaerobically stabilized low-lignin-content MSW. On the other hand, both the fulvic acid (FA) and hydrophilic (HyI) fractions remained constant regardless of stabilization technique. The target value developed for low-lignin-content MSW was quite different than developed countries mainly due to low residual biodegradable organic carbon content in stabilized low-lignin-content MSW. Copyright © 2014 Elsevier Ltd. All rights reserved.

The use of organic markers in the differentiation of organic inputs to aquatic systems

NASA Astrophysics Data System (ADS)

Reeves, A. D.

1995-04-01

In previous projects the estuarine distributions of a variety of molecular organic markers have been described and discussed in relation to sources, transport mechanisms and fates of anthropogenic and biogenic inputs to estuaries. Molecular markers have been used successfully to establish terrestrial inputs to marine water and to trace pollutants in water-ways. One of the components selected for study was lignin. Lignin compounds are phenolic polymers that occur as major constituents of the cell walls of vascular plants. Their source, natural abundance, wide distribution and resistance to microbial degradation render them good terrestrial markers and, via their phenolic aldehyde oxidation products, afford characterisation of their source material. In previous work, ratios of various lignin components suggest that permanently suspended material contains a significant proportion of degraded angiosperm tissues whereas, in resuspended material, a component of gymnosperm material is indicated. Comparison of the lignin concentrations in the suspended material with those in underlying sediment reveals that the permanently suspended material is preferentially enriched in lignin. This is due, at least in part, to the relative buoyancy of lignin-containing prticles which causes them to float in near-surface water. This paper considers whether such methodology can be usefully applied to the determination of terrestrial inputs to lentic environments.

Sonocatalytic-Fenton reaction for enhanced OH radical generation and its application to lignin degradation.

PubMed

Ninomiya, Kazuaki; Takamatsu, Hiromi; Onishi, Ayaka; Takahashi, Kenji; Shimizu, Nobuaki

2013-07-01

The present study demonstrated that the combined use of the sonocatalytic reaction (using ultrasound and titanium dioxide) and the Fenton reaction exhibited synergistically enhanced hydroxyl (OH) radical generation. Dihydroxybenzoic acid (DHBA) concentration as index of OH radical generation was 13 and 115 μM at 10 min in the sonocatalytic reaction and Fenton reaction, respectively. On the other hand, the DHBA concentration was 378 μM at 10 min in the sonocatalytic-Fenton reaction. The sonocatalytic-Fenton reaction was used for degradation of lignin. The lignin degradation ratio was 1.8%, 49.9%, and 60.0% at 180 min in the sonocatalytic reaction, Fenton reaction, and sonocatalytic-Fenton reaction, respectively. Moreover, the sonocatalytic-Fenton reaction was applied to pretreatment of lignocellulosic biomass to enhance subsequent enzymatic saccharification. The cellulose saccharification ratio was 11%, 14%, 16% and 25% at 360 min of pretreatment by control reaction, the sonocatalytic reaction, Fenton reaction, and sonocatalytic-Fenton reaction, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Optimization of organosolv pretreatment of rice straw for enhanced biohydrogen production using Enterobacter aerogenes.

PubMed

Asadi, Nooshin; Zilouei, Hamid

2017-03-01

Ethanol organosolv pretreated rice straw was used to produce biohydrogen using Enterobacter aerogenes. The effect of temperature (120-180°C), residence time (30-90min), and ethanol concentration (45-75%v/v) on the hydrogen yield, residual biomass, and lignin recovery was investigated using RSM. In contrast to the residual solid and lignin recovery, no considerable trend could be observed for the changes in the hydrogen yield at different treatment severities. The maximum hydrogen yield of 19.73mlg -1 straw was obtained at the ethanol concentration of 45%v/v and 180°C for 30min. Furthermore, the potential amount of biohydrogen was estimated in the top ten rice producing nations using the experimental results. Approximately 355.8kt of hydrogen and 11.3Mt of lignin could globally be produced. Based on a Monte Carlo analysis, the production of biohydrogen from rice straw has the lowest risk in China and the highest in Japan. Copyright © 2016 Elsevier Ltd. All rights reserved.

The effect of phenolic and polyphenolic compounds on the development of drug resistance.

PubMed

Birosová, Lucia; Mikulásová, Mária; Chromá, Magdaléna

2005-12-01

The effect of two phenolic compounds vanillin (4-hydroxy-3-methoxybenzaldehyde) and lignin on the development of drug/antibiotic resistance in Salmonella typhimurium was studied. Using the modified Ames test we have shown that vanillin alone has negligible effect on spontaneous mutability to ciprofloxacin and gentamicin resistance. At the tested concentrations vanillin reduces the toxicity of 4-nitroquinoline-N-oxide (4NQO) and reduces the ability of this compound to induce mutations leading to ciprofloxacin but not to gentamicin resistance. Lignin at higher concentrations increases mutagenicity to ciprofloxacin resistance and possess considerable inhibition effect on the spontaneous and 4NQO induced mutability to gentamicin resistance.

Microbial degradation of plant leachate alters lignin phenols and trihalomethane precursors

USGS Publications Warehouse

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.

Flux and Seasonality of Dissolved Organic Matter From the Northern Dvina (Severnaya Dvina) River, Russia

NASA Astrophysics Data System (ADS)

Johnston, Sarah Ellen; Shorina, Natalia; Bulygina, Ekaterina; Vorobjeva, Taisya; Chupakova, Anna; Klimov, Sergey I.; Kellerman, Anne M.; Guillemette, Francois; Shiklomanov, Alexander; Podgorski, David C.; Spencer, Robert G. M.

2018-03-01

Pan-Arctic riverine dissolved organic carbon (DOC) fluxes represent a major transfer of carbon from land-to-ocean, and past scaling estimates have been predominantly derived from the six major Arctic rivers. However, smaller watersheds are constrained to northern high-latitude regions and, particularly with respect to the Eurasian Arctic, have received little attention. In this study, we evaluated the concentration of DOC and composition of dissolved organic matter (DOM) via optical parameters, biomarkers (lignin phenols), and ultrahigh resolution mass spectrometry in the Northern Dvina River (a midsized high-latitude constrained river). Elevated DOC, lignin concentrations, and aromatic DOM indicators were observed throughout the year in comparison to the major Arctic rivers with seasonality exhibiting a clear spring freshet and also some years a secondary pulse in the autumn concurrent with the onset of freezing. Chromophoric DOM absorbance at a350 was strongly correlated to DOC and lignin across the hydrograph; however, the relationships did not fit previous models derived from the six major Arctic rivers. Updated DOC and lignin fluxes were derived for the pan-Arctic watershed by scaling from the Northern Dvina resulting in increased DOC and lignin fluxes (50 Tg yr-1 and 216 Gg yr-1, respectively) compared to past estimates. This leads to a reduction in the residence time for terrestrial carbon in the Arctic Ocean (0.5 to 1.8 years). These findings suggest that constrained northern high-latitude rivers are underrepresented in models of fluxes based from the six largest Arctic rivers with important ramifications for the export and fate of terrestrial carbon in the Arctic Ocean.

Synergetic effect of dilute acid and alkali treatments on fractional application of rice straw.

PubMed

Sun, Shaolong; Chen, Weijing; Tang, Jianing; Wang, Bing; Cao, Xuefei; Sun, Shaoni; Sun, Run-Cang

2016-01-01

The biorefinery based on an effective and economical process is to fractionate the three primary constituents (cellulose, hemicelluloses, and lignin) from lignocellulosic biomass, in which the constituents can be respectively converted into high-value-added products. In this study, a successive treatment with dilute acid (0.25-1.0 % aqueous H 2 SO 4 , 100-150 °C, 0.5-3.0 h) and alkali (1.5 % aqueous NaOH, 80 °C, 3 h) was performed to produce xylooligosaccharides (XOS), high-purity lignin, and cellulose-rich substrates to produce glucose for ethanol production from rice straw (RS). During the dilute acid pretreatment, the maximum production of XOS (12.8 g XOS/100 g RS) with a relatively low level of byproducts was achieved at a relatively low temperature (130 °C) and a low H 2 SO 4 concentration (0.5 %) for a reaction time of 2.0 h. During the alkali post-treatment, 14.2 g lignin with a higher purity of 99.2 % and 30.3 g glucose with a higher conversion rate by enzymatic hydrolysis were obtained from the successively treated substrates with 100 g RS as starting material. As the pretreatment temperature, H 2 SO 4 concentration, or time increased, more β - O -4 linkages in lignins were cleaved, which resulted in an increase of phenolic OH groups in lignin macromolecules. The signal intensities of G 2 and G 6 in HSQC spectra gradually reduced and vanished, indicating that a condensation reaction probably occurred at C-2 and C-6 of guaiacyl with the side chains of other lignin. The present study demonstrated that the successive treatments with dilute acid and alkali had a synergetic effect on the fractionation of the three main constituents in RS. It is believed that the results obtained will enhance the availability of the combined techniques in the lignocellulosic biorefinery for the application of the main components, cellulose, hemicelluloses, and lignin as biochemical and biofuels.

Effects of Down- and Up-regulated Lignin Biosynthesis in Populus of Soil Carbon Transformation and Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiang, Vincent, L.; Pregitzer, Kurt, S.

2010-03-30

Our objective is to understand how rates of soil C formation and plant biomass are influenced by changes in plant growth and performance resulting from lowered lignin and altered lignin S/G ratios. A greenhouse study of the effects of altered lignin in SOC formation and plant biomass has been completed as of November 2009. Wild-type (control) and three transgenic aspen lines expressing reduced stem lignin concentrations and/or increased syringyl (S) to guaiacyl (G) ratio lignin were grown in greenhouse mesocosms. Soil was collected from the Colorado Central Plains Experimental Range (CPER) northeast of Fort Collins, Colorado. The Colorado soil ismore » an Olney fine sandy loam (fine-loamy, mixed, superactive, mesic Ultic Haplargrid). Plants at the surface mineral soil up to 5 cm depth were removed and the underlying soil was sampled to a depth of 30 cm. Soils were immediately shipped to Reno, NV. This C4 soil was then used to trace belowground C inputs by the C3 plants into the soil using the 13C natural abundance methods as described in the DOE proposal. Transgenic quaking aspen were generated by the Forest Biotechnology Group at North Carolina State University (NCSU) using Agrobacterium-mediated transformation, the seedlings were then shipped to Reno, NV. Rooted seedlings were transferred from sterile agar into small pots with 250 g of C4 grass-dominated soil and kept in mist chambers in a greenhouse for four to six weeks. Plants were arranged randomly in adjacent greenhouse benches, soil blanks were placed randomly among the plants and treated in the same manner as pots with plants. Growth measurements were conducted for all plants in both groups and consisted of height, width at base of stem, number of leaves and length and width of every leaf in every tree. Plants were grown for a period of 120-140 days. At harvest, the aboveground portions of the trees were separated into leaves, litter, and stems. Soils were immediately frozen after harvest and roots were subsequently removed from thawed soil. Roots were further separated into coarse (> 1mm) and fine (< 1mm) roots. All tissue samples were dried for 48 h at 65 ºC, weighed, and then milled for analysis. Fine roots were analyzed for C and N concentrations and 13C (± 0.25‰). All other plant tissues were analyzed for C and N concentrations. Soils were analyzed for available soil nutrients, after harvest and root extraction, soils (including soil blanks pots) were analyzed for C and N concentrations and 13C using the same procedure as the fine roots. Growth measurements from both experiments showed that plant lines differed in heights, number of leaves, total biomass, and total leaf area; but did not differ in average leaf size or stem width. The low lignin line (23) and the control line (271) were similar to each other for all measured characteristics and were significantly larger than the low lignin + high S/G ratio lines (72 and 75). C/N ratios were highest for low lignin plants (line 23) in the woody tissue (roots and stems). The soil C concentrations and total C contents in the soil did not vary significantly among lines. There were no significant difference among lines in the amount (g) of new soil C, however, the soil from the control line (271) and low lignin line (23) had the highest new C concentration and total new C input into the soil. All soils with plants lost some of the existing “old” C, but the loss of old C was not significantly different among lines. Our findings support our first hypothesis, that high S/G ratio lines (72, 75, and 93) have less biomass, and soil C formation is affected as a result of the lower biomass. Our second hypothesis, that low lignin lines (23) would have more biomass and greater soil C formation, was partially supported. Although line 23 did not significantly out-perform the control line (271), the values for all measured growth and soil C characteristics were either comparable or greater than those for 271. The second part of this hypothesis, that line 23 would mobilize more old soil C and alter C/N ratios, was only partially supported by our data. Line 23 did not mobilize more old soil C, but the woody tissue C/N ratios were significantly higher than other lines, suggesting that tissue from line 23 plants is possibly more recalcitrant to decomposition. The comparable performance to the control lines coupled with the reduced lignin in the wood structure gives line 23 an advantage over line 271 in terms of pulping efficiency. The higher C/N ratios in the woody tissue could also suggest it has an advantage for C sequestration in tissue.« less

Native lignin structure of Miscanthus x giganteus and its changes during acetic and formic acid fractionation.

PubMed

Villaverde, Juan José; Li, Jiebing; Ek, Monica; Ligero, Pablo; de Vega, Alberto

2009-07-22

Milled wood lignin (MWL) and acetic and formic acid lignin (AL and FL) from Miscanthus x giganteus bark were produced, respectively, before and after organosolv fractionations under optimal conditions, in terms of organic and hydrochloric acid concentrations, liquid/wood ratio, and reaction time. In order to study the M. x giganteus native lignin structure and its modifications during the fractionation process, the lignins were studied by two-dimensional heteronuclear single quantum coherence (2D-(HSQC)), (13)C- and (31)P nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR), size-exclusion chromatography (SEC) both before and after thioacidolysis, and elemental analysis. In addition, chemical composition analysis was performed on ash, Klason lignin, and carbohydrate content. The analyses demonstrated that M. x giganteus native lignin (MWL) is highly acylated at the C(gamma) of the lignin side chain (46%), possibly with p-coumarate and/or acetate groups. This is newsworthy since several earlier studies showed that acylation at the gamma-carbon commonly occurs in C(3) and CAM grasses, whereas M. x giganteus is a C(4) grass. Furthermore, M. x giganteus showed a low S/G ratio (0.7) and a predominance of beta-O-4' linkages (up to 93% of all linkages). AL and FL lose part of these linkages during organosolv fractionation (up to 21 and 32%, respectively). The p-coumarate groups resist fractionation processes and are still present in high quantities in AL and FL. During the fractionation process, lignin is acetylated (acetic acid process) and condensed, with the G units condensing more than S units. M. x giganteus MWL contains a high content of carbohydrates (22.8%), suggesting that it is a lignin-carbohydrate complex (LCC). AL and FL showed low carbohydrate contents because of the breaking down of the LCC structures. AL and FL have high molecular weights and low polydispersities, and are high in phenolic content, qualities that make these suitable for different applications. These results suggest that refinement of M. x giganteus via organosolv processes could potentially turn this grass into a valuable source of both fiber and lignin.

Pan-arctic trends in terrestrial dissolved organic matter from optical measurements

NASA Astrophysics Data System (ADS)

Mann, Paul; Spencer, Robert; Hernes, Peter; Six, Johan; Aiken, George; Tank, Suzanne; McClelland, James; Butler, Kenna; Dyda, Rachael; Holmes, Robert

2016-03-01

Climate change is causing extensive warming across arctic regions resulting in permafrost degradation, alterations to regional hydrology, and shifting amounts and composition of dissolved organic matter (DOM) transported by streams and rivers. Here, we characterize the DOM composition and optical properties of the six largest arctic rivers draining into the Arctic Ocean to examine the ability of optical measurements to provide meaningful insights into terrigenous carbon export patterns and biogeochemical cycling. The chemical composition of aquatic DOM varied with season, spring months were typified by highest lignin phenol and dissolved organic carbon (DOC) concentrations with greater hydrophobic acid content, and lower proportions of hydrophilic compounds, relative to summer and winter months. Chromophoric DOM (CDOM) spectral slope (S275-295) tracked seasonal shifts in DOM composition across river basins. Fluorescence and parallel factor analysis identified seven components across the six Arctic rivers. The ratios of 'terrestrial humic-like' versus 'marine humic-like' fluorescent components co-varied with lignin monomer ratios over summer and winter months, suggesting fluorescence may provide information on the age and degradation state of riverine DOM. CDOM absorbance (a350) proved a sensitive proxy for lignin phenol concentrations across all six river basins and over the hydrograph, enabling for the first time the development of a single pan-arctic relationship between a350 and terrigenous DOC (R2 = 0.93). Combining this lignin proxy with high-resolution monitoring of a350, pan-arctic estimates of annual lignin flux were calculated to range from 156 to 185 Gg, resulting in shorter and more constrained estimates of terrigenous DOM residence times in the Arctic Ocean (spanning 7 months to 2½ years). Furthermore, multiple linear regression models incorporating both absorbance and fluorescence variables proved capable of explaining much of the variability in lignin composition across rivers and seasons. Our findings suggest that synoptic, high-resolution optical measurements can provide improved understanding of northern high-latitude organic matter cycling and flux, and prove an important technique for capturing future climate-driven changes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gough, M.A.; Fauzi, R.; Mantoura, C.

The vascular land plant biopolymers lignin and cutin were surveyed in the surface sediments of coastal and open ocean waters by controlled alkaline CuO oxidation/reaction. Two contrasting oceanic regimes were studied: the northwest Mediterranean (NWM) Sea, which receives significant particulate terrigenous debris through riverine discharge; and the northeast Atlantic (NEA) Ocean, with poorly characterized terrestrial carbon inputs. In the NWM products of lignin and cutin co-occurred at all stations, elevated levels (ca. 0.5-3.0 mg lignin phenols/100 mg organic carbon; ca. 0.01-0.09 mg cutin acids/100 mg organic carbon) were observed for near-shore deltaic and shelf sediments. The influence of terrestrial landmore » plant inputs extended across the shelf and through the slope to the abyssal plain, providing molecular evidence for advective offshore transfer of terrestrial carbon. Mass balance estimates for the basin suggest riverine inputs account for the majority of surface sedimentary ligin/cutin, most of which (>90%) is deposited on the shelf. Products of CuO oxidation of lignin and cutin were also detected in NEA surface sediments, at levels comparable to those observed for the NWM continental slope, and were detectable at low concentrations in the sediments of the abyssal plains (>4,000 m depth). While atmospheric deposition of lignin/cutin-derived material cannot be discounted in this open ocean system, lateral advective transfer of enriched shelf sediments is inferred as a possible transport process. A progressive enrichment in cutin-derived material relative to lignin was observed offshore, with evidence of an increase in the degree of oxidative alteration of lignin residues. Preliminary mass balance calculations applied to the global ocean margin suggest riverine sources of both particulate lignin and cutin are important and that most (>95%) deposition of recognizable land plant biopolymers occurs in shelf seas. 74 refs., 7 figs., 5 tabs.« less

Interactions of tissue and fertilizer nitrogen on decomposition dynamics of lignin-rich conifer litter

USGS Publications Warehouse

Perakis, Steven S.; Matkins, Joselin J.; Hibbs, David E.

2012-01-01

High tissue nitrogen (N) accelerates decomposition of high-quality leaf litter in the early phases of mass loss, but the influence of initial tissue N variation on the decomposition of lignin-rich litter is less resolved. Because environmental changes such as atmospheric N deposition and elevated CO2 can alter tissue N levels within species more rapidly than they alter the species composition of ecosystems, it is important to consider how within-species variation in tissue N may shape litter decomposition and associated N dynamics. Douglas-fir (Pseudotsuga menziesii ) is a widespread lignin-rich conifer that dominates forests of high carbon (C) storage across western North America, and displays wide variation in tissue and litter N that reflects landscape variation in soil N. We collected eight unique Douglas-fir litter sources that spanned a two-fold range in initial N concentrations (0.67–1.31%) with a narrow range of lignin (29–35%), and examined relationships between initial litter chemistry, decomposition, and N dynamics in both ambient and N fertilized plots at four sites over 3 yr. High initial litter N slowed decomposition rates in both early (0.67 yr) and late (3 yr) stages in unfertilized plots. Applications of N fertilizer to litters accelerated early-stage decomposition, but slowed late-stage decomposition, and most strongly affected low-N litters, which equalized decomposition rates across litters regardless of initial N concentrations. Decomposition of N-fertilized litters correlated positively with initial litter manganese (Mn) concentrations, with litter Mn variation reflecting faster turnover of canopy foliage in high N sites, producing younger litterfall with high N and low Mn. Although both internal and external N inhibited decomposition at 3 yr, most litters exhibited net N immobilization, with strongest immobilization in low-N litter and in N-fertilized plots. Our observation for lignin-rich litter that high initial N can slow decomposition yet accelerate N release differs from findings where litter quality variation across species promotes coupled C and N release during decomposition. We suggest reevaluation of ecosystem models and projected global change effects to account for a potential decoupling of ecosystem C and N feedbacks through litter decomposition in lignin-rich conifer forests.

Quantitative solid-state 13C nuclear magnetic resonance spectrometric analyses of wood xylen: effect of increasing carbohydrate content

USGS Publications Warehouse

Bates, A.L.; Hatcher, P.G.

1992-01-01

Isolated lignin with a low carbohydrate content was spiked with increasing amounts of alpha-cellulose, and then analysed by solid-state 13C nuclear magnetic resonance (NMR) using cross-polarization with magic angle spinning (CPMAS) and dipolar dephasing methods in order to assess the quantitative reliability of CPMAS measurement of carbohydrate content and to determine how increasingly intense resonances for carbohydrate carbons affect calculations of the degree of lignin's aromatic ring substitution and methoxyl carbon content. Comparisons were made of the carbohydrate content calculated by NMR with carbohydrate concentrations obtained by phenol-sulfuric acid assay and by the calculation from the known amounts of cellulose added. The NMR methods used in this study yield overestimates for carbohydrate carbons due to resonance area overlap from the aliphatic side chain carbons of lignin. When corrections are made for these overlapping resonance areas, the NMR results agree very well with results obtained by other methods. Neither the calculated methoxyl carbon content nor the degree of aromatic ring substitution in lignin, both calculated from dipolar dephasing spectra, change with cellulose content. Likewise, lignin methoxyl content does not correlate with cellulose abundance when measured by integration of CPMAS spectra. ?? 1992.

The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

PubMed

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

2016-09-08

Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of supramolecular structures on thermoplastic zein-lignin bionanocomposites.

PubMed

Oliviero, Maria; Verdolotti, Letizia; Di Maio, Ernesto; Aurilia, Marco; Iannace, Salvatore

2011-09-28

The effect of alkaline lignin (AL) and sodium lignosulfonate (LSS) on the structure of thermoplastic zein (TPZ) was studied. Protein structural changes and the nature of the physical interaction between lignin and zein were investigated by means of X-ray diffraction and Fourier transform infrared (FT-IR) spectroscopy and correlated with physical properties. Most relevant protein structural changes were observed at low AL concentration, where strong H-bondings between the functional groups of AL and the amino acids in zein induced a destructuring of inter- and intramolecular interactions in α-helix, β-sheet, and β-turn secondary structures. This destructuring allowed for an extensive protein conformational modification which, in turn, resulted in a strong improvement of the physical properties of the bionanocomposite.

Lacustrine lignin biomarker record reveals a severe drought during the late Younger Dryas in southern Taiwan

NASA Astrophysics Data System (ADS)

Ding, Xiaodong; Bao, Hongyan; Zheng, Liwei; Li, Dawei; Kao, Shuh-Ji

2017-03-01

The Younger Dryas (YD) event, which punctuated the last glacial-Holocene transition period and had a profound impact on global climate, is the most well studied millennial-scale climate event although the triggering mechanism remains debate. Weakened Asian summer monsoon during the YD is recorded in oxygen isotopes of stalagmite from Mainland China. However, lacustrine climate record of the YD event has not been reported from the subtropical land-ocean boundary of the Asian continent near the Pacific warm pool. We provide a lignin biomarker record covering the last deglaciation and early Holocene (17-9 ka BP) from the Dongyuan Lake, southern Taiwan, located at the frontal zone of typhoon invasion. The lignin phenol ratio S/V shows that the vegetation in the catchments had shifted from gymnosperm dominant to angiosperm dominant plants since 12.2 ka BP. Significantly decreased lignin concentrations (TLP and λ8) and elevated lignin degradation parameters ((Ad/Al)v, P/(V + S), DHBA/V) in combination with other organic proxies (TOC, δ13Corg) during the late YD suggest a severe drought had occurred in southern Taiwan during this specific period. Changes in the lignin proxies from the Dongyuan Lake lagged the climate changes registered in stalagmite records by around 500-800 years, suggesting a slow response of vegetation and soil processes to rapid climate changes.

Detecting volatile compounds from Kraft lignin degradation in the headspace of microbial cultures by selected ion flow tube mass spectrometry (SIFT-MS).

PubMed

Gibson, Andrew; Malek, Lada; Dekker, Robert F H; Ross, Brian

2015-05-01

Selected Ion Flow Tube Mass Spectrometry (SIFT-MS) was used to quantify methanol and other volatile compounds in the headspace of one bacterial and 12 fungal lignin-degrading microbial cultures. Cultures were grown in 250 mL Erlenmeyer flasks capped with aluminum foil containing 40 mL of nutrient media using Kraft lignin (0.3% w/v) as the sole carbon source. Analysis was done using SIFT-MS with H3O(+) and NO(+) precursors. Product ions were identified with multiple ion mode (MIM). Full scan (FS) mode was used to identify other compounds of interest. Absidia cylindrospora, Ischnoderma resinosum and Pholiota aurivella increased headspace methanol concentration by 136 ppb, 1196 ppb and 278 ppb, respectively, while Flammulina velutipes and Laetiporus sulphureus decreased concentration below ambient levels. F. velutipes and L. sulphureus were found to produce products of methanol oxidation (formaldehyde and formic acid) and were likely metabolizing methanol. Some additional unidentified compounds generated by the fungal cultures are intriguing and will require further study. SIFT-MS can be used to quantify methanol and other volatile compounds in the headspace of microbial cultures and has the potential to be a rapid, sensitive, non-invasive tool useful in elucidating the mechanisms of lignin degradative pathways. Copyright © 2015 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howe, Daniel T.; Taasevigen, Danny; Garcia-Perez, Manuel

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 themore » 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.« less

Synthesis and characterization of carbon cryogel microspheres from lignin-furfural mixtures for biodiesel production.

PubMed

Zainol, Muzakkir Mohammad; Amin, Nor Aishah Saidina; Asmadi, Mohd

2015-08-01

The aim of this work was to study the potential of biofuel and biomass processing industry side-products as acid catalyst. The synthesis of carbon cryogel from lignin-furfural mixture, prepared via sol-gel polycondensation at 90°C for 0.5h, has been investigated for biodiesel production. The effect of lignin to furfural (L/F) ratios, lignin to water (L/W) ratios and acid concentration on carbon cryogel synthesis was studied. The carbon cryogels were characterized and tested for oleic acid conversion. The thermally stable amorphous spherical carbon cryogel has a large total surface area with high acidity. Experimental results revealed the optimum FAME yield and oleic acid conversion of 91.3wt.% and 98.1wt.%, respectively were attained at 65°C for 5h with 5wt.% catalyst loading and 20:1 methanol to oleic acid molar ratio. Therefore, carbon cryogel is highly potential for heterogeneous esterification of free fatty acid to biodiesel. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nuclear magnetic resonance studies of ancient buried wood-II. Observations on the origin of coal from lignite to bituminous coal

USGS Publications Warehouse

Hatcher, P.G.; Breger, I.A.; Szeverenyi, N.; Maciel, G.E.

1982-01-01

Coalified logs ranging in age from Late Pennsylvania to Miocene and in rank from lignite B to bituminous coal were analyzed by 13C nuclear magnetic resonance (NMR) utilizing the cross-polarization, magic-angle spinning technique, as well as by infrared spectroscopy. The results of this study indicate that at least three major stages of coalification can be observed as wood gradually undergoes transformation to bituminous coal. The first stage involves hydrolysis and loss of cellulose from wood with retention and differential concentration of the resistant lignin. The second stage involves conversion of the lignin residues directly to coalified wood of lignitic rank, during which the oxygen content of intermediate diagenetic products remains constant as the hydrogen content and the carbon content increases. These changes are thought to involve loss of methoxyl groups, water, and C3 side chains from the lignin. In the third major stage of coalification, the coalified wood increases in rank to subbituminous and bituminous coal; during this stage the oxygen content decreases, hydrogen remains constant, and the carbon content increases. These changes are thought to result from loss of soluble humic acids that are rich in oxygen and that are mobilized during compaction and dewatering. Relatively resistant resinous substances are differentially concentrated in the coal during this stage. The hypothesis that humic acids are formed as mobile by-products of the coalification of lignin and function only as vehicles for removal of oxygen represents a dramatic departure from commonly accepted views that they are relatively low-molecular-weight intermediates formed during the degradation of lignin that then condense to form high-molecular-weight coal structures. ?? 1982.

Production of Monomeric Aromatic Compounds from Oil Palm Empty Fruit Bunch Fiber Lignin by Chemical and Enzymatic Methods.

PubMed

Tang, Pei-Ling; Hassan, Osman; Maskat, Mohamad Yusof; Badri, Khairiah

2015-01-01

In this study, oil palm empty fruit bunch (OPEFBF) was pretreated with alkali, and lignin was extracted for further degradation into lower molecular weight phenolic compounds using enzymes and chemical means. Efficiency of monomeric aromatic compounds production from OPEFBF lignin via chemical (nitrobenzene versus oxygen) and enzymatic [cutinase versus manganese peroxidase (MnP)] approaches was investigated. The effects of sodium hydroxide concentration (2, 5, and 10% wt.) and reaction time (30, 90, and 180 minutes) on the yield of aromatic compounds were studied. The results obtained indicated that nitrobenzene oxidation produced the highest yield (333.17 ± 49.44 ppm hydroxybenzoic acid, 5.67 ± 0.25 ppm p-hydroxybenzaldehyde, 25.57 ± 1.64 ppm vanillic acid, 168.68 ± 23.23 ppm vanillin, 75.44 ± 6.71 ppm syringic acid, 815.26 ± 41.77 ppm syringaldehyde, 15.21 ± 2.19 ppm p-coumaric acid, and 44.75 ± 3.40 ppm ferulic acid), among the tested methods. High sodium hydroxide concentration (10% wt.) was needed to promote efficient nitrobenzene oxidation. However, less severe oxidation condition was preferred to preserve the hydroxycinnamic acids (p-coumaric acid and ferulic acid). Cutinase-catalyzed hydrolysis was found to be more efficient than MnP-catalyzed oxidation in the production of aromatic compounds. By hydrolyzed 8% wt. of lignin with 0.625 mL cutinase g(-1) lignin at pH 8 and 55°C for 24 hours, about 642.83 ± 14.45 ppm hydroxybenzoic acid, 70.19 ± 3.31 ppm syringaldehyde, 22.80 ± 1.04 ppm vanillin, 27.06 ± 1.20 ppm p-coumaric acid, and 50.19 ± 2.23 ppm ferulic acid were produced.

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

NASA Astrophysics Data System (ADS)

Edmunds, Charles Warren

Increasing concerns over greenhouse gas emissions and the finite supply of fossil fuels lead to the goal of utilizing lignocellulosic feedstocks for biofuels, platform chemicals, and biocomposites. Lignin is responsible for the recalcitrance of lignocellulosic biomass and is a major barrier to its deconstruction. Great progress has been made in mapping and modifying the lignin biosynthetic pathway. However, the link between the genetic modification, resulting chemical and physical properties of the wood, and how these properties influence the thermomechanical and recalcitrance to biological and chemical degradation needs further investigation. In this dissertation, the study of modified Populus trichocarpa and Pinus taeda were utilized to accomplish this goal. Thermo-mechanical properties of genetically modified P. trichocarpa with altered lignin content and/or lignin structure were measured with a series of tools including; dynamic mechanical analysis, nuclear magnetic resonance, and wet chemistry techniques. Results demonstrated lignin content and lignin structure likely influence the glass transition temperature (Tg), and that decreased lignin content and the corresponding higher proportion of cell wall carbohydrates may contribute to increased molecular mobility in the wood polymer structure. The effect of lignin biosynthetic pathway modification on biological degradation of these transgenic wood specimens was of interest. However, experimental methods for fungal treatment on small young greenhouse-grown wood specimens are not well established. Therefore, a project was undertaken to develop a method for fungal inoculation and incubation for these unique specimens. Several parameters were tested, and a fungal treatment method was identified with sufficient weight loss after decay and significant reduction in variation of weight loss between replicates compared to previous experiments by direct inoculation of wood with liquid malt extract fungal culture. Utilizing the fungal treatment method which was developed, fungal pretreatment as a potential low-input and environmentally-friendly alternative to conventional pretreatment methods was tested using the white-rot fungus, Ceriporiopsis subvermispora, on wildtype and transgenic P. trichocarpa. In addition to fungal treatment, hot water and dilute acid treatments followed by enzymatic hydrolysis was tested. Results showed no clear relationship between the initial lignin content or syringyl/guaiacyl lignin monomer ratio and weight loss due to fungal treatment. P-hydroxyphenyl lignin monomer degradation of up to 60% during the fungal treatment were observed in cinnamate 3-hydroxylase down-regulated genetic lines. It was demonstrated that fungal treatment in wildtype and several transgenic lines resulted in substantial improvements in sugar yields, up to 2.4-fold increase in glucose yield and 6.7-fold increase in xylose yield after enzymatic hydrolysis. However, some genetic lines showed little benefit from fungal pretreatment, and in general hot water and dilute acid pretreatments showed similar or increased glucose yield compared to fungal treatment. The goal of the last project was to characterize P. taeda which was genetically modified for S lignin production or decreased lignin content. In addition, the amenability to pretreatment and enzymatic hydrolysis were analyzed using hot water and dilute acid pretreatments followed by enzymatic hydrolysis. In the transgenic lines modified for production of syringyl lignin, Maule staining demonstrated the intermittent deposition of syringyl lignin in the secondary xylem, while thioacidolysis showed 13% concentration of S lignin, and solid state NMR demonstrated the occurrence of beta-O-4 linkages in S lignin units. In transgenic lines modified for reduced lignin content, lignin reduction up to 33% was observed, and pretreatment and enzymatic hydrolysis demonstrated increased cellulose conversion in lowlignin samples. These results highlight the potential of softwood to be a viable bioenergy/biochemical feedstock and opens up exciting new avenue of research.

Effects of N-ammonoxidized lignins amendment on N availability and soil fertility: An incubation study

NASA Astrophysics Data System (ADS)

María De la Rosa, José; López-Martín, María; Liebner, Falk; Knicker, Heike

2013-04-01

The shift towards a biobased economy will probably generate the application of bioenergy by-products and charred residues to the soil as either amendments or fertilizers. The process of ammonoxidation (application of gaseous oxygen and aqueous ammonia under ambient pressure breaks down aromatic lignin moieties and introduces N in the form of urea, amides and amines), converts lignin, a major by-product of the pulp and paper industry, or other ligneous materials into artificial humic matter (N-lignin). The use of N-ammonoxidized lignin as soil improvers is in theory an economically viable solution, especially interesting for agricultural areas of Mediterranean countries, in which additional factors such as water shortage and fires contribute to declining N availability by lowering nutrient diffusion, litter input or sequestration of N in charred structures. However, limited research has been done to determine how this will influence C and N dynamics and soil fertility. Therefore we performed pot experiments in which a perennial ryegrass (Lolium perenne L.) was grown on a typical Andalusian soil (chromic Luvisol) after amendment of N-lignins highly enriched in 15N (Sarkanda and Indulin ammonoxidized lignins) for 75 days. For comparison, the incubation was also carried out on soils fertilized with 15NO3 and unfertilized (control). The application of ammonoxidized lignins altered the pH and electrical conductivity of the soil. At higher concentrations a retardation of seed germination was evidenced, an observation that needs further considerations before N-enriched technical lignins can be applied in agriculture. After 75 days, the plant shoots from the pots amended with15N-Indulin and 15N-Sarkanda accumulated 8% and 20%, respectively of the initial 15N (15N0). The N was efficiently sequestered from fast release or leaching and most of 15N0 remained in the soil (64%) in the 15N-Indulin pots. In contrast, the 15N-Sarkanda pots showed a lower efficiency in the N retention. The N-sequestration potential of ammonoxidized lignins seems to be mainly due to a quick N transfer into newly formed microbial biomass. However, the efficiency of this transfer depends on the kind of used N-lignin. The notable increase in the 15N of the grass production (> 20%) evidences a more efficient use of N derived from the soil amendment of the Indulin pots. Solid-state NMR spectroscopy revealed that the N of the added N-lignins was quickly transformed into peptide-type N, most tentatively of microbial origin, without major alteration of the lignin backbone. This indicates that in soils the competition for nutrients favors N immobilization into biomass and its subsequent sequestration within recalcitrant biopolymers rather than its stabilization by covalent binding to lignins.

Multivariate Analysis of the Determinants of the End-Product Quality of Manure-Based Composts and Vermicomposts Using Bayesian Network Modelling.

PubMed

Faverial, Julie; Cornet, Denis; Paul, Jacky; Sierra, Jorge

2016-01-01

Previous studies indicated that the quality of tropical composts is poorer than that of composts produced in temperate regions. The aim of this study was to test the type of manure, the use of co-composting with green waste, and the stabilization method for their ability to improve compost quality in the tropics. We produced 68 composts and vermicomposts that were analysed for their C, lignin and NPK contents throughout the composting process. Bayesian networks were used to assess the mechanisms controlling compost quality. The concentration effect, for C and lignin, and the initial blend quality, for NPK content, were the main factors affecting compost quality. Cattle manure composts presented the highest C and lignin contents, and poultry litter composts exhibited the highest NPK content. Co-composting improved quality by enhancing the concentration effect, which reduced the impact of C and nutrient losses. Vermicomposting did not improve compost quality; co-composting without earthworms thus appears to be a suitable stabilization method under the conditions of this study because it produced high quality composts and is easier to implement.

A thioacidolysis method tailored for higher‐throughput quantitative analysis of lignin monomers

PubMed Central

Foster, Cliff; Happs, Renee M.; Doeppke, Crissa; Meunier, Kristoffer; Gehan, Jackson; Yue, Fengxia; Lu, Fachuang; Davis, Mark F.

2016-01-01

Abstract Thioacidolysis is a method used to measure the relative content of lignin monomers bound by β‐O‐4 linkages. Current thioacidolysis methods are low‐throughput as they require tedious steps for reaction product concentration prior to analysis using standard GC methods. A quantitative thioacidolysis method that is accessible with general laboratory equipment and uses a non‐chlorinated organic solvent and is tailored for higher‐throughput analysis is reported. The method utilizes lignin arylglycerol monomer standards for calibration, requires 1–2 mg of biomass per assay and has been quantified using fast‐GC techniques including a Low Thermal Mass Modular Accelerated Column Heater (LTM MACH). Cumbersome steps, including standard purification, sample concentrating and drying have been eliminated to help aid in consecutive day‐to‐day analyses needed to sustain a high sample throughput for large screening experiments without the loss of quantitation accuracy. The method reported in this manuscript has been quantitatively validated against a commonly used thioacidolysis method and across two different research sites with three common biomass varieties to represent hardwoods, softwoods, and grasses. PMID:27534715

A thioacidolysis method tailored for higher-throughput quantitative analysis of lignin monomers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harman-Ware, Anne E.; Foster, Cliff; Happs, Renee M.

Thioacidolysis is a method used to measure the relative content of lignin monomers bound by β-O-4 linkages. Current thioacidolysis methods are low-throughput as they require tedious steps for reaction product concentration prior to analysis using standard GC methods. A quantitative thioacidolysis method that is accessible with general laboratory equipment and uses a non-chlorinated organic solvent and is tailored for higher-throughput analysis is reported. The method utilizes lignin arylglycerol monomer standards for calibration, requires 1-2 mg of biomass per assay and has been quantified using fast-GC techniques including a Low Thermal Mass Modular Accelerated Column Heater (LTM MACH). Cumbersome steps, includingmore » standard purification, sample concentrating and drying have been eliminated to help aid in consecutive day-to-day analyses needed to sustain a high sample throughput for large screening experiments without the loss of quantitation accuracy. As a result, the method reported in this manuscript has been quantitatively validated against a commonly used thioacidolysis method and across two different research sites with three common biomass varieties to represent hardwoods, softwoods, and grasses.« less

A thioacidolysis method tailored for higher-throughput quantitative analysis of lignin monomers

DOE PAGES

Harman-Ware, Anne E.; Foster, Cliff; Happs, Renee M.; ...

2016-09-14

Thioacidolysis is a method used to measure the relative content of lignin monomers bound by β-O-4 linkages. Current thioacidolysis methods are low-throughput as they require tedious steps for reaction product concentration prior to analysis using standard GC methods. A quantitative thioacidolysis method that is accessible with general laboratory equipment and uses a non-chlorinated organic solvent and is tailored for higher-throughput analysis is reported. The method utilizes lignin arylglycerol monomer standards for calibration, requires 1-2 mg of biomass per assay and has been quantified using fast-GC techniques including a Low Thermal Mass Modular Accelerated Column Heater (LTM MACH). Cumbersome steps, includingmore » standard purification, sample concentrating and drying have been eliminated to help aid in consecutive day-to-day analyses needed to sustain a high sample throughput for large screening experiments without the loss of quantitation accuracy. As a result, the method reported in this manuscript has been quantitatively validated against a commonly used thioacidolysis method and across two different research sites with three common biomass varieties to represent hardwoods, softwoods, and grasses.« less

Robust enzymatic hydrolysis of Formiline-pretreated oil palm empty fruit bunches (EFB) for efficient conversion of polysaccharide to sugars and ethanol.

PubMed

Cui, Xingkai; Zhao, Xuebing; Zeng, Jing; Loh, Soh Kheang; Choo, Yuen May; Liu, Dehua

2014-08-01

Oil palm empty fruit bunch (EFB) was pretreated by Formiline process to overcome biomass recalcitrance and obtain hemicellulosic syrup and lignin. Higher formic acid concentration led to more lignin removal but also higher degree of cellulose formylation. Cellulose digestibility could be well recovered after deformylation with a small amount of lime. After digested by enzyme loading of 15 FPU+10 CBU/g solid for 48 h, the polysaccharide conversion could be over 90%. Simultaneous saccharification and fermentation (SSF) results demonstrated that ethanol concentration reached 83.6 g/L with approximate 85% of theoretic yield when performed at an initial dry solid consistency of 20%. A mass balance showed that via Formiline pretreatment 0.166 kg of ethanol could be produced from 1 kg of dry EFB with co-production of 0.14 kg of high-purity lignin and 5.26 kg hemicellulosic syrup containing 2.8% xylose. Formiline pretreatment thus can be employed as an entry for biorefining of EFB. Copyright © 2014 Elsevier Ltd. All rights reserved.

Distinct Litter Stabilization Dynamics Pathways for Decomposition of Pine Needle and Fine Root Within Soil

NASA Astrophysics Data System (ADS)

Mambelli, S.; Filley, T. R.; Bird, J.; Dawson, T.; Torn, M. S.

2008-12-01

The chemical composition of litter imparts a strong control on the initial rates of microbial decay but it is unclear how plant chemistry influences the ultimate stabilization of soil organic matter (SOM) and the nature of the products stabilized. We determined the concentration and 13C enrichment of lignin phenols and substituted fatty acids (SFA) in SOM fractions from an experiment in which 13C- and 15N-labeled needles or fine roots were added to the mineral soil in a Ponderosa pine (Pinus ponderosa) forest in the Sierra Nevada, CA, USA. 1.5 y after litter addition, we analyzed bulk soil (< 2 mm), free light fraction (LF, mean residence time (MRT) ~5 y) and alkali/acid insoluble humin (MRT ~270 y) fractions. Needles contained nearly 2 and 3x the lignin and SFA content per organic carbon unit as did roots. Lignin and SFA decreased from the free LF to the bulk soil to the humin fraction; and molecular properties were more similar within a SOM fraction regardless of the litter source. However, LF and humin from the root addition contained more lignin than from the needle addition. Based upon the relative movement of litter-derived 13C and 15N into SOM fractions during 1.5 y, it was proposed that the 13C accumulation in the humin fraction for needles was derived from high C/N, needle-derived biopolymer molecular fragments that are surficially associated with particles. In contrast, the root-derived material entering SOM fractions was much lower in C/N and was likely from microbial by-products. Consistent with this hypothesis, both lignin and SFA in the LF and humin fractions amended with enriched needles were highly enriched (+ 30-60 permil) with respect to the SOM fractions from soils amended with roots. These differences were large even considering the lower concentration of SFA and lignin in root material. Although the chemistry and MRT of LF and humin were dramatically different, the extent of 13C-enrichment among lignin and SFA were comparable for the needle experiment while most lignin phenols for the humin from the root addition had greater 13C content than SFA. This indicates that molecular fragments of plant biopolymers can readily associate with both labile and stabilized SOM fractions. At the same time, these results suggest that distinct decomposition and stabilization pathways exist for litters, such as needles vs. roots, of different chemical quality.

Lignin biomarkers and pollen in the postglacial sediment of an Alaskan Lake

NASA Astrophysics Data System (ADS)

Hu, Feng Sheng; Hedges, John I.; Gordon, Elizabeth S.; Brubaker, Linda B.

1999-05-01

We analyzed a 12,000-yr sediment core from Wien Lake, central Alaska, for a suite of phenolic products from CuO oxidation of lignin polymers and compared their composition with pollen data from the same core to assess lignin phenols as sedimentary biomarkers. Inferences of the gross taxonomic origin of sediment organic matter from lignin-phenol composition agree with vegetational reconstructions based on pollen assemblages. In particular, the ratios of syringyl to vanillyl phenols are consistently higher before 6500 yr BP, when angiosperms dominated or codominated the regional vegetation, than after 6500 yr BP, when gymnosperms dominated. However, the ratios of cinnamyl ( p-coumaric and ferulic acids) to total vanillyl phenols (C/V) do not show patterns expected from the abundance of woody plants. C/V ratios are particularly high (0.7-0.85) after 6500 yr BP when pollen spectra suggest closed boreal forests dominated by Picea, and the stratigraphic patterns are strikingly similar between C/V and Picea pollen concentrations. CuO oxidation of modern pollen of P. glauca and P. mariana yields exceptionally high amounts of cinnamyl phenols (8.90 and 6.41 mg/100 mg OC for P. glauca and P. mariana, respectively). In particular, p-coumaric acid is obtained in large amounts (8.87 and 6.41 mg/100 mg OC for P. glauca and P. mariana, respectively) versus vanillyl phenols (0.25 and 0.49 mg/100 mg OC for P. glauca and P. mariana, respectively) and ferulic acid (0.03 and 0.00 mg/100 mg OC for P. glauca and P. mariana, respectively). Thus lignin phenols derived from fossil Picea pollen preserved in sediments likely drive the C/V profile of the Wien Lake core. These data imply that if Picea pollen concentrations are sufficiently high, the amount of nonwoody tissue in sediments may be grossly overestimated when the lignin composition of gymnosperm needles is used as the end member of nonwoody tissues. Given that pollen grains are among the most resistant components of sedimentary organic matter and that p-coumaric acid is labile, it is important to consider pollen as a nonwoody tissue type when lignin biomarkers are used to determine the sources of vascular-plant material in sediments.

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

PubMed

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.

Chronic nitrogen deposition influences the chemical dynamics ...

EPA Pesticide Factsheets

Atmospheric nitrogen deposition induces a forest carbon sink across broad parts of the Northern Hemisphere; this carbon sink may partly result from slower litter decomposition. Although microbial responses to experimental nitrogen deposition have been well-studied, evidence linking these microbial responses to changes in the degradation of specific compounds in decaying litter is sparse. We used wet chemistry and Fourier transform infrared spectroscopy (FTIR) methodologies to study the effects of chronic simulated nitrogen deposition on leaf litter and fine root chemistry during a three-year decomposition experiment at four northern hardwood forests in the north-central USA. Leaf litter and fine roots were highly different in initial chemistry such as concentrations of acid-insoluble fraction (AIF, or Klason lignin) and condensed tannins (CTs). These initial differences persisted over the course of decomposition. Results from gravimetrically-defined AIF and lignin/carbohydrate reference IR peak ratios both provide evidence that lignin in fine roots was selectively preserved under simulated nitrogen deposition. Lignin/carbohydrate peak ratios were strongly correlated with AIF, suggesting that AIF is a good predictor of lignin. Because AIF is abundant in fine roots, slower AIF degradation was the major driver of the slower fine root decomposition under nitrogen enrichment, explaining 73.9 % of the additional root mass retention. Nitrogen enrichment also slowed the

Lignin triggers irreversible cellulase loss during pretreated lignocellulosic biomass saccharification.

PubMed

Gao, Dahai; Haarmeyer, Carolyn; Balan, Venkatesh; Whitehead, Timothy A; Dale, Bruce E; Chundawat, Shishir Ps

2014-01-01

Non-productive binding of enzymes to lignin is thought to impede the saccharification efficiency of pretreated lignocellulosic biomass to fermentable sugars. Due to a lack of suitable analytical techniques that track binding of individual enzymes within complex protein mixtures and the difficulty in distinguishing the contribution of productive (binding to specific glycans) versus non-productive (binding to lignin) binding of cellulases to lignocellulose, there is currently a poor understanding of individual enzyme adsorption to lignin during the time course of pretreated biomass saccharification. In this study, we have utilized an FPLC (fast protein liquid chromatography)-based methodology to quantify free Trichoderma reesei cellulases (namely CBH I, CBH II, and EG I) concentration within a complex hydrolyzate mixture during the varying time course of biomass saccharification. Three pretreated corn stover (CS) samples were included in this study: Ammonia Fiber Expansion(a) (AFEX™-CS), dilute acid (DA-CS), and ionic liquid (IL-CS) pretreatments. The relative fraction of bound individual cellulases varied depending not only on the pretreated biomass type (and lignin abundance) but also on the type of cellulase. Acid pretreated biomass had the highest levels of non-recoverable cellulases, while ionic liquid pretreated biomass had the highest overall cellulase recovery. CBH II has the lowest thermal stability among the three T. reesei cellulases tested. By preparing recombinant family 1 carbohydrate binding module (CBM) fusion proteins, we have shown that family 1 CBMs are highly implicated in the non-productive binding of full-length T. reesei cellulases to lignin. Our findings aid in further understanding the complex mechanisms of non-productive binding of cellulases to pretreated lignocellulosic biomass. Developing optimized pretreatment processes with reduced or modified lignin content to minimize non-productive enzyme binding or engineering pretreatment-specific, low-lignin binding cellulases will improve enzyme specific activity, facilitate enzyme recycling, and thereby permit production of cheaper biofuels.

Signatures of Biomass Burning Aerosols in the Plume of a Saltmarsh Wildfire in South Texas.

PubMed

Myers-Pigg, Allison N; Griffin, Robert J; Louchouarn, Patrick; Norwood, Matthew J; Sterne, Amanda; Cevik, Basak Karakurt

2016-09-06

The most conventional and abundant tracers of biomass combustion in aerosol particles include potassium and biomarkers derived from thermally altered cellulose/hemicellulose (anhydrosugars) and lignin (methoxyphenols). However, little is known of the role biomass combustion plays as a particulate source of major plant polymers to the atmosphere. Here, concentrations of solvent-extractable anhydrosugars and methoxyphenols are compared to the yields of polymeric lignin oxidation products (LOPs) during a smoke plume event in Houston, Texas. Downwind aerosol samples (PM2.5) were collected surrounding a two-day wildfire in the McFaddin National Wildlife Refuge, 125 km southeast of Houston, which was 12-16 h directly downwind during the peak of the burn. Concentrations of all organic markers, potassium, and calcium increased by a factor of 2-13 within 1-2 days of the start of the fire and dropped to prefire levels 3 days after the peak event. Source signatures of anhydrosugars and methoxyphenols during the peak of the plume were identical to those of grass charcoals collected from the site, confirming the use of charcoals as end-members for source input reconstruction during atmospheric transport. An enrichment factor of 20 in the anhydrosugar to methoxyphenol ratio of aerosols versus charcoals can be explained partially by differences in degradation rate constants between the biomarker groups. LOPs comprised 73-91% of all lignin material in the aerosols, pointing to fires as major sources of primary biogenic aerosol particles in which lignin phenols occur predominantly in polymeric form.

Production of short-chain fatty acids from the biodegradation of wheat straw lignin by Aspergillus fumigatus.

PubMed

Baltierra-Trejo, Eduardo; Sánchez-Yáñez, Juan Manuel; Buenrostro-Delgado, Otoniel; Márquez-Benavides, Liliana

2015-11-01

The wheat straw lignin-rich fraction (WSLig-RF) can be used as a raw material for the production of metabolites for industrial use if ligninolytic mitosporic fungi are used for its biodegradation into aromatics and short-chain fatty acids (SCFAs, i.e., SCFA2-6). Although methods for the production of SCFA2-6 have been described previously, quantitative data of SCFA2-6 production have not been reported. The objectives of this study were to investigate the biodegradation of different concentrations of WSLig-RF by Aspergillus fumigatus and to identify whether SCFA2-6 production was dependent on the concentration of aromatics. A. fumigatus generated 2805mgL(-1) acetic acid when mixed with WSLig-RF at a concentration of 20gL(-1). Thus, aromatics are a substrate for the biosynthesis of SCFA2-6, and their production depends on the concentration of WSLig-RF aromatics. Copyright © 2015 Elsevier Ltd. All rights reserved.

Integrating plant litter quality, soil organic matter stabilization, and the carbon saturation concept.

PubMed

Castellano, Michael J; Mueller, Kevin E; Olk, Daniel C; Sawyer, John E; Six, Johan

2015-09-01

Labile, 'high-quality', plant litters are hypothesized to promote soil organic matter (SOM) stabilization in mineral soil fractions that are physicochemically protected from rapid mineralization. However, the effect of litter quality on SOM stabilization is inconsistent. High-quality litters, characterized by high N concentrations, low C/N ratios, and low phenol/lignin concentrations, are not consistently stabilized in SOM with greater efficiency than 'low-quality' litters characterized by low N concentrations, high C/N ratios, and high phenol/lignin concentrations. Here, we attempt to resolve these inconsistent results by developing a new conceptual model that links litter quality to the soil C saturation concept. Our model builds on the Microbial Efficiency-Matrix Stabilization framework (Cotrufo et al., 2013) by suggesting the effect of litter quality on SOM stabilization is modulated by the extent of soil C saturation such that high-quality litters are not always stabilized in SOM with greater efficiency than low-quality litters. © 2015 John Wiley & Sons Ltd.

Pan-arctic trends in terrestrial dissolved organic matter from optical measurements

USGS Publications Warehouse

Mann, Paul J.; Spencer, Robert G.M.; Hernes, Peter J.; Six, Johan; Aiken, George R.; Tank, Suzanne E.; McClelland, James W.; Butler, Kenna D.; Dyda, Rachael Y.; Holmes, Robert M.

2016-01-01

Climate change is causing extensive warming across Arctic regions resulting in permafrost degradation, alterations to regional hydrology and shifting amounts and composition of dissolved organic matter (DOM) transported by streams and rivers. Here, we characterize the DOM composition and optical properties of the six largest Arctic rivers draining into the Arctic Ocean to examine the ability of optical measurements to provide meaningful insights into terrigenous carbon export patterns and biogeochemical cycling. The chemical composition of aquatic DOM varied with season, spring months were typified by highest lignin phenol and dissolved organic carbon (DOC) concentrations with greater hydrophobic acid content, and lower proportions of hydrophilic compounds, relative to summer and winter months. Chromophoric DOM (CDOM) spectral slope (S275–295) tracked seasonal shifts in DOM composition across river basins. Fluorescence and parallel factor analysis identified seven components across the six Arctic rivers. The ratios of “terrestrial humic-like” vs. “marine humic-like” fluorescent components co-varied with lignin monomer ratios over summer and winter months, suggesting fluorescence may provide information on the age and degradation state of riverine DOM. CDOM absorbance (a350) proved a sensitive proxy for lignin phenol concentrations across all six river basins and over the hydrograph, enabling for the first time the development of a single pan-arctic relationship between a350 and terrigenous DOC (R2 = 0.93). Combining this lignin proxy with high-resolution monitoring of a350, pan-arctic estimates of annual lignin flux were calculated to range from 156 to 185 Gg, resulting in shorter and more constrained estimates of terrigenous DOM residence times in the Arctic Ocean (spanning 7 months to 2½ years). Furthermore, multiple linear regression models incorporating both absorbance and fluorescence variables proved capable of explaining much of the variability in lignin composition across rivers and seasons. Our findings suggest that synoptic, high-resolution optical measurements can provide improved understanding of northern high-latitude organic matter cycling and flux, and prove an important technique for capturing future climate-driven changes.

Pan-arctic trends in terrestrial dissolved organic matter from optical measurements

USGS Publications Warehouse

Mann, Paul J.; Spencer, Robert G. M.; Hernes, Peter J.; Six, Johan; Aiken, George R.; Tank, Suzanne E.; McClelland, James W.; Butler, Kenna D.; Dyda, Rachael Y.; Holmes, Robert M.

2016-01-01

Climate change is causing extensive warming across Arctic regions resulting in permafrost degradation, alterations to regional hydrology and shifting amounts and composition of dissolved organic matter (DOM) transported by streams and rivers. Here, we characterize the DOM composition and optical properties of the six largest Arctic rivers draining into the Arctic Ocean to examine the ability of optical measurements to provide meaningful insights into terrigenous carbon export patterns and biogeochemical cycling. The chemical composition of aquatic DOM varied with season, spring months were typified by highest lignin phenol and dissolved organic carbon (DOC) concentrations with greater hydrophobic acid content, and lower proportions of hydrophilic compounds, relative to summer and winter months. Chromophoric DOM (CDOM) spectral slope (S275–295) tracked seasonal shifts in DOM composition across river basins. Fluorescence and parallel factor analysis identified seven components across the six Arctic rivers. The ratios of “terrestrial humic-like” vs. “marine humic-like” fluorescent components co-varied with lignin monomer ratios over summer and winter months, suggesting fluorescence may provide information on the age and degradation state of riverine DOM. CDOM absorbance (a350) proved a sensitive proxy for lignin phenol concentrations across all six river basins and over the hydrograph, enabling for the first time the development of a single pan-arctic relationship between a350 and terrigenous DOC (R2 = 0.93). Combining this lignin proxy with high-resolution monitoring of a350, pan-arctic estimates of annual lignin flux were calculated to range from 156 to 185 Gg, resulting in shorter and more constrained estimates of terrigenous DOM residence times in the Arctic Ocean (spanning 7 months to 2½ years). Furthermore, multiple linear regression models incorporating both absorbance and fluorescence variables proved capable of explaining much of the variability in lignin composition across rivers and seasons. Our findings suggest that synoptic, high-resolution optical measurements can provide improved understanding of northern high-latitude organic matter cycling and flux, and prove an important technique for capturing future climate-driven changes.

Terrestrial plant biopolymers in marine sediments

NASA Astrophysics Data System (ADS)

Gough, Mark A.; Fauzi, R.; Mantoura, C.; Preston, Martin

1993-03-01

The vascular land plant biopolymers lignin and cutin were surveyed in the surface sediments of coastal and open ocean waters by controlled alkaline CuO oxidation/reaction. Two contrasting oceanic regimes were studied: the northwest Mediterranean (NWM) Sea, which receives significant particulate terrigenous debris through riverine discharge; and the northeast Atlantic (NEA) Ocean, with poorly characterised terrestrial carbon inputs. In the NWM products of lignin and cutin co-occurred at all stations, elevated levels (ca. 0.5-3.0 mg lignin phenols/100 mg organic carbon; ca. 0.01-0.09 mg cutin acids/100 mg organic carbon) were observed for near-shore deltaic and shelf sediments. The influence of terrestrial land plant inputs extended across the shelf and through the slope to the abyssal plain, providing molecular evidence for advective offshore transfer of terrestrial carbon. Mass balance estimates for the basin suggest riverine inputs account for the majority of surface sedimentary lignin/cutin, most of which (>90%) is deposited on the shelf. Products of CuO oxidation of lignin and cutin were also detected in NEA surface sediments, at levels comparable to those observed for the NWM continental slope, and were detectable at low concentrations ( ca. 0.5 μgg-1 in the sediments of the abyssal plains (>4,000 m depth). While atmospheric deposition of lignin/cutin-derived material cannot be discounted in this open ocean system, lateral advective transfer of enriched shelf sediments is inferred as a possible transport process. A progressive enrichment in cutin-derived material relative to lignin was observed offshore, with evidence of an increase in the degree of oxidative alteration of lignin residues. To account for these observations, preferential offshore transport of finer and more degraded material is proposed. Nonspecific oxidation products dominated the gas chromatograms of NEA sediments, which appear to originate from marine sources of sedimentary organic carbon. Preliminary mass balance calculations applied to the global ocean margin suggest riverine sources of both particulate lignin and cutin are important and that most (>95%) deposition of recognisable land plant biopolymers occurs in shelf seas.

Pyrolysis characteristics and kinetics of lignin derived from enzymatic hydrolysis residue of bamboo pretreated with white-rot fungus.

PubMed

Yan, Keliang; Liu, Fang; Chen, Qing; Ke, Ming; Huang, Xin; Hu, Weiyao; Zhou, Bo; Zhang, Xiaoyu; Yu, Hongbo

2016-01-01

The lignocellulose biorefinery based on the sugar platform usually focuses on polysaccharide bioconversion, while lignin is only burned for energy recovery. Pyrolysis can provide a novel route for the efficient utilization of residual lignin obtained from the enzymatic hydrolysis of lignocellulose. The pyrolysis characteristics of residual lignin are usually significantly affected by the pretreatment process because of structural alteration of lignin during pretreatment. In recent years, biological pretreatment using white-rot fungi has attracted extensive attention, but there are only few reports on thermal conversion of lignin derived from enzymatic hydrolysis residue (EHRL) of the bio-pretreated lignocellulose. Therefore, the study investigated the pyrolysis characteristics and kinetics of EHRL obtained from bamboo pretreated with Echinodontium taxodii in order to evaluate the potential of thermal conversion processes of EHRL. Fourier transform infrared spectroscopy spectra showed that EHRL of bamboo treated with E. taxodii had the typical lignin structure, but aromatic skeletal carbon and side chain of lignin were partially altered by the fungus. Thermogravimetric analysis indicated that EHRL pyrolysis at different heating rates could be divided into two depolymerization stages and covered a wide temperature range from 500 to 900 K. The thermal decomposition reaction can be well described by two third-order reactions. The kinetics study indicated that the EHRL of bamboo treated with white-rot fungus had lower apparent activation energies, lower peak temperatures of pyrolysis reaction, and higher char residue than the EHRL of raw bamboo. Pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) was applied to characterize the fast pyrolysis products of EHRL at 600 ℃. The ratios of guaiacyl-type to syringyl-type derivatives yield (G/S) and guaiacyl-type to p-hydroxy-phenylpropane-type derivatives yield (G/H) for the treated sample were increased by 33.18 and 25.30 % in comparison with the raw bamboo, respectively. The structural alterations of lignin during pretreatment can decrease the thermal stability of EHRL from the bio-treated bamboo and concentrate the guaiacyl-type derivatives in the fast pyrolysis products. Thus, the pyrolysis can be a promising route for effective utilization of the enzymatic hydrolysis residue from bio-pretreated lignocellulose.

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

NASA Astrophysics Data System (ADS)

Stanzione, Joseph F., III

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

Lignin from bamboo shoot shells as an activator and novel immobilizing support for α-amylase.

PubMed

Gong, Weihua; Ran, Zhanxiang; Ye, Fayin; Zhao, Guohua

2017-08-01

This study examined the feasibility of α-amylase activation and immobilization, using lignin from bamboo shoot shells (BSS). Our results demonstrated that BSS lignin is an excellent α-amylase activator and it elevated α-amylase activity more than two-fold at a concentration of 5mg/ml. For immobilization of α-amylase via adsorption, BSS lignin was incubated in an α-amylase solution (5mg/ml) for 20min, and the maximum specific activity, amount of loaded protein and activity recovery were 92.4U/mg, 19.0mg/g and 111%, respectively. In contrast to its free counterpart, immobilized α-amylase improved the catalytic efficiency and storage stability, under comparable working conditions (temperature and pH). Regarding its convenient usage, immobilized enzyme can be suspended in advance, but a suspension incubated at 60°C should be used within 30min. The residual activity after 14 re-uses remained at a reasonable level (53.2%). In conclusion, this study reveals a novel support for enzyme immobilization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Efficient removal of lignin with the maintenance of hemicellulose from kenaf by two-stage pretreatment process.

PubMed

Wan Azelee, Nur Izyan; Md Jahim, Jamaliah; Rabu, Amir; Abdul Murad, Abdul Munir; Abu Bakar, Farah Diba; Md Illias, Rosli

2014-01-01

The enhancement of lignocellulose hydrolysis using enzyme complexes requires an efficient pretreatment process to obtain susceptible conditions for the enzyme attack. This study focuses on removing a major part of the lignin layer from kenaf (Hibiscus cannabinus) while simultaneously maintaining most of the hemicellulose. A two-stage pretreatment process is adopted using calcium hydroxide, Ca(OH)₂, and peracetic acid, PPA, to break the recalcitrant lignin layer from other structural polysaccharides. An experimental screening of several pretreatment chemicals, concentrations, temperatures and solid-liquid ratios enabled the production of an optimally designed pretreatment process for kenaf. Our results showed that the pretreatment process has provide 59.25% lignin removal while maintaining 87.72% and 96.17% hemicellulose and cellulose, respectively, using 1g of Ca(OH)₂/L and a 8:1 (mL:g) ratio of liquid-Ca(OH)₂ at 50 °C for 1.5 h followed by 20% peracetic acid pretreatment at 75 °C for 2 h. These results validate this mild approach for aiding future enzymatic hydrolysis. Copyright © 2013 Elsevier Ltd. All rights reserved.

Photocatalytic degradation of lignin on synthesized Ag-AgCl/ZnO nanorods under solar light and preliminary trials for methane fermentation.

PubMed

Li, Huifang; Lei, Zhongfang; Liu, Chunguang; Zhang, Zhenya; Lu, Baowang

2015-01-01

New photocatalysts, Ag-AgCl/ZnO nanorods, were successfully synthesized in this study by using microwave assisted chemical precipitation and deposition-precipitation-photoreduction methods. The optimal preparation condition was determined as pH 9 in distilled water and 40min for UV light photoreduction of Ag (i.e. Ag40-AgCl/ZnO) by degradation of methyl orange. This work investigated the feasibility of using Ag40-AgCl/ZnO to degrade lignin under natural solar light and then subsequent methane production with influencing factors like solution pH, dosage of catalyst and initial lignin concentration being considered. OH radicals were found to play the most important role in the photocatalytic process, and the new prepared catalyst possessed stable photocatalytic activity after 7 cycles' utilization. During the subsequent biogasification, the degraded lignin obtained from 120min photocatalysis yielded 184ml methane and 325ml biogas for per gram of removed total organic carbon, increased by 10.9% and 23.1%, respectively compared to the control. Copyright © 2014 Elsevier Ltd. All rights reserved.

Atmospheric carbon dioxide, irrigation, and fertilization effects on phenolic and nitrogen concentrations in loblolly pine (Pinus taeda) needles

Treesearch

Fitzgerald L. Booker; Christopher A. Maier

2001-01-01

Concentrations of total soluble phenolics, catechin, proanthocyanidins (PA), lignin and nitrogen (N) were measured in loblolly pine (Pinus taeda L.) needles exposed to either ambient CO2 concentration ([CO2]), ambient plus 175 or ambient plus 350 µmol O2 mol-1 in branch chambers...

Switchgrass Biomass Quality as Affected by Nitrogen Rate, Harvest Time, and Storage

DOE PAGES

Ibrahim, Mostafa; Hong, Chang Oh.; Singh, Shikha; ...

2017-01-25

The purpose of this study was to assess the changes in switchgrass (Panicum virgatum L.) biomass quality as affected by N rate, harvest time, and storage. This research was conducted near Bristol, SD, in 2010 and 2011. Treatments included three N rates (0, 56, and 112 kg N ha –1) applied annually and each N rate replicated four times. After a killing frost, all of the plots were harvested and baled in large round bales in October 2010 and November 2011. An area of about 30 m 2 from each plot was left unharvested to represent storage of standing switchgrassmore » over the winter and to determine dry matter yields. Switchgrass was analyzed for hemicellulose, cellulose, lignin, mineral elements, N, and C. In the first season, storage of the fall harvested switchgrass bales numerically increased the concentrations of hemicellulose, lignin, and N. In the second season, they increased significantly. Mineral elements significantly increased in both sampling seasons. Delaying harvest until spring decreased lignin, N, and mineral elements concentration, and increased cellulose and hemicellulose concentrations, but also reduced biomass yield. Results from this study suggest that delaying the switchgrass harvest until spring increased the overall feedstock quality for ethanol production, but yield reductions must be considered to determine the overall economic impact of a delayed harvest.« less

Switchgrass Biomass Quality as Affected by Nitrogen Rate, Harvest Time, and Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ibrahim, Mostafa; Hong, Chang Oh.; Singh, Shikha

The purpose of this study was to assess the changes in switchgrass (Panicum virgatum L.) biomass quality as affected by N rate, harvest time, and storage. This research was conducted near Bristol, SD, in 2010 and 2011. Treatments included three N rates (0, 56, and 112 kg N ha –1) applied annually and each N rate replicated four times. After a killing frost, all of the plots were harvested and baled in large round bales in October 2010 and November 2011. An area of about 30 m 2 from each plot was left unharvested to represent storage of standing switchgrassmore » over the winter and to determine dry matter yields. Switchgrass was analyzed for hemicellulose, cellulose, lignin, mineral elements, N, and C. In the first season, storage of the fall harvested switchgrass bales numerically increased the concentrations of hemicellulose, lignin, and N. In the second season, they increased significantly. Mineral elements significantly increased in both sampling seasons. Delaying harvest until spring decreased lignin, N, and mineral elements concentration, and increased cellulose and hemicellulose concentrations, but also reduced biomass yield. Results from this study suggest that delaying the switchgrass harvest until spring increased the overall feedstock quality for ethanol production, but yield reductions must be considered to determine the overall economic impact of a delayed harvest.« less

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

PubMed

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.

Nuclear magnetic resonance studies of ancient buried wood-I. Observations on the origin of coal to the brown coal stage

USGS Publications Warehouse

Hatcher, P.G.; Breger, I.A.; Earl, W.L.

1981-01-01

Various wood fragments buried in sediments under anaerobic conditions for from 450 yr to approximately 8 Myr have been examined by solid-state 13C nuclear magnetic resonance. Cellulose and other carbohydrates, the major components of Holocene wood, have been shown to be gradually hydrolyzed or otherwise lost under the conditions of burial. Lignin structures, however, are preserved relatively unchanged and become concentrated by difference as the carbohydrates disappear. Thus, a fragment of coalified wood isolated from a Miocene brown coal was found to be still composed of approximately 75% lignin and 25% cellulose. On the basis of our observations, we suggest that coalification of woody tissue progresses directly from lignin to coal and that such coalification may be retarded until most of the cellulose disappears. ?? 1981.

Multivariate Analysis of the Determinants of the End-Product Quality of Manure-Based Composts and Vermicomposts Using Bayesian Network Modelling

PubMed Central

Faverial, Julie; Cornet, Denis; Paul, Jacky

2016-01-01

Previous studies indicated that the quality of tropical composts is poorer than that of composts produced in temperate regions. The aim of this study was to test the type of manure, the use of co-composting with green waste, and the stabilization method for their ability to improve compost quality in the tropics. We produced 68 composts and vermicomposts that were analysed for their C, lignin and NPK contents throughout the composting process. Bayesian networks were used to assess the mechanisms controlling compost quality. The concentration effect, for C and lignin, and the initial blend quality, for NPK content, were the main factors affecting compost quality. Cattle manure composts presented the highest C and lignin contents, and poultry litter composts exhibited the highest NPK content. Co-composting improved quality by enhancing the concentration effect, which reduced the impact of C and nutrient losses. Vermicomposting did not improve compost quality; co-composting without earthworms thus appears to be a suitable stabilization method under the conditions of this study because it produced high quality composts and is easier to implement. PMID:27314950

Selection of the best chemical pretreatment for lignocellulosic substrate Prosopis juliflora.

PubMed

Naseeruddin, Shaik; Srilekha Yadav, K; Sateesh, L; Manikyam, Ananth; Desai, Suseelendra; Venkateswar Rao, L

2013-05-01

Pretreatment is a pre-requisite step in bioethanol production from lignocellulosic biomass required to remove lignin and increase the porosity of the substrate for saccharification. In the present study, chemical pretreatment of Prosopis juliflora was performed using alkali (NaOH, KOH, and NH3), reducing agents (Na2S2O4, Na2SO3) and NaClO2 in different concentration ranges at room temperature (30±2 °C) to remove maximum lignin with minimum sugar loss. Further, biphasic acid hydrolysis of the various pretreated substrates was performed at mild temperatures. Considering the amount of holocellulose hydrolyzed and inhibitors released during hydrolysis, best chemical pretreatment was selected. Among all the chemicals investigated, pretreatment with sodium dithionite at concentration of 2% (w/v) removed maximum lignin (80.46±1.35%) with a minimum sugar loss (2.56±0.021%). Subsequent biphasic acid hydrolysis of the sodium dithionite pretreated substrate hydrolyzed 40.09±1.22% of holocellulose and released minimum amount of phenolics (1.04±0.022 g/L) and furans (0.41±0.012 g/L) in the hydrolysate. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biochemical Composition Suggests Different Roles of Leaf Litter and Fine Roots in Soil Carbon Formation

NASA Astrophysics Data System (ADS)

Xia, M.; Pregitzer, K. S.; Talhelm, A. F.

2012-12-01

Plant litter is a major source of soil organic carbon (C). This litter is not homogenous, but instead primarily composed of fine root and leaf litter that adapted to different physiological functions. These unique functions suggest that root and leaf litter likely have different biochemical traits, and thus different decomposition patterns. However, few studies have compared their substrate quality and contributions to soil C. Also, much less attention has been given to fine roots although they can represent a substantial litter production. Here we hypothesize that 1) leaf litter and fine roots have different substrate quality as they are highly different in biochemical composition; 2) the biochemical composition of leaf litter and fine roots responds differently to the simulated nitrogen (N) deposition. To test these hypotheses, we collected leaf litter and fine roots of Acer saccharum (the dominant species in the northern temperate ecosystems we studied) in both ambient and N addition treatment plots at four sites of Michigan N deposition gradient study. We quantified ten biochemical components thought to be important on decomposition. Strikingly, we found a consistently three-fold higher lignin concentration in fine roots than that in leaf litter (P< 0.01). On average, lignin concentration of fine roots was 45.4±0.3% while that of leaf litter was 13.5±0.2%. Lignin has been considered highly recalcitrant and hypothesized as the major precursor of humus substance. Condensed tannin (CT) concentration in fine roots (13.13±0.51%) was also substantially higher than that in leaf litter (P< 0.01, 4.63±0.42 %). Tissue CT can inhibit litter decay by both precipitating proteins and by having antimicrobial properties. In contrast, fine roots exhibited lower concentrations of non-structural carbohydrates (NSC), soluble phenolics, and holocellulose (hemicelluloses & cellulose) than leaf litter (P< 0.01). These components are considered more easily accessible, and may stimulate the decay of lignin by providing required energy. Therefore, fine roots of Acer saccharum have a relatively recalcitrant nature based on their distinct biochemical composition, suggesting fine roots may be the major driver of soil carbon formation in the ecosystems we studied. Litter type and N addition had significant interactions on lignin, holocellulose, and NSC (P< 0.05), indicating these traits of different litter types respond differently to N addition. In leaf litter, the concentrations of lignin, NSC, and bound CT were affected by N addition (P< 0.05). By contrast, N addition only reduced the soluble protein concentration in fine roots (P< 0.05). Hence, substrate quality of leaf litter and fine roots responds differently to the simulated N deposition, and may eventually lead to different responses in decomposition pattern. This is one of few studies comparing the detailed biochemical profile of leaf litter and fine roots in a dominant tree species. Different biochemical traits of fine roots and leaf litter may reflect the different specializations for their physiological functions. This work highlights the importance of fine root in the soil carbon formation due to its recalcitrant nature, and emphasizes the necessity of differentiating the responses of leaf litter and fine root decompositions to environmental changes when modeling biogeochemical cycles.

Production of Monomeric Aromatic Compounds from Oil Palm Empty Fruit Bunch Fiber Lignin by Chemical and Enzymatic Methods

PubMed Central

Tang, Pei-Ling; Hassan, Osman; Maskat, Mohamad Yusof; Badri, Khairiah

2015-01-01

In this study, oil palm empty fruit bunch (OPEFBF) was pretreated with alkali, and lignin was extracted for further degradation into lower molecular weight phenolic compounds using enzymes and chemical means. Efficiency of monomeric aromatic compounds production from OPEFBF lignin via chemical (nitrobenzene versus oxygen) and enzymatic [cutinase versus manganese peroxidase (MnP)] approaches was investigated. The effects of sodium hydroxide concentration (2, 5, and 10% wt.) and reaction time (30, 90, and 180 minutes) on the yield of aromatic compounds were studied. The results obtained indicated that nitrobenzene oxidation produced the highest yield (333.17 ± 49.44 ppm hydroxybenzoic acid, 5.67 ± 0.25 ppm p-hydroxybenzaldehyde, 25.57 ± 1.64 ppm vanillic acid, 168.68 ± 23.23 ppm vanillin, 75.44 ± 6.71 ppm syringic acid, 815.26 ± 41.77 ppm syringaldehyde, 15.21 ± 2.19 ppm p-coumaric acid, and 44.75 ± 3.40 ppm ferulic acid), among the tested methods. High sodium hydroxide concentration (10% wt.) was needed to promote efficient nitrobenzene oxidation. However, less severe oxidation condition was preferred to preserve the hydroxycinnamic acids (p-coumaric acid and ferulic acid). Cutinase-catalyzed hydrolysis was found to be more efficient than MnP-catalyzed oxidation in the production of aromatic compounds. By hydrolyzed 8% wt. of lignin with 0.625 mL cutinase g−1 lignin at pH 8 and 55°C for 24 hours, about 642.83 ± 14.45 ppm hydroxybenzoic acid, 70.19 ± 3.31 ppm syringaldehyde, 22.80 ± 1.04 ppm vanillin, 27.06 ± 1.20 ppm p-coumaric acid, and 50.19 ± 2.23 ppm ferulic acid were produced. PMID:26798644

Dissolved Organic Matter Compositional Change and Biolability During Two Storm Runoff Events in a Small Agricultural Watershed

NASA Astrophysics Data System (ADS)

Eckard, Robert S.; Pellerin, Brian A.; Bergamaschi, Brian A.; Bachand, Philip A. M.; Bachand, Sandra M.; Spencer, Robert G. M.; Hernes, Peter J.

2017-10-01

Agricultural watersheds are globally pervasive, supporting fundamentally different organic matter source, composition, and concentration profiles in comparison to natural systems. Similar to natural systems, agricultural storm runoff exports large amounts of organic carbon from agricultural land into waterways. But intense management of upper soil layers, waterway channelization, wetland and riparian habitat removal, and postharvest vegetation removal promise to uniquely drive organic matter release to waterways. During a winter first flush and a subsequent storm event, this study investigated the influence of a small agricultural watershed on dissolved organic matter (DOM) source, composition, and biolability. Storm water discharge released strongly terrestrial yet biolabile (23 to 32%) dissolved organic carbon (DOC). Following a 21 day bioassay, a parallel factor analysis identified an 80% reduction in a protein-like (phenylpropyl) component (C2) that was previously correlated to lignin phenol concentration, and a 10% reduction in a humic-like, terrestrially sourced component (C4). Storm-driven releases tripled DOC concentration (from 2.8 to 8.7 mg L-1) during the first flush event in comparison to base flow and were terrestrially sourced, with an eightfold increase in vascular plant derived lignin phenols (23.0 to 185 μg L-1). As inferred from system hydrology, lignin composition, and nitrate as a groundwater tracer, an initial pulse of dilute water from the upstream watershed caused a counterclockwise DOC hysteresis loop. DOC concentrations peaked after 3.5 days, with the delay between peak discharge and peak DOC attributed to storm water hydrology and a period of initial water repellency of agricultural soils, which delayed DOM leaching.

Spectroscopic determination of leaf biochemistry using band-depth analysis of absorption features and stepwise multiple linear regression

USGS Publications Warehouse

Kokaly, R.F.; Clark, R.N.

1999-01-01

We develop a new method for estimating the biochemistry of plant material using spectroscopy. Normalized band depths calculated from the continuum-removed reflectance spectra of dried and ground leaves were used to estimate their concentrations of nitrogen, lignin, and cellulose. Stepwise multiple linear regression was used to select wavelengths in the broad absorption features centered at 1.73 ??m, 2.10 ??m, and 2.30 ??m that were highly correlated with the chemistry of samples from eastern U.S. forests. Band depths of absorption features at these wavelengths were found to also be highly correlated with the chemistry of four other sites. A subset of data from the eastern U.S. forest sites was used to derive linear equations that were applied to the remaining data to successfully estimate their nitrogen, lignin, and cellulose concentrations. Correlations were highest for nitrogen (R2 from 0.75 to 0.94). The consistent results indicate the possibility of establishing a single equation capable of estimating the chemical concentrations in a wide variety of species from the reflectance spectra of dried leaves. The extension of this method to remote sensing was investigated. The effects of leaf water content, sensor signal-to-noise and bandpass, atmospheric effects, and background soil exposure were examined. Leaf water was found to be the greatest challenge to extending this empirical method to the analysis of fresh whole leaves and complete vegetation canopies. The influence of leaf water on reflectance spectra must be removed to within 10%. Other effects were reduced by continuum removal and normalization of band depths. If the effects of leaf water can be compensated for, it might be possible to extend this method to remote sensing data acquired by imaging spectrometers to give estimates of nitrogen, lignin, and cellulose concentrations over large areas for use in ecosystem studies.We develop a new method for estimating the biochemistry of plant material using spectroscopy. Normalized band depths calculated from the continuum-removed reflectance spectra of dried and ground leaves were used to estimate their concentrations of nitrogen, lignin, and cellulose. Stepwise multiple linear regression was used to select wavelengths in the broad absorption features centered at 1.73 ??m, 2.10 ??m, and 2.301 ??m that were highly correlated with the chemistry of samples from eastern U.S. forests. Band depths of absorption features at these wavelengths were found to also be highly correlated with the chemistry of four other sites. A subset of data from the eastern U.S. forest sites was used to derive linear equations that were applied to the remaining data to successfully estimate their nitrogen, lignin, and cellulose concentrations. Correlations were highest for nitrogen (R2 from 0.75 to 0.94). The consistent results indicate the possibility of establishing a single equation capable of estimating the chemical concentrations in a wide variety of species from the reflectance spectra of dried leaves. The extension of this method to remote sensing was investigated. The effects of leaf water content, sensor signal-to-noise and bandpass, atmospheric effects, and background soil exposure were examined. Leaf water was found to be the greatest challenge to extending this empirical method to the analysis of fresh whole leaves and complete vegetation canopies. The influence of leaf water on reflectance spectra must be removed to within 10%. Other effects were reduced by continuum removal and normalization of band depths. If the effects of leaf water can be compensated for, it might be possible to extend this method to remote sensing data acquired by imaging spectrometers to give estimates of nitrogen, lignin, and cellulose concentrations over large areas for use in ecosystem studies.

Molecular Signature of Organic Carbon Along a Salinity Gradient in Suwannee River Plume

NASA Astrophysics Data System (ADS)

Liu, Y.; Bianchi, T. S.; Ward, N. D.; Arellano, A. R.; Paša-Tolić, L.; Tolic, N.; Kuo, L. J.

2016-12-01

Humic and fulvic acid isolates from Suwannee River dissolved organic matter (DOM) have served as reference standards for the International Humic Substances Society (IHSS) for many decades. The large database on Suwannee DOM provides an excellent framework to further expand the application of Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS) in characterizing the chemical composition of aquatic DOM. In this study, we examined the DOM signature of the lower Suwannee River and plume region at 5 stations along a salinity gradient (0 to 28) using FT-ICR-MS. The chemical characteristics of DOM show distinct differences across this steep salinity gradient. In general, samples collected from the coastal station have lower carbon number and are less aromatic. Molecular level analysis reveals that the magnitude weighted proportion of lipids increased as salinity increased. Interestingly, a similar trend was observed for lignin-like compounds. Target quantification of lignin-phenols showed that while the concentrations of these compounds were lower at the coastal station, the DOC-normalized concentrations were not significantly different between the river and coastal stations. In addition to traditional DOM moieties, we identified for the first time, halogenated organic compounds (HOC). We observed more chlorinated compounds in DOM and increased Cl/C as salinity increased. A relatively high proportion of halogenated lipids (compared to non-halogenated) were observed in the total pool of HOC across all stations. Although not significant in relative proportion, halogenated lignin-like compounds were the most abundant HOC moieties in our samples. CO2 concentrations decreased and became more 13C-enriched along the salinity gradient, ranging from 3,990 ppm (13CO2 = -17.3‰) at salinity 0 to 520 ppm (13CO2 = -7.5‰) at salinity 28, indicating high levels of DOM degradation in the river and a shift to primary production in the marine receiving waters, which is consistent with trends of lipid and lignin-like compounds observed with FT-ICR-MS.

New insights into the origin of perylene in geological samples

NASA Astrophysics Data System (ADS)

Grice, Kliti; Lu, Hong; Atahan, Pia; Asif, Muhammad; Hallmann, Christian; Greenwood, Paul; Maslen, Ercin; Tulipani, Svenja; Williford, Kenneth; Dodson, John

2009-11-01

The origin of the polycyclic aromatic hydrocarbon (PAH) perylene in sediments and petroleum has been a matter of continued debate. Reported to occur in Phanerozoic organic matter (OM), fossil crinoids and tropical termite mounds, its mechanism of formation remains unclear. While a combustion source can be excluded, structural similarities to perylene quinone-like components present in e.g. fungi, plants, crinoids and insects, potentially suggest a product-precursor relationship. Here, we report perylene concentrations, 13C/ 12C, and D/H ratios from a Holocene sediment profile from the Qingpu trench, Yangtze Delta region, China. Perylene concentrations differ from those of pyrogenic PAHs, and rise to prominence in a stratigraphic interval that was dominated by woody vegetation as determined by palynology including fungal spores. In this zone, perylene concentrations exhibit an inverse relationship to the lignin marker guaiacol, D/H ratios between -284‰ and -317‰, similar to the methoxy groups in lignin, as well as co-variation with spores from wood-degrading fungi. 13C/ 12C of perylene differs from that of land plant wax alkanes and falls in the fractionation range expected for saprophytic fungi that utilise lignin, which is isotopically lighter than cellulose and whole wood. During progressive lignin degradation, the relative carbon isotopic ratio of the perylene decreases. We therefore hypothesise a relationship of perylene to the activity of wood-degrading fungi. To support our hypothesis, we analysed a wide range of Phanerozoic sediments and oils, and found perylene to generally be present in subordinate amounts before the evolutionary rise of vascular plants, and to be generally absent from marine-sourced oils, few exceptions being attributed perhaps to a contribution of marine and/or terrestrial-derived fungi, anoxia (especially under marine conditions) and/or contamination of core material by fungi. A series of low-molecular-weight aromatic quinones bearing the perylene-backbone were detected in Devonian and Cretaceous sediments, potentially representing precursor components to perylene.

Simulated Nitrogen Deposition has Minor Effects on Ecosystem Pools and Fluxes of Energy, Elements, and Biochemicals in a Northern Hardwoods Forest

NASA Astrophysics Data System (ADS)

Talhelm, A. F.; Pregitzer, K. S.; Burton, A. J.; Xia, M.; Zak, D. R.

2017-12-01

The elemental and biochemical composition of plant tissues is an important influence on primary productivity, decomposition, and other aspects of biogeochemistry. Human activity has greatly altered biogeochemical cycles in ecosystems downwind of industrialized regions through atmospheric nitrogen deposition, but most research on these effects focuses on individual elements or steps in biogeochemical cycles. Here, we quantified pools and fluxes of biomass, the four major organic elements (carbon, oxygen, hydrogen, nitrogen), four biochemical fractions (lignin, structural carbohydrates, cell walls, and soluble material), and energy in a mature northern hardwoods forest in Michigan. We sampled the organic and mineral soil, fine and coarse roots, leaf litter, green leaves, and wood for chemical analyses. We then combined these data with previously published and archival information on pools and fluxes within this forest, which included replicated plots receiving either ambient deposition or simulated nitrogen deposition (3 g N m-2 yr-1 for 18 years). Live wood was the largest pool of energy and all elements and biochemical fractions. However, the production of wood, leaf litter, and fine roots represented similar fluxes of carbon, hydrogen, oxygen, cell wall material, and energy, while nitrogen fluxes were dominated by leaf litter and fine roots. Notably, the flux of lignin via fine roots was 70% higher than any other flux. Experimental nitrogen deposition had relatively few significant effects, increasing foliar nitrogen, increasing the concentration of lignin in the soil organic horizon and decreasing pools of all elements and biochemical fractions in the soil organic horizon except nitrogen, lignin, and structural carbohydrates. Overall, we found that differences in tissue chemistry concentrations were important determinants of ecosystem-level pools and fluxes, but that nitrogen deposition had little effect on concentrations, pools, or fluxes in this mature forest. Disclaimer: The views expressed in this poster are those of the authors and do not necessarily represent the views or policies of the U.S. EPA.

Lignosulfonate and elevated pH can enhance enzymatic saccharification of lignocelluloses

PubMed Central

2013-01-01

Background Nonspecific (nonproductive) binding (adsorption) of cellulase by lignin has been identified as a key barrier to reduce cellulase loading for economical sugar and biofuel production from lignocellulosic biomass. Sulfite Pretreatment to Overcome Recalcitrance of Lignocelluloses (SPORL) is a relatively new process, but demonstrated robust performance for sugar and biofuel production from woody biomass especially softwoods in terms of yields and energy efficiencies. This study demonstrated the role of lignin sulfonation in enhancing enzymatic saccharification of lignocelluloses – lignosulfonate from SPORL can improve enzymatic hydrolysis of lignocelluloses, contrary to the conventional belief that lignin inhibits enzymatic hydrolysis due to nonspecific binding of cellulase. Results The study found that lignosulfonate from SPORL pretreatment and from a commercial source inhibits enzymatic hydrolysis of pure cellulosic substrates at low concentrations due to nonspecific binding of cellulase. Surprisingly, the reduction in enzymatic saccharification efficiency of a lignocellulosic substrate was fully recovered as the concentrations of these two lignosulfonates increased. We hypothesize that lignosulfonate serves as a surfactant to enhance enzymatic hydrolysis at higher concentrations and that this enhancement offsets its inhibitive effect from nonspecific binding of cellulase, when lignosulfonate is applied to lignocellulosic solid substrates. Lignosulfonate can block nonspecific binding of cellulase by bound lignin on the solid substrates, in the same manner as a nonionic surfactant, to significantly enhance enzymatic saccharification. This enhancement is linearly proportional to the amount of lignosulfonate applied which is very important to practical applications. For a SPORL-pretreated lodgepole pine solid, 90% cellulose saccharification was achieved at cellulase loading of 13 FPU/g glucan with the application of its corresponding pretreatment hydrolysate coupled with increasing hydrolysis pH to above 5.5 compared with only 51% for the control run without lignosulfonate at pH 5.0. The pH-induced lignin surface modification at pH 5.5 further reduced nonspecific binding of cellulase by lignosulfonate. Conclusions The results reported in this study suggest significant advantages for SPORL-pretreatment in terms of reducing water usage and enzyme dosage, and simplifying process integration, i.e., it should eliminate washing of SPORL solid fraction for direct simultaneous enzymatic saccharification and combined fermentation of enzymatic and pretreatment hydrolysates (SSCombF). Elevated pH 5.5 or higher, rather than the commonly believed optimal and widely practiced pH 4.8-5.0, should be used in conducting enzymatic saccharification of lignocelluloses. PMID:23356796

Synthesis and application of nano-, meso- and macroporous sorbents based on lignin for detoxication of biological fluids

NASA Astrophysics Data System (ADS)

Chopabayeva, Nazira N.; Mukanov, Kanatbek N.; Tasmagambet, Amandyk T.

2014-05-01

Novel nano-, meso- and macroporous sorbents based on hydrolysis lignin have been synthesized by catalytic o-alkylation of biolpolymer with epoxy resin ED-20 and subsequent amination of formed α-oxyde derivative. Composition, structure, morphology and physical, chemical properties of ion-exchangers were investigated by FTIR, SEM, TEM, porosimetry and potentiometric titration method. It has been established that alkaline activated lignin shows an increase of SBET to 20.9 m2/g while modification leads to decrease of SBET more than double (from 9.2 to 5.2 m2/g) that of an untreared sample (14.5 m2/g). Synthesized sorbents are characterized by approximately identical mesoporous structure and mainly contained a pore size of 10-14 nm. The results clearly demonstrate the efficiency of lignin based sorbents for the removal of water and lipid soluble toxic metabolites from blood serum of diabetic retinopathy patients. Samples reduced the high level of total cholesterol, including its most atherogenic fractions (LDL-C, VLDL-C), triglyceride to the level of optimum compensated diabetes without significant removal of HDL-C. Concentration of glucose was decreased to physiological norms.

Chemical intervention in bacterial lignin degradation pathways: Development of selective inhibitors for intradiol and extradiol catechol dioxygenases.

PubMed

Sainsbury, Paul D; Mineyeva, Yelena; Mycroft, Zoe; Bugg, Timothy D H

2015-06-01

Bacterial lignin degradation could be used to generate aromatic chemicals from the renewable resource lignin, provided that the breakdown pathways can be manipulated. In this study, selective inhibitors of enzymatic steps in bacterial degradation pathways were developed and tested for their effects upon lignin degradation. Screening of a collection of hydroxamic acid metallo-oxygenase inhibitors against two catechol dioxygenase enzymes, protocatechuate 3,4-dioxygenase (3,4-PCD) and 2,3-dihydroxyphenylpropionate 1,2-dioxygenase (MhpB), resulted in the identification of selective inhibitors D13 for 3,4-PCD (IC50 15μM) and D3 for MhpB (IC50 110μM). Application of D13 to Rhodococcus jostii RHA1 in minimal media containing ferulic acid led to the appearance of metabolic precursor protocatechuic acid at low concentration. Application of 1mM disulfiram, an inhibitor of mammalian aldehyde dehydrogenase, to R. jostii RHA1, gave rise to 4-carboxymuconolactone on the β-ketoadipate pathway, whereas in Pseudomonas fluorescens Pf-5 disulfiram treatment gave rise to a metabolite found to be glycine betaine aldehyde. Copyright © 2015 Elsevier Inc. All rights reserved.

Toward the complete utilization of rice straw: Methane fermentation and lignin recovery by a combinational process involving mechanical milling, supporting material and nanofiltration.

PubMed

Sasaki, Kengo; Okamoto, Mami; Shirai, Tomokazu; Tsuge, Yota; Fujino, Ayami; Sasaki, Daisuke; Morita, Masahiko; Matsuda, Fumio; Kikuchi, Jun; Kondo, Akihiko

2016-09-01

Rice straw was mechanically milled using a process consuming 1.9MJ/kg-biomass, and 10g/L of unmilled or milled rice straw was used as the carbon source for methane fermentation in a digester containing carbon fiber textile as the supporting material. Milling increased methane production from 226 to 419mL/L/day at an organic loading rate of 2180mg-dichromate chemical oxygen demand/L/day, corresponding to 260mLCH4/gVS. Storage of the fermentation effluent at room temperature decreased the weight of the milled rice straw residue from 3.81 to 1.00g/L. The supernatant of the effluent was subjected to nanofiltration. The black concentrates deposited on the nanofiltration membranes contained 53.0-57.9% lignin. Solution nuclear magnetic resonance showed that lignin aromatic components such as p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) were retained primarily, and major lignin interunit structures such as the β-O-4-H/G unit were absent. This combinational process will aid the complete utilization of rice straw. Copyright © 2016. Published by Elsevier Ltd.

Comparative study for hardwood and softwood forest biomass: chemical characterization, combustion phases and gas and particulate matter emissions.

PubMed

Amaral, Simone Simões; de Carvalho, João Andrade; Costa, Maria Angélica Martins; Soares Neto, Turíbio Gomes; Dellani, Rafael; Leite, Luiz Henrique Scavacini

2014-07-01

Two different types of typical Brazilian forest biomass were burned in the laboratory in order to compare their combustion characteristics and pollutant emissions. Approximately 2 kg of Amazon biomass (hardwood) and 2 kg of Araucaria biomass (softwood) were burned. Gaseous emissions of CO2, CO, and NOx and particulate matter smaller than 2.5 μm (PM2.5) were evaluated in the flaming and smoldering combustion phases. Temperature, burn rate, modified combustion efficiency, emissions factor, and particle diameter and concentration were studied. A continuous analyzer was used to quantify gas concentrations. A DataRam4 and a Cascade Impactor were used to sample PM2.5. Araucaria biomass (softwood) had a lignin content of 34.9%, higher than the 23.3% of the Amazon biomass (hardwood). CO2 and CO emissions factors seem to be influenced by lignin content. Maximum concentrations of CO2, NOx and PM2.5 were observed in the flaming phase. Copyright © 2014 Elsevier Ltd. All rights reserved.

Cloning and characterization of a cDNA encoding a novel extracellular peroxidase from Trametes versicolor.

PubMed

Collins, P J; O'Brien, M M; Dobson, A D

1999-03-01

The white rot basidiomycete Trametes versicolor secretes a large number of peroxidases which are believed to be involved in the degradation of polymeric lignin. These peroxidases have been classified previously as lignin peroxidases or manganese peroxidases (MnP). We have isolated a novel extracellular peroxidase-encoding cDNA sequence from T. versicolor CU1, the transcript levels of which are repressed by low concentrations of Mn2+ and induced by nitrogen and carbon but not induced in response to a range of stresses which have been reported to induce MnP expression.

Cloning and Characterization of a cDNA Encoding a Novel Extracellular Peroxidase from Trametes versicolor

PubMed Central

Collins, Patrick J.; O’Brien, Margaret M.; Dobson, Alan D. W.

1999-01-01

The white rot basidiomycete Trametes versicolor secretes a large number of peroxidases which are believed to be involved in the degradation of polymeric lignin. These peroxidases have been classified previously as lignin peroxidases or manganese peroxidases (MnP). We have isolated a novel extracellular peroxidase-encoding cDNA sequence from T. versicolor CU1, the transcript levels of which are repressed by low concentrations of Mn2+ and induced by nitrogen and carbon but not induced in response to a range of stresses which have been reported to induce MnP expression. PMID:10049906

Characterization of Novel Sorghum brown midrib Mutants from an EMS-Mutagenized Population

PubMed Central

Sattler, Scott E.; Saballos, Ana; Xin, Zhanguo; Funnell-Harris, Deanna L.; Vermerris, Wilfred; Pedersen, Jeffrey F.

2014-01-01

Reducing lignin concentration in lignocellulosic biomass can increase forage digestibility for ruminant livestock and saccharification yields of biomass for bioenergy. In sorghum (Sorghum bicolor (L.) Moench) and several other C4 grasses, brown midrib (bmr) mutants have been shown to reduce lignin concentration. Putative bmr mutants isolated from an EMS-mutagenized population were characterized and classified based on their leaf midrib phenotype and allelism tests with the previously described sorghum bmr mutants bmr2, bmr6, and bmr12. These tests resulted in the identification of additional alleles of bmr2, bmr6, and bmr12, and, in addition, six bmr mutants were identified that were not allelic to these previously described loci. Further allelism testing among these six bmr mutants showed that they represented four novel bmr loci. Based on this study, the number of bmr loci uncovered in sorghum has doubled. The impact of these lines on agronomic traits and lignocellulosic composition was assessed in a 2-yr field study. Overall, most of the identified bmr lines showed reduced lignin concentration of their biomass relative to wild-type (WT). Effects of the six new bmr mutants on enzymatic saccharification of lignocellulosic materials were determined, but the amount of glucose released from the stover was similar to WT in all cases. Like bmr2, bmr6, and bmr12, these mutants may affect monolignol biosynthesis and may be useful for bioenergy and forage improvement when stacked together or in combination with the three previously described bmr alleles. PMID:25187038

Correlation between the distribution of lignin and pectin and distribution of sorbed metal ions (lead and zinc) on coir (Cocos nucifera L.).

PubMed

Conrad, Kathrine

2008-11-01

Plant fibres are capacious for sorption of metal ions, and can be used in water cleaning. Knowledge about the sorption will help in selection of the fibre and optimisation of its chemical modification, if any. The aim of this paper is to investigate the connection, if any, between the distribution of lignin and pectin and the loading of Pb and Zn on coir (mesocarp fibres from Cocos nucifera L.). The coir consisted mainly of xylem and a fibre sheath. The lignin was evenly distributed in the cell walls of the fibre sheath, but in the xylem, there was no detectable content in the compound middle lamella, and a smaller content of lignin in the secondary walls than in the walls of the fibre sheath. The only detectable content of pectin in the fibre sheath walls was in the middle lamella, cell corners and extracellular matrix, while in the xylem, the pectin was almost evenly distributed in the wall, with a higher concentration in the middle lamella and cell corners. All cell walls facing the lacuna had a high content of pectin. The metal ions were mainly loaded on the xylem and cell walls facing the lacuna, maybe with an additional trend to be loaded on the large fibres. Lead was distributed on and across the whole secondary wall. Zinc was loaded on the secondary walls, but there was no information about the distribution across the wall. If there is a simple correlation between the loading of metal ions and the distribution of lignin or pectin, these investigations point at no correlation with lignin and a positive correlation with pectin. It has to be stressed that these conclusions are made on limited material and are therefore preliminary in nature.

Penicillium sp. strain that efficiently adsorbs lignosulfonate in the presence of sulfate ion.

PubMed

Aoyama, Akihisa; Kurane, Ryuichiro; Nagai, Kazuo

2013-03-01

Lignin is one of the major water insoluble substances that support the physical properties of plants and can be solubilized by sulfite or alkaline treatment in accordance with pulpification. The lignin derivatives produced by both the sulfite and the kraft processes are called lignosulfonate (LS) and kraft lignin (KL), respectively, and both derivatives show a broad spectrum of optical absorbance from ultraviolet to visible light. When the spore suspension of an isolated Penicillium sp., Penicillium sp. A, was inoculated to a medium containing 0.1% commercial LS, absorbance at 480 nm (A480) almost completely disappeared after 5 days of cultivation. Maximum decolorization of the culture broth was observed when the microbe was cultured in the 0.8% LS medium reaching 88%, and the amount of LS removed was calculated to be 7 g/L. In a similar assay with the dark-liquid containing KL, 80% of the A480 of a 20% (v/v) dark-liquid medium disappeared after 5 days of culturing and the amount of KL removed was calculated to be 2.9 g/L. These values significantly exceeded the previously reported amounts with respect to substrate concentration and decolorization. Furthermore, since similar results were obtained in the cases of both LS and KL, it is expected that the present strain is able to non-specifically adsorb a wide range of lignin derivatives, because most of the colored substances were recovered in the culture sediments. Thus, the strain can be used to clean up waste fluids containing water soluble lignin derivatives, adsorb lignin derivatives in waste fluids before dehydration. Copyright © 2012 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

The Inhibition of Hepatic and Renal Glucuronidation of p-Nitrophenol and 4-Methylumbelliferone by Oil Palm Empty Fruit Bunch Lignin and Its Main Oxidation Compounds

PubMed Central

Salleh, Norliyana Mohamad; Ismail, Sabariah; Ibrahim, Mohamad Nasir Mohamad

2017-01-01

Background: In order to develop oil palm empty fruit bunch (EFB) lignin as a nutraceutical and health supplement, the investigation of its potential in interacting with other drugs via inhibition of drug-metabolizing enzymes (DMEs) would ensure product safety. Objective: The study was aimed to investigate the in vitro effect of oil palm EFB lignin and its main oxidation compounds on phase II DME UDP-glucuronosyltransferases (UGTs) in rat liver and kidney microsomes. Materials and Methods: The p-nitrophenol (p-NP) and 4-methylumbelliferone (4-MU) were employed as probe substrates in glucuronidation assays. The effect of soda oil palm EFB lignin on Vmax, Km, CLint, Ki, and mode of inhibition of 4-MU glucuronidation in RLM was also determined. Results: The inhibitory potency of oil palm EFB lignin for both p-NP and 4-MU glucuronidation in rat liver microsome (RLM) and rat kidneys microsomes (RKM) was found to be in the rank order of soda > kraft > organosolv. However, the inhibitory potency of its main oxidation compounds were in the rank order of vanillin > syringaldehyde > p-hydroxybenzaldehyde. Soda oil palm EFB lignin exhibited mixed-type inhibition against 4-MU glucuronidation in RLM, showing the change in apparent Vmax and with only a minor effect on Km compared with control. Conclusions: The findings showed that effect of oil palm EFB lignin on both p-NP and 4-MU glucuronidation in RLM and RKM was enhanced by the presence of vanillin as well as flavonoids. Kinetic study showed that soda oil palm EFB lignin exhibited strong inhibition on UGT activity in RLM with mixed-type inhibition mode. SUMMARY The inhibitory potential of oil palm EFB lignin extracts for p-NP and 4-MU glucuronidation in RLM and RKM can be listed in the following rank order: soda > kraft > organosolvThe inhibitory potential of oil palm EFB lignin main oxidation compounds for p-NP and 4-MU glucuronidation in RLM and RKM can be listed in the following rank order: vanillin > syringaldehyde > p-hydroxybenzaldehydeResults suggested that the effect of oil palm EFB lignin on p-NP and 4-MU glucuronidation activity in both RLM and RKM was enhanced by the presence of vanillin as well as total flavonoid contentResults also suggested that oil palm EFB lignin may inhibit glucuronidation of substrate by UGT enzymes, especially UGT1A6, particularly in rat liver Abbreviations used: p-NP: p-Nitrophenol, 4-MU: 4-Methylumbelliferone, EFB: Empty fruit bunch, DME: Drug-metabolizing enzymes, UGT: UDPglucuronosyltransferase, Vmax: Maximal reaction velocity, Km: Michaelis-Menten constant, CLint: Intrinsic clearance, Ki: Dissociation constant of an inhibitor enzyme complex, 4-MUG: 4-Methylumbelliferone glucuronide, DMSO: Dimethyl sulfoxide, IC50: Half maximal inhibitory concentration, p-NPG: p-Nitrophenol glucuronide, RKM: Rat kidneys microsomes, RLM: Rat liver microsome, UDPGA: UDPglucuronic acid, TCA: trichloroacetic acid, MPA: mycophenolic acid PMID:28479734

The Inhibition of Hepatic and Renal Glucuronidation of p-Nitrophenol and 4-Methylumbelliferone by Oil Palm Empty Fruit Bunch Lignin and Its Main Oxidation Compounds.

PubMed

Salleh, Norliyana Mohamad; Ismail, Sabariah; Ibrahim, Mohamad Nasir Mohamad

2017-01-01

In order to develop oil palm empty fruit bunch (EFB) lignin as a nutraceutical and health supplement, the investigation of its potential in interacting with other drugs via inhibition of drug-metabolizing enzymes (DMEs) would ensure product safety. The study was aimed to investigate the in vitro effect of oil palm EFB lignin and its main oxidation compounds on phase II DME UDP-glucuronosyltransferases (UGTs) in rat liver and kidney microsomes. The p -nitrophenol ( p -NP) and 4-methylumbelliferone (4-MU) were employed as probe substrates in glucuronidation assays. The effect of soda oil palm EFB lignin on V max , K m , CL int , K i , and mode of inhibition of 4-MU glucuronidation in RLM was also determined. The inhibitory potency of oil palm EFB lignin for both p -NP and 4-MU glucuronidation in rat liver microsome (RLM) and rat kidneys microsomes (RKM) was found to be in the rank order of soda > kraft > organosolv. However, the inhibitory potency of its main oxidation compounds were in the rank order of vanillin > syringaldehyde > p -hydroxybenzaldehyde. Soda oil palm EFB lignin exhibited mixed-type inhibition against 4-MU glucuronidation in RLM, showing the change in apparent V max and with only a minor effect on K m compared with control. The findings showed that effect of oil palm EFB lignin on both p -NP and 4-MU glucuronidation in RLM and RKM was enhanced by the presence of vanillin as well as flavonoids. Kinetic study showed that soda oil palm EFB lignin exhibited strong inhibition on UGT activity in RLM with mixed-type inhibition mode. The inhibitory potential of oil palm EFB lignin extracts for p -NP and 4-MU glucuronidation in RLM and RKM can be listed in the following rank order: soda > kraft > organosolvThe inhibitory potential of oil palm EFB lignin main oxidation compounds for p -NP and 4-MU glucuronidation in RLM and RKM can be listed in the following rank order: vanillin > syringaldehyde > p-hydroxybenzaldehydeResults suggested that the effect of oil palm EFB lignin on p -NP and 4-MU glucuronidation activity in both RLM and RKM was enhanced by the presence of vanillin as well as total flavonoid contentResults also suggested that oil palm EFB lignin may inhibit glucuronidation of substrate by UGT enzymes, especially UGT1A6, particularly in rat liver Abbreviations used: p -NP: p -Nitrophenol, 4-MU: 4-Methylumbelliferone, EFB: Empty fruit bunch, DME: Drug-metabolizing enzymes, UGT: UDPglucuronosyltransferase, V max : Maximal reaction velocity, K m : Michaelis-Menten constant, CLint: Intrinsic clearance, K i : Dissociation constant of an inhibitor enzyme complex, 4-MUG: 4-Methylumbelliferone glucuronide, DMSO: Dimethyl sulfoxide, IC50: Half maximal inhibitory concentration, p -NPG: p -Nitrophenol glucuronide, RKM: Rat kidneys microsomes, RLM: Rat liver microsome, UDPGA: UDPglucuronic acid, TCA: trichloroacetic acid, MPA: mycophenolic acid.

Immobilized ligninolytic enzymes: An innovative and environmental responsive technology to tackle dye-based industrial pollutants - A review.

PubMed

Bilal, Muhammad; Asgher, Muhammad; Parra-Saldivar, Roberto; Hu, Hongbo; Wang, Wei; Zhang, Xuehong; Iqbal, Hafiz M N

2017-01-15

In the twenty-first century, chemical and associated industries quest a transition prototype from traditional chemical-based concepts to a greener, sustainable and environmentally-friendlier catalytic alternative, both at the laboratory and industrial scale. In this context, bio-based catalysis offers numerous benefits along with potential biotechnological and environmental applications. The bio-based catalytic processes are energy efficient than conventional methodologies under moderate processing, generating no and negligible secondary waste pollution. Thanks to key scientific advances, now, solid-phase biocatalysts can be economically tailored on a large scale. Nevertheless, it is mandatory to recover and reprocess the enzyme for their commercial feasibility, and immobilization engineering can efficiently accomplish this challenge. The first part of the present review work briefly outlines the immobilization of lignin-modifying enzymes (LMEs) including lignin peroxidase (LiP), manganese peroxidase (MnP) and laccase of white-rot fungi (WRF). Whereas, in the second part, a particular emphasis has been given on the recent achievements of carrier-immobilized LMEs for the degradation, decolorization, or detoxification of industrial dyes and dye-based industrial wastewater effluents. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of elevated atmospheric CO2 concentration on growth and leaf litter decomposition of Quercus acutissima and Fraxinus rhynchophylla

PubMed Central

Cha, Sangsub; Chae, Hee-Myung; Lee, Sang-Hoon; Shim, Jae-Kuk

2017-01-01

The atmospheric carbon dioxide (CO2) level is expected to increase substantially, which may change the global climate and carbon dynamics in ecosystems. We examined the effects of an elevated atmospheric CO2 level on the growth of Quercus acutissima and Fraxinus rhynchophylla seedlings. We investigated changes in the chemical composition of leaf litter, as well as litter decomposition. Q. acutissima and F. rhynchophylla did not show differences in dry weight between ambient CO2 and enriched CO2 treatments, but they exhibited different patterns of carbon allocation, namely, lower shoot/root ratio (S/R) and decreased specific leaf area (SLA) under CO2-enriched conditions. The elevated CO2 concentration significantly reduced the nitrogen concentration in leaf litter while increasing lignin concentrations and carbon/nitrogen (C/N) and lignin/N ratios. The microbial biomass associated with decomposing Q. acutissima leaf litter was suppressed in CO2 enrichment chambers, while that of F. rhynchophylla was not. The leaf litter of Q. acutissima from the CO2-enriched chambers, in contrast with F. rhynchophylla, contained much lower nutrient concentrations than that of the litter in the ambient air chambers. Consequently, poorer litter quality suppressed decomposition. PMID:28182638

Effect of elevated atmospheric CO2 concentration on growth and leaf litter decomposition of Quercus acutissima and Fraxinus rhynchophylla.

PubMed

Cha, Sangsub; Chae, Hee-Myung; Lee, Sang-Hoon; Shim, Jae-Kuk

2017-01-01

The atmospheric carbon dioxide (CO2) level is expected to increase substantially, which may change the global climate and carbon dynamics in ecosystems. We examined the effects of an elevated atmospheric CO2 level on the growth of Quercus acutissima and Fraxinus rhynchophylla seedlings. We investigated changes in the chemical composition of leaf litter, as well as litter decomposition. Q. acutissima and F. rhynchophylla did not show differences in dry weight between ambient CO2 and enriched CO2 treatments, but they exhibited different patterns of carbon allocation, namely, lower shoot/root ratio (S/R) and decreased specific leaf area (SLA) under CO2-enriched conditions. The elevated CO2 concentration significantly reduced the nitrogen concentration in leaf litter while increasing lignin concentrations and carbon/nitrogen (C/N) and lignin/N ratios. The microbial biomass associated with decomposing Q. acutissima leaf litter was suppressed in CO2 enrichment chambers, while that of F. rhynchophylla was not. The leaf litter of Q. acutissima from the CO2-enriched chambers, in contrast with F. rhynchophylla, contained much lower nutrient concentrations than that of the litter in the ambient air chambers. Consequently, poorer litter quality suppressed decomposition.

Tree foliar chemistry in an African savanna and its relation to life history strategies and environmental filters.

PubMed

Colgan, Matthew S; Martin, Roberta E; Baldeck, Claire A; Asner, Gregory P

2015-01-01

Understanding the relative importance of environment and life history strategies in determining leaf chemical traits remains a key objective of plant ecology. We assessed 20 foliar chemical properties among 12 African savanna woody plant species and their relation to environmental variables (hillslope position, precipitation, geology) and two functional traits (thorn type and seed dispersal mechanism). We found that combinations of six leaf chemical traits (lignin, hemi-cellulose, zinc, boron, magnesium, and manganese) predicted the species with 91% accuracy. Hillslope position, precipitation, and geology accounted for only 12% of the total variance in these six chemical traits. However, thorn type and seed dispersal mechanism accounted for 46% of variance in these chemical traits. The physically defended species had the highest concentrations of hemi-cellulose and boron. Species without physical defense had the highest lignin content if dispersed by vertebrates, but threefold lower lignin content if dispersed by wind. One of the most abundant woody species in southern Africa, Colophospermum mopane, was found to have the highest foliar concentrations of zinc, phosphorus, and δ(13)C, suggesting that zinc chelation may be used by this species to bind metallic toxins and increase uptake of soil phosphorus. Across all studied species, taxonomy and physical traits accounted for the majority of variability in leaf chemistry.

Lignin-assisted exfoliation of molybdenum disulfide in aqueous media and its application in lithium ion batteries.

PubMed

Liu, Wanshuang; Zhao, Chenyang; Zhou, Rui; Zhou, Dan; Liu, Zhaolin; Lu, Xuehong

2015-06-07

In this article, alkali lignin (AL)-assisted direct exfoliation of MoS2 mineral into single-layer and few-layer nanosheets in water is reported for the first time. Under optimized conditions, the concentration of MoS2 nanosheets in the obtained dispersion can be as high as 1.75 ± 0.08 mg mL(-1), which is much higher than the typical reported concentrations (<1.0 mg mL(-1)) using synthetic polymers or compounds as surfactants. The stabilizing mechanism primarily lies in the electrostatic repulsion between negative charged AL, as suggested by zeta-potential measurements. When the exfoliated MoS2 nanosheets are applied as electrode materials for lithium ion batteries, they show much improved electrochemical performance compared with the pristine MoS2 mineral because of the enhanced ion and electron transfer kinetics. This facile, scalable and eco-friendly aqueous-based process in combination with renewable and ultra-low-cost lignin opens up possibilities for large-scale fabrication of MoS2-based nanocomposites and devices. Moreover, herein we demonstrate that AL is also an excellent surfactant for exfoliation of many other types of layered materials, including graphene, tungsten disulfide and boron nitride, in water, providing rich opportunities for a wider range of applications.

Quantification of acidic compounds in complex biomass-derived streams

DOE PAGES

Karp, Eric M.; Nimlos, Claire T.; Deutch, Steve; ...

2016-05-10

Biomass-derived streams that contain acidic compounds from the degradation of lignin and polysaccharides (e.g. black liquor, pyrolysis oil, pyrolytic lignin, etc.) are chemically complex solutions prone to instability and degradation during analysis, making quantification of compounds within them challenging. Here we present a robust analytical method to quantify acidic compounds in complex biomass-derived mixtures using ion exchange, sample reconstitution in pyridine and derivatization with BSTFA. The procedure is based on an earlier method originally reported for kraft black liquors and, in this work, is applied to identify and quantify a large slate of acidic compounds in corn stover derived alkalinemore » pretreatment liquor (APL) as a function of pretreatment severity. Analysis of the samples is conducted with GCxGC-TOFMS to achieve good resolution of the components within the complex mixture. The results reveal the dominant low molecular weight components and their concentrations as a function of pretreatment severity. Application of this method is also demonstrated in the context of lignin conversion technologies by applying it to track the microbial conversion of an APL substrate. Here as well excellent results are achieved, and the appearance and disappearance of compounds is observed in agreement with the known metabolic pathways of two bacteria, indicating the sample integrity was maintained throughout analysis. Finally, it is shown that this method applies more generally to lignin-rich materials by demonstrating its usefulness in analysis of pyrolysis oil and pyrolytic lignin.« less

Optimizing bio-physical conditions and pre-treatment options for breaking lignin barrier of maize stover feed using white rot fungi.

PubMed

Atuhaire, Andrew M; Kabi, Fred; Okello, Samuel; Mugerwa, Swidiq; Ebong, Cyprian

2016-12-01

The greatest limitation to utilization of maize stover by ruminants as a feed is the high concentration of lignin, which limits fibre digestibility. However, ruminants can effectively utilize maize stover if its nutritive value is improved using white rot fungal species. This study was designed to determine optimal bio-physical conditions for mycelial growth and select the most ideal fungal species and pre-treatment options for improving nutritive value of maize stover. Four popular edible Pleurotus fungal species (viz. Pleurotus florida, Pleurotus ostreatus, Pleurotus sajor caju and Pleurotus pulmonarius ) were subjected to varying temperatures, pH levels, hydrogen peroxide (H 2 O 2 ) concentration and illumination to establish the extent of mycelial growth rate. Inclusion of H 2 O 2 was used to determine optimal levels for preservation and prevention of contamination from other indigenous microbiota. Effects of pre-treatment options on chemical composition and nutritive value of maize stover were also examined. Mycelial growth rate of Pleurotus species on potato dextrose agar (PDA) varied ( P  < 0.05) with temperature, pH level and H 2 O 2 concentration following a quadratic trend. Optimal temperature, pH and H 2 O 2 concentration for mycelial growth on PDA were 25 °C, 5 and 0.01 mL/L, respectively. Under the different bio-physical conditions, P. sajor caju had the highest mycelia density and growth rate. Chemical composition of solid-state fermented maize stover differed ( P  < 0.05) among the Pleurotus species. Maize stover fermented with P. sajor caju had the highest crude protein (CP) of 86.6 g/kg DM, in-vitro dry matter digestibility (IVDMD) of 731 g/kg DM, in-vitro organic matter digestibility (IVOMD) of 670.4 g/kg DM and metabolizable energy (ME) of 10.0 MJ/kg DM but with the lowest lignin (sa) of 50 g/kg DM. At 25 °C, P. sajor caju had the highest mycelial growth rate on PDA and highest lignin (sa) breakdown in the maize stover substrate. It was, therefore, selected as the most ideal fungal species for improving nutritive value of maize stover. Pre-treatment of maize stover with Lactobacillus plantarum and molasses under anaerobic condition for 7 days before inoculation with P. sajor caju resulted into a substrate with the highest ( P  < 0.05) CP (96.6 g/kg DM), IVDMD (752.3 g/kg DM), IVOMD (687.2 g/kg DM) and ME (10.2 MJ/kg DM). However, neutral detergent fiber exclusive of residual ash (NDFom) and lignin (sa) fractions decreased ( P  < 0.05) as a result of subjecting maize stover to pre-treatment with L. plantarum and molasses prior to fermentation with P. sajor caju. Therefore, pre-treatment of maize stover with L. plantarum and molasses for 7 days prior to fermentation with P. sajor caju for 14 days in darkness at 25 °C offered the greatest potential for breaking the lignin barrier.

Improving Processing and Performance of Pure Lignin Carbon Fibers through Hardwood and Herbaceous Lignin Blends.

PubMed

Hosseinaei, Omid; Harper, David P; Bozell, Joseph J; Rials, Timothy G

2017-07-01

Lignin/lignin blends were used to improve fiber spinning, stabilization rates, and properties of lignin-based carbon fibers. Organosolv lignin from Alamo switchgrass ( Panicum virgatum ) and yellow poplar ( Liriodendron tulipifera ) were used as blends for making lignin-based carbon fibers. Different ratios of yellow poplar:switchgrass lignin blends were prepared (50:50, 75:25, and 85:15 w/w ). Chemical composition and thermal properties of lignin samples were determined. Thermal properties of lignins were analyzed using thermogravimetric analysis and differential scanning calorimetry. Thermal analysis confirmed switchgrass and yellow poplar lignin form miscible blends, as a single glass transition was observed. Lignin fibers were produced via melt-spinning by twin-screw extrusion. Lignin fibers were thermostabilized at different rates and subsequently carbonized. Spinnability of switchgrass lignin markedly improved by blending with yellow poplar lignin. On the other hand, switchgrass lignin significantly improved thermostabilization performance of yellow poplar fibers, preventing fusion of fibers during fast stabilization and improving mechanical properties of fibers. These results suggest a route towards a 100% renewable carbon fiber with significant decrease in production time and improved mechanical performance.

Improving Processing and Performance of Pure Lignin Carbon Fibers through Hardwood and Herbaceous Lignin Blends

PubMed Central

Hosseinaei, Omid; Bozell, Joseph J.; Rials, Timothy G.

2017-01-01

Lignin/lignin blends were used to improve fiber spinning, stabilization rates, and properties of lignin-based carbon fibers. Organosolv lignin from Alamo switchgrass (Panicum virgatum) and yellow poplar (Liriodendron tulipifera) were used as blends for making lignin-based carbon fibers. Different ratios of yellow poplar:switchgrass lignin blends were prepared (50:50, 75:25, and 85:15 w/w). Chemical composition and thermal properties of lignin samples were determined. Thermal properties of lignins were analyzed using thermogravimetric analysis and differential scanning calorimetry. Thermal analysis confirmed switchgrass and yellow poplar lignin form miscible blends, as a single glass transition was observed. Lignin fibers were produced via melt-spinning by twin-screw extrusion. Lignin fibers were thermostabilized at different rates and subsequently carbonized. Spinnability of switchgrass lignin markedly improved by blending with yellow poplar lignin. On the other hand, switchgrass lignin significantly improved thermostabilization performance of yellow poplar fibers, preventing fusion of fibers during fast stabilization and improving mechanical properties of fibers. These results suggest a route towards a 100% renewable carbon fiber with significant decrease in production time and improved mechanical performance. PMID:28671571

Hydrodynamic sorting and transport of terrestrially derived organic carbon in sediments of the Mississippi and Atchafalaya Rivers

NASA Astrophysics Data System (ADS)

Bianchi, Thomas S.; Galler, John J.; Allison, Mead A.

2007-06-01

Over the course of two years, four cruises were conducted at varying levels of discharge in the lower Mississippi and Atchafalaya Rivers (MR and AR) where grab samples were collected from sand- and mud-dominated sediments. The tetramethylammonium hydroxide (TMAH) thermochemolysis method was used to determine sources of terrestrially derived organic carbon (OC) in these two sediment types, to examine the effects of hydrodynamic sorting on lignin sources in river sediments. Average lignin concentrations in the lower MR were 1.4 ± 1.1 mg gOC -1 at English Turn (ET) and 10.4 ± 27.4 mg gOC -1 at Venice. Using these concentrations, annual lignin fluxes to the Gulf of Mexico, from tidal and estuarine mud remobilization at ET and Venice, were 3.1 ± 2.5 × 10 5 kg and 11.4 ± 30.0 × 10 5 kg, respectively. Much of the lignin-derived materials in muddy sediments appeared to be derived from non-woody grass-like sources - which should decay more quickly than the woody materials typically found in the sandy deposits. The average total OC% (1.93 ± 0.47) of English Turn sands yields an annual flux of 0.34 ± 0.09 × 10 9 kg. Lignin flux in the English Turn sands (3.6 ± 2.6 mg gC -1) using the numbers above would be 12.2 ± 9.4 × 10 5 kg. The extensive amounts of sand-sized woody materials (coffee-grinds) found in the sandy sediments in both the AR and MR are likely derived from woody plant materials. This is the first time it has been demonstrated that sandy sediments in the MR provide an equally important pathway (compared to muds) for the transport of terrestrially derived organic matter to the northern Gulf of Mexico. Using the AR average %OC in sand (1.16 ± 0.72), we estimated an annual flux of OC to the shelf of 0.13 ± 0.07 × 10 9 kg. Lignin flux for AR sands was estimated to be 12.4 ± 12.1 × 10 5 kg. Despite the high error associated with these numbers, we observe for the first time that the flux of lignin in sandy sediments in the AR to the northern Gulf of Mexico is comparable to that found in the MR. These results further support the likelihood of grain-size related hydrodynamic sorting of terrestrially derived organic carbon in the lower Mississippi and Atchafalaya Rivers, suggesting that there is a distinct sandy sediment organic fraction contributed by major rivers to the global carbon cycle.

Multi-scale processes of beech wood disintegration and pretreatment with 1-ethyl-3-methylimidazolium acetate/water mixtures.

PubMed

Viell, Jörn; Inouye, Hideyo; Szekely, Noemi K; Frielinghaus, Henrich; Marks, Caroline; Wang, Yumei; Anders, Nico; Spiess, Antje C; Makowski, Lee

2016-01-01

The valorization of biomass for chemicals and fuels requires efficient pretreatment. One effective strategy involves the pretreatment with ionic liquids which enables enzymatic saccharification of wood within a few hours under mild conditions. This pretreatment strategy is, however, limited by water and the ionic liquids are rather expensive. The scarce understanding of the involved effects, however, challenges the design of alternative pretreatment concepts. This work investigates the multi length-scale effects of pretreatment of wood in 1-ethyl-3-methylimidazolium acetate (EMIMAc) in mixtures with water using spectroscopy, X-ray and neutron scattering. The structure of beech wood is disintegrated in EMIMAc/water mixtures with a water content up to 8.6 wt%. Above 10.7 wt%, the pretreated wood is not disintegrated, but still much better digested enzymatically compared to native wood. In both regimes, component analysis of the solid after pretreatment shows an extraction of few percent of lignin and hemicellulose. In concentrated EMIMAc, xylan is extracted more efficiently and lignin is defunctionalized. Corresponding to the disintegration at macroscopic scale, SANS and XRD show isotropy and a loss of crystallinity in the pretreated wood, but without distinct reflections of type II cellulose. Hence, the microfibril assembly is decrystallized into rather amorphous cellulose within the cell wall. The molecular and structural changes elucidate the processes of wood pretreatment in EMIMAc/water mixtures. In the aqueous regime with >10.7 wt% water in EMIMAc, xyloglucan and lignin moieties are extracted, which leads to coalescence of fibrillary cellulose structures. Dilute EMIMAc/water mixtures thus resemble established aqueous pretreatment concepts. In concentrated EMIMAc, the swelling due to decrystallinization of cellulose, dissolution of cross-linking xylan, and defunctionalization of lignin releases the mechanical stress to result in macroscopic disintegration of cells. The remaining cell wall constituents of lignin and hemicellulose, however, limit a recrystallization of the solvated cellulose. These pretreatment mechanisms are beyond common pretreatment concepts and pave the way for a formulation of mechanistic requirements of pretreatment with simpler pretreatment liquors.

Effect of additives on adsorption and desorption behavior of xylanase on acid-insoluble lignin from corn stover and wheat straw.

PubMed

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

2015-06-01

The competitive adsorption between cellulases and additives on lignin in the hydrolysis of lignocelluloses has been confirmed, whereas the effect of additives on the interaction between xylanase and lignin is not clear. In this work, the effects of additives, poly(ethylene glycol) 2000, poly(ethylene glycol) 6000, Tween 20, and Tween 80, on the xylanase adsorption/desorption onto/from acid-insoluble lignin from corn stover (CS-lignin) and wheat straw (WS-lignin) were investigated. The results indicated that the additives could adsorb onto isolated lignin and reduce the xylanase adsorption onto lignin. Compared to CS-lignin, more additives could adsorb onto WS-lignin, making less xylanase adsorbed onto WS-lignin. In addition, the additives could enhance desorption of xylanase from lignin, which might be due to the competitive adsorption between xylanase and additives on lignin. The released xylanase from lignin still exhibited hydrolytic capacity in the hydrolysis of isolated xylan and xylan in corn stover. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Wenwen; Simmons, Blake; Singh, Seema

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

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

DOE PAGES

Zhao, Wenwen; Simmons, Blake; Singh, Seema; ...

2016-09-26

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

[Effects of hot-NaOH pretreatment on Jerusalem artichoke stalk composition and subsequent enzymatic hydrolysis].

PubMed

Wang, Qing; Qiu, Jingwen; Li, Yang; Shen, Fei

2015-10-01

In order to explore the possibility of Jerusalem artichoke stalk for bioenergy conversion, we analyzed the main composition of whole stalk, pitch, and core of the stalk. Meanwhile, these parts were pretreated with different NaOH concentrations at 121 degrees C. Afterwards, enzymatic hydrolysis was performed to evaluate the pretreatment efficiency. Jerusalem artichoke stalk was characterized by relatively high lignin content (32.0%) compared with traditional crop stalks. The total carbohydrate content was close to that of crop stalks, but with higher cellulose content (40.5%) and lower hemicellulose (19.6%) than those of traditional crop stalks. After pretreatment, the lignin content in the whole stalk, pitch, and core decreased by 13.1%-13.4%, 8.3%-13.5%, and 19.9%-27.2%, respectively, compared with the unpretreated substrates. The hemicellulose content in the whole stalk, pitch, and core decreased 87.8%-96.9%, 87.6%-95.0%, and 74.0%-90.2%, respectively. Correspondingly, the cellulose content in the pretreated whole stalk, pitch, and core increased by 56.5%-60.2%, 52.2%-55.4%, and 62.7%-73.2%, respectively. Moreover, increase of NaOH concentration for pretreatment could improve the enzymatic hydrolysis of the whole stalk and pitch by 2.3-2.6 folds and 10.3-18.5 folds, respectively. The hydrolysis of pretreated stalk core decreased significantly as 2.0 mol/L NaOH was employed, although the increased NaOH concentration can also improve its hydrolysis performance. Based on these results, hot-NaOH can be regarded as an option for Jerusalem artichoke stalk pretreatment. Increasing NaOH concentration was beneficial to hemicellulose and lignin removal, and consequently improved sugar conversion. However, the potential decrease of sugar conversion of the pretreated core by higher NaOH concentration suggested further optimization on the pretreatment conditions should be performed.

Optical Proxies for Dissolved Organic Matter in Estuaries and Coastal Waters

NASA Astrophysics Data System (ADS)

Osburn, C. L.; Montgomery, M. T.; Boyd, T. J.; Bianchi, T. S.; Coffin, R. B.; Paerl, H. W.

2016-02-01

The flux of terrestrial dissolved organic carbon (DOC) into the coastal ocean from rivers and estuaries is a major part of the ocean's carbon cycle. Absorbing and fluorescing properties of chromophoric dissolved organic matter (CDOM) often are used to fingerprint its sources and to track fluxes of terrestrial DOM into the ocean. They also are used as proxies for organic matter to calibrate remote sensing observations from air and space and from in situ platforms. In general, strong relationships hold for large river dominated estuaries (e.g., the Mississippi River) but little is known about how widely such relationships can be developed in estuaries that have relatively small or multiple riverine inputs. Results are presented from a comparison of six diverse estuarine systems: the Atchafalaya River (ARE), the Mackenzie River (MRE), the Chesapeake Bay (CBE), Charleston Harbor (CHE), Puget Sound (PUG), and the Neuse River (NRE). Mean DOM concentrations ranged from 100 to 700 µM and dissolved lignin concentrations ranged from ca. 3-30 µg L-1. Overall trends were linear between CDOM measured at 350 nm (a350) and DOC concentration (R2=0.77) and between a350 and lignin (R2=0.87). Intercepts of a350 vs lignin were not significantly different from zero (P=0.43) suggesting that most of the CDOM was terrestrial in nature. Deviations from these regressions were strongest in the Neuse River Estuary, the most eutrophic of the six estuaries studied. After this calibration procedure, fluorescence modeling via parallel factor analysis (PARAFAC) was used to make estimates of terrigenous and planktonic DOC in these estuaries.

Characterization of novel sorghum brown midrib mutants from an EMS-mutagenized population

DOE PAGES

Sattler, Scott E.; Saballos, Ana; Xin, Zhanguo; ...

2014-09-02

Reducing lignin concentration in lignocellulosic biomass can increase forage digestibility for ruminant livestock and saccharification yields of biomass for bioenergy. In sorghum ( Sorghum bicolor (L.) Moench) and several other C4 grasses, brown midrib ( bmr) mutants have been shown to reduce lignin concentration. Putative bmr mutants isolated from an EMS-mutagenized population were characterized and classified based on their leaf midrib phenotype and allelism tests with the previously described sorghum bmr mutants bmr2, bmr6, and bmr12. These tests resulted in the identification of additional alleles of bmr2, bmr6,and bmr12, and, in addition, six bmr mutants were identified that were notmore » allelic to these previously described loci. Further allelism testing among these six bmr mutants showed that they represented four novel bmr loci. Based on this study, the number of bmr loci uncovered in sorghum has doubled. The impact of these lines on agronomic traits and lignocellulosic composition was assessed in a 2-yr field study. Most of the identified bmr lines showed reduced lignin concentration of their biomass relative to wild-type (WT). Effects of the six new bmr mutants on enzymatic saccharification of lignocellulosic materials were determined, but the amount of glucose released from the stover was similar to WT in all cases. Like bmr2, bmr6, and bmr12, these mutants may affect monolignol biosynthesis and may be useful for bioenergy and forage improvement when stacked together or in combination with the three previously described bmr alleles.« less

Biomass enzymatic saccharification is determined by the non-KOH-extractable wall polymer features that predominately affect cellulose crystallinity in corn.

PubMed

Jia, Jun; Yu, Bin; Wu, Leiming; Wang, Hongwu; Wu, Zhiliang; Li, Ming; Huang, Pengyan; Feng, Shengqiu; Chen, Peng; Zheng, Yonglian; Peng, Liangcai

2014-01-01

Corn is a major food crop with enormous biomass residues for biofuel production. Due to cell wall recalcitrance, it becomes essential to identify the key factors of lignocellulose on biomass saccharification. In this study, we examined total 40 corn accessions that displayed a diverse cell wall composition. Correlation analysis showed that cellulose and lignin levels negatively affected biomass digestibility after NaOH pretreatments at p<0.05 & 0.01, but hemicelluloses did not show any significant impact on hexoses yields. Comparative analysis of five standard pairs of corn samples indicated that cellulose and lignin should not be the major factors on biomass saccharification after pretreatments with NaOH and H2SO4 at three concentrations. Notably, despite that the non-KOH-extractable residues covered 12%-23% hemicelluloses and lignin of total biomass, their wall polymer features exhibited the predominant effects on biomass enzymatic hydrolysis including Ara substitution degree of xylan (reverse Xyl/Ara) and S/G ratio of lignin. Furthermore, the non-KOH-extractable polymer features could significantly affect lignocellulose crystallinity at p<0.05, leading to a high biomass digestibility. Hence, this study could suggest an optimal approach for genetic modification of plant cell walls in bioenergy corn.

Biomass Enzymatic Saccharification Is Determined by the Non-KOH-Extractable Wall Polymer Features That Predominately Affect Cellulose Crystallinity in Corn

PubMed Central

Wu, Leiming; Wang, Hongwu; Wu, Zhiliang; Li, Ming; Huang, Pengyan; Feng, Shengqiu; Chen, Peng; Zheng, Yonglian; Peng, Liangcai

2014-01-01

Corn is a major food crop with enormous biomass residues for biofuel production. Due to cell wall recalcitrance, it becomes essential to identify the key factors of lignocellulose on biomass saccharification. In this study, we examined total 40 corn accessions that displayed a diverse cell wall composition. Correlation analysis showed that cellulose and lignin levels negatively affected biomass digestibility after NaOH pretreatments at p<0.05 & 0.01, but hemicelluloses did not show any significant impact on hexoses yields. Comparative analysis of five standard pairs of corn samples indicated that cellulose and lignin should not be the major factors on biomass saccharification after pretreatments with NaOH and H2SO4 at three concentrations. Notably, despite that the non-KOH-extractable residues covered 12%–23% hemicelluloses and lignin of total biomass, their wall polymer features exhibited the predominant effects on biomass enzymatic hydrolysis including Ara substitution degree of xylan (reverse Xyl/Ara) and S/G ratio of lignin. Furthermore, the non-KOH-extractable polymer features could significantly affect lignocellulose crystallinity at p<0.05, leading to a high biomass digestibility. Hence, this study could suggest an optimal approach for genetic modification of plant cell walls in bioenergy corn. PMID:25251456

Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods.

PubMed

Barnette, Anna L; Lee, Christopher; Bradley, Laura C; Schreiner, Edward P; Park, Yong Bum; Shin, Heenae; Cosgrove, Daniel J; Park, Sunkyu; Kim, Seong H

2012-07-01

The non-centrosymmetry requirement of sum frequency generation (SFG) vibration spectroscopy allows the detection and quantification of crystalline cellulose in lignocellulose biomass without spectral interferences from hemicelluloses and lignin. This paper shows a correlation between the amount of crystalline cellulose in biomass and the SFG signal intensity. Model biomass samples were prepared by mixing commercially available cellulose, xylan, and lignin to defined concentrations. The SFG signal intensity was found sensitive to a wide range of crystallinity, but varied non-linearly with the mass fraction of cellulose in the samples. This might be due to the matrix effects such as light scattering and absorption by xylan and lignin, as well as the non-linear density dependence of the SFG process itself. Comparison with other techniques such as XRD, FT-Raman, FT-IR and NMR demonstrate that SFG can be a complementary and sensitive tool to assess crystalline cellulose in biomass. Copyright © 2012 Elsevier Ltd. All rights reserved.

The mechanisms of hydrothermal deconstruction of lignocellulose: New insights from thermal–analytical and complementary studies

PubMed Central

Ibbett, Roger; Gaddipati, Sanyasi; Davies, Scott; Hill, Sandra; Tucker, Greg

2011-01-01

Differential Scanning Calorimetry, Dynamic Mechanical Thermal Analysis, gravimetric and chemical techniques have been used to study hydrothermal reactions of straw biomass. Exothermic degradation initiates above 195 °C, due to breakdown of the xylose ring from hemicellulose, which may be similar to reactions occurring during the early stage pyrolysis of dry biomass, though activated at lower temperature through water mediation. The temperature and magnitude of the exotherm reduce with increasing acid concentration, suggesting a reduction in activation energy and a change in the balance of reaction pathways. The presence of xylan oligomers in auto-catalytic hydrolysates is believed to be due to a low rate constant rather than a specific reaction mechanism. The loss of the lignin glass transition indicates that the lignin phase is reorganised under high temperature auto-catalytic conditions, but remains partially intact under lower temperature acid-catalytic conditions. This shows that lignin degradation reactions are activated thermally but are not effectively catalysed by aqueous acid. PMID:21763128

Adsorption of methyl orange using activated carbon prepared from lignin by ZnCl2 treatment

NASA Astrophysics Data System (ADS)

Mahmoudi, K.; Hamdi, N.; Kriaa, A.; Srasra, E.

2012-08-01

Lignocellulosic materials are good and cheap precursors for the production of activated carbon. In this study, activated carbons were prepared from the lignin at different temperatures (200 to 500°C) by ZnCl2. The effects influencing the surface area of the resulting activated carbon are activation temperature, activation time and impregnation ratio. The optimum condition, are found an impregnation ratio of 2, an activation temperature of 450°C, and an activation time of 2 h. The results showed that the surface area and micropores volume of activated carbon at the experimental conditions are achieved to 587 and 0.23 cm3 g-1, respectively. The adsorption behavior of methyl orange dye from aqueous solution onto activated lignin was investigated as a function of equilibrium time, pH and concentration. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. A maximum adsorption capacity of 300 mg g-1 of methyl orange by activated carbon was achieved.

Woody Plant Invasion of Grassland: Lignin and Aliphatic Biopolymer Chemistry and Carbon Isotope Composition in Physical Fractions

NASA Astrophysics Data System (ADS)

Gamblin, D.; Boutton, T.; Liao, J.; Jastrow, J.; Filley, T.

2003-12-01

Significant changes in the apportionment of organic carbon in grassland and savanna soils have been document as a result of woody plant encroachment. In the Rio Grande Plains of Texas, C4 grasslands (d13C = -14 0/00) have undergone succession to trees and shrubs of a subtropical thorn woodland (d13C = -27 0/00) over the past 150 y which has resulted in increased soil organic carbon storage. Large differences in the turnover times of physical fractions in this system indicate selective preservation mechanisms which may include physical protection or inherent biochemical recalcitrance. To elucidate mechanisms of SOC sequestration during woody plant succession in this system, we are investigating the chemistry and compound-specific stable carbon isotope composition of lignin and aliphatic biopolymers in specific physical (size, density) soil fractions within a chronosequence that includes remnant grasslands (Time 0) and woody plant stands ranging in age from 10-130 y. The soil fraction data is being compared to biopolymer and isotope chemistry of the root, stem and/or leaf tissue of 20 of the dominant genus of plants in the system. Lignin phenols and suberin and cutin-derived hydroxyfatty acids are being isolated using alkaline CuO oxidation and tetramethylammonium hydroxide thermochemolysis. A comparison of the macroaggregate (greater than 250 um), microaggregate (53-250 um), and free silt and clay fractions in the oldest stand indicates that lignin is the most concentrated (organic carbon normalized values) in macroaggregates and is significantly less degraded, as determined by relative yields of oxidized and reduced lignin phenols. Additionally, the intra-aggregate silt and clay fraction from the macroaggregates contains less than half of the organic carbon normalized lignin phenols and is relatively more oxidized than what is found in the total macroaggregate pool. From these preliminary results it appears that the bulk macroaggregate pool contains the least degraded/freshest lignin of the physical fractions. This is consistent with the relatively shorter residence times determined for this fraction in this system. Continuing work includes compound specific isotope analysis of isolated lignin and hydroxyl fatty acids to elucidate biopolymer-specific turnover times which will provide important clues into the mechanisms of SOM storage and biopolymer recalcitrance.

DOM composition in an agricultural watershed: assessing patterns and variability in the context of spatial scales

USGS Publications Warehouse

Hernes, Peter J.; Spencer, Robert G. M.; Dyda, Rachel Y.; Pellerin, Brian A.; Bachand, Philip A. M.; Bergamaschi, Brian A.

2013-01-01

Willow Slough, a seasonally irrigated agricultural watershed in the Sacramento River valley, California, was sampled synoptically in order to investigate the extent to which dissolved organic carbon (DOC) concentrations and compositions from throughout the catchment are represented at the mouth. DOC concentrations ranged from 1.8 to 13.9 mg L−1, with the lowest values in headwater 1st and 2nd order streams, and the highest values associated with flood irrigation. Carbon-normalized vanillyl phenols varied from 0.05 to 0.67 mg 100 mg OC−1 (0.37 mean), indicative of considerable contributions from vascular plants. DOC concentrations and compositions at the mouth appear to be primarily influenced by land use (agriculture) in the lower reaches, and therefore very little of the headwater chemistry (1st and 2nd order streams) can be discerned from the chemistry at or near the mouth (3rd and 4th order streams), indicating the need for synoptic sampling to capture the breadth of organic carbon cycling within a catchment. Field sampling during irrigation showed the large impact that flood irrigation can have on DOC concentrations and compositions, likely a primary cause of significantly elevated Willow Slough DOC concentrations during the summer irrigation season. Optical proxies exhibited varying degrees of correlation with chemical measurements, with strongest relationships to DOC and dissolved lignin (r2 = 0.95 and 0.73, respectively) and weaker relationships to carbon-normalized lignin yields and C:V (r2 from 0.31 to 0.42). Demonstrating the importance of matching scale to processes, we found no relationship between dissolved lignin concentrations and total suspended sediments (TSS) across all sites, in contrast to the strong relationship observed in weekly samples at the mouth. As DOC concentrations and compositions at the mouth of Willow Slough are closely tied to anthropogenic activities within the catchment, future changes in land-use driven by climate change, water availability, and economic pressures on crop types will also bring about changes in the overall biogeochemistry.

The properties of syringyl, guaiacyl and p-hydroxyphenyl artificial lignins

PubMed Central

Bland, D. E.; Logan, A. F.

1965-01-01

1. Artificial lignins have been produced on potato parenchyma. 2. The methoxyl-free lignin and 4-hydroxy-3-methoxy (guaiacyl) lignins could be estimated by the sulphuric acid method but the 4-hydroxy-3,5-dimethoxy (syringyl) lignins could not. 3. Permanganate oxidation of isolated p-coumaric lignin gave 4-hydroxybenzoic acid, 4-hydroxyisophthalic acid and small amounts of hydroxytrimesic acid and 4-hydroxyphthalic acid. Ferulic lignin gave vanillic acid and 5-carboxyvanillic acid and also small amounts of 4-hydroxybenzoic acid and dehydrodivanillic acid. The sinapic lignin gave traces of syringic acid and of 4-hydroxybenzoic acid. 4. The p-coumaric lignin is a highly condensed polymer. The ferulic lignin is partly uncondensed and partly condensed through the 5-position like gymnosperm lignin. The sinapic lignin shows no evidence of condensation and is probably an ether-linked polymer. PMID:14340102

Secondary Metabolism in Brassica Rapa Under Hypergravity

NASA Astrophysics Data System (ADS)

Levine, Lanfang; Darnell, Rebecca; Allen, Joan; Musgrave, Mary; Bisbee, Patricia

Effect of altered gravity on secondary metabolism is of critical importance not only from the viewpoint of plant evolution, but also of productivity (carbon partition between edible and non-edible parts), plant fitness, as well as culinary and nutraceutical values to human diet. Previous work found that lignin content decreases in microgravity as the need for mechanical support decreases, while the response of other small molecular secondary metabolites to microgravity varies. Our recent ISS experiment showed that 3-butenyl glucosinolate (a predominant glucosinolate in Brassica rapa) increased in stems of B. rapa grown in the microgravity conditions. To further elucidate the role of gravity in plant secondary metabolism, a series of hypergravity (the other end of gravity spectrum) experiments were carried out using the 24-ft centrifuge at Ames Research Center. Thirteen-day-old B. rapa L. (cv. Astroplants) were transferred to the Plant Growth Facility attached to the centrifuge following previous experimental conditions, and subsequently grown for 16 days. Plants were harvested, immediately frozen in liquid nitrogen, and lyophilized prior to analysis for glucosinolates and lignin. In general, glucosinolate concentration was the highest in stems, followed by leaves, then roots. Glucosinolate concentration was significantly lower in stems of the 2-g and 4-g plants - averaging 4.6 and 2.5 ng/g DW, respectively - compared with the stationary control plants, which averaged 7.9 ng/g DW. Similarly, there was a 2.2-fold and 7.5-fold decrease in 3-butenyl glucosinolate in roots of the 2-g and 4-g plants, respectively, compared with the control (2.6 ng/g DW). There was a significant decrease in 3-butenyl glucosinolate concentration in leaves of the 4-g compared to leaves of the control plants (2.6 and 4.5 ng/g DW, respectively); however, there was no effect of 2-g on leaf glucosinolate concentration. Increasing gravity from 1-g to 2-g to 4-g generally resulted in further decreases in glucosinolate accumulation. Combining these results with the findings from ISS confirmed a negative correlation between glucosinolate and gravity. Lignin in the same plant materials is currently under investigation. A positive relationship between lignin and gravity is expected. This project was supported by NASA grant NAG10-329 and NNX07AT77G.

Molecular docking and molecular dynamics simulation analyses of urea with ammoniated and ammoxidized lignin.

PubMed

Li, Wenzhuo; Zhang, Song; Zhao, Yingying; Huang, Shuaiyu; Zhao, Jiangshan

2017-01-01

Ammoniated lignin, prepared through the Mannich reaction of lignin, has more advantages as a slow-release carrier of urea molecules than ammoxidized lignin and lignin. The advantages of the ammoniated lignin include its amine groups added and its high molecular mass kept as similar as that of lignin. Three organic molecules including guaiacyl, 2-hydroxybenzylamine and 5-carbamoylpentanoic acid are monomers respectively in lignin, ammoniated lignin and ammoxidized lignin. We studied the difference between the interactions of lignin, ammoniated lignin and ammoxidized lignin with respect to urea, based on radial distribution functions (RDFs) results from molecular dynamics (MD) simulations. Glass transition temperature (T g ) and solubility parameter (δ) of ammoniated and ammoxidized lignin have been calculated by MD simulations in the constant-temperature and constant-pressure ensemble (NPT). Molecular docking results showed the interaction sites of the urea onto the ammoniated and ammoxidized lignin and three different interaction modes were identified. Root mean square deviation (RMSD) values could indicate the mobilities of the urea molecule affected by the three different interaction modes. A series of MD simulations in the constant-temperature and constant-volume ensemble (NVT) helped us to calculate the diffusivity of urea which was affected by the content of urea in ammoniated and ammoxidized lignin. Copyright © 2016 Elsevier Inc. All rights reserved.

Prototyping hexagonal light concentrators using high-reflectance specular films for the Large-Sized Telescopes of the Cherenkov Telescope Array

NASA Astrophysics Data System (ADS)

Okumura, A.; Dang, T. V.; Ono, S.; Tanaka, S.; Hayashida, M.; Hinton, J.; Katagiri, H.; Noda, K.; Teshima, M.; Yamamoto, T.; Yoshida, T.

2017-12-01

We have developed a prototype hexagonal light concentrator for the Large-Sized Telescopes of the Cherenkov Telescope Array. To maximize the photodetection efficiency of the focal-plane camera pixels for atmospheric Cherenkov photons and to lower the energy threshold, a specular film with a very high reflectance of 92-99% has been developed to cover the inner surfaces of the light concentrators. The prototype has a relative anode sensitivity (which can be roughly regarded as collection efficiency) of about 95 to 105% at the most important angles of incidence. The design, simulation, production procedure, and performance measurements of the light-concentrator prototype are reported.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Lignin nanoparticle synthesis

DOEpatents

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

2015-08-11

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

Can species-specific differences in foliar chemistry influence leaf litter decomposition in grassland species?

NASA Astrophysics Data System (ADS)

Sanaullah, M.; Chabbi, A.; Rumpel, C.

2009-04-01

The influence of litter quality on its rate of decomposition is a crucial aspect of C cycle. In this study we concentrated on grassland ecosystems where leaf litter is one of the major sources of C input. To quantify the contribution of initial leaf chemistry within different plant species, the decomposition of chemically different leaf litter of three grassland species (Lolium perenne, Festuca arundinacea and Dactylis glomerata) was monitored, using the litter bag technique. Litter of different maturity stages i.e. green (fresh leaves) and brown litter (brown leaves were still attached to the plant), were incubated on bare soil surface. Samples were taken at different time intervals (0, 2, 4, 8, 20 and 44 weeks) and were analyzed for mass loss, organic C and N contents and stable isotopic signatures (C and N). Changes in litter chemistry were addressed by determining lignin-derived phenols after CuO oxidation and non-cellulosic polysaccharides after acid hydrolysis followed by gas chromatography. Green litter was chemically different from brown litter due to higher initial N and lower lignin contents. While in grassland species, both L. perenne and D. glomerata were similar in their initial chemical composition compared with F. arundinacea. Green litter showed higher rate of degradation. In green litter, Percent lignin remaining of initial (% OI) followed the similar decomposition pattern as of C remaining indicating lignin as controlling factor in decomposition. Constant Acid-to-Aldehyde ratios of lignin-derived phenols (vanillyl and syringyl) did not suggest any transformation in lignin structures. In green litter, increase in non-cellulosic polysaccharides ratios (C6/C5 and deoxy/C5) proposed microbial-derived sugars, while there was no significant increase in these ratios in brown litter. In conclusion, due to the differences in initial chemical composition (initial N and lignin contents), green litter decomposition was higher than brown litter in all grassland species. Regardless of similarities in initial composition of grassland species, green and brown litter of Lolium perenne decomposed more rapidly compared with other two species. So, Species related differences in initial litter chemistry did not control its degradation.

The Effect of Plant Source on the Structural Properties of Lignin-based Polyurethane Blends

NASA Astrophysics Data System (ADS)

Lang, Jason; Dadmun, Mark

The development of polyurethane materials based on incorporating lignin from a variety of plant sources (softwood, hardwood, and non-wood) were synthesized. Further experiments study the physical properties of the resulting lignin-based polyurethane as a function of the lignin structure, which varies with plant source. Here, we report the effect that internal crosslinking of the lignin structure has on the modulus, hardness, glass transition temperature, and thermal decomposition of the synthesized lignin-based polyurethane composites. The lignins used in this work were a softwood kraft lignin, hardwood lignosulfonate, and a wheat straw soda lignin. The lignin, acting as a polyol and the hardblock segment, reacts with TDI-endcapped PPG (2,300 MN) as the rubbery softblock component to produce lignin-based polyurethanes with varying lignin content (10, 20, 30, 40, 50, and 60 wt%). Results show that the wheat straw lignin provides the superior mechanical properties and thermal resistance. These properties are correlated to the two-phase morphology of the resultant polyurethane.

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

PubMed

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

2010-05-01

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

[Experimental investigation of the straw pre-treatment to enhance its high solid anaerobic digestion].

PubMed

Jiang, Jian-Guo; Zhao, Zhen-Zhen; Du, Xue-Juan; Sui, Ji-Chao; Wu, Shi-Yao

2007-04-01

The straw contains a high content of lignin, which cannot be well utilized by anaerobic bacteria in high solid anaerobic digestion process. This paper presents the experimental investigation of the straw pre-treatment, which aims to destroy the complex structure of the lignin to enhance its high solid anaerobic digestion. The straw is pre-treated in different solutions including NaOH, ammonia, H2SO4, and carbamide. The pre-treating effects are expressed by COD concentration dissolved in the solutions and the 14-day biogas generation in the enhanced aerogenic experiment. Different affecting factors, such as the concentration of the chemical solution, the species of the straw, the pre-treatment reaction time, the reaction temperature and the size of the straw, are investigated. The results show that NaOH solution is the most effective pre-treatment chemical among the four different solutions. The experimental results still indicate that the accumulative biogas production can be 1 500 mL (10 g straw) in 14 days after pre-treatment in 4 mg/L NaOH solution and the dissolved COD in the solution reaches 39 000 mg/L after 24 hours. In addition, the experiment shows that the lignin content in the straw is reduced from 28% to 19% after pre-treatment in 1.5% (in weight) NaOH solution, and it can improve the straw treatment efficiency using high solid anaerobic digestion process.

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

DOEpatents

Stahl, Shannon S; Rahimi, Alireza

2015-03-03

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

Effects of organosolv and ammonia pretreatments on lignin properties and its inhibition for enzymatic hydrolysis

DOE PAGES

Yoo, Chang Geun; Li, Mi; Meng, Xianzhi; ...

2017-04-05

Lignin offers structural support and protection for plant cell walls; but, it also contributes to biomass recalcitrance and the costs of biofuel production via the biological pathway. Organosolv and ammonia pretreatments have been developed to reduce biomass recalcitrance and improve sugar release performance during enzymatic hydrolysis. It is believed that lignin properties are related to its inhibition on enzymatic hydrolysis; therefore, understanding the characteristics of lignin is a key for effective biomass conversion to biofuels. In this study, an organosolv pretreatment using 60% ethanol with 1.25% H 2SO 4 significantly deconstructed poplar lignin and reduced its molecular weights due tomore » the cleavage of lignin inter-unit linkages. The organosolv pretreatment increased the contents of phenolic OH units and the lignin residue showed a high cellulase maximum adsorption capacity. Ammonia pretreatment with 5% ammonium hydroxide was not as effective as organosolv pretreatment on lignin deconstruction. Organosolv lignin residue had lower lignin S/G ratio than the untreated one. Furthermore, when compared to the organosolv lignin residue and untreated lignin, ammonia lignin residue had a higher cellulase adsorption affinity. In addition, the effects of lignin on cellulose hydrolysis was investigated and the results suggested that the presence of lignin with cellulose substrates reduced cellulose hydrolysis, and its inhibitory effect was primarily determined by the lignin properties after each pretreatment. The organosolv pretreatment resulted in a slightly lower cellulase binding strength (249.7 mL g -1) on poplar lignin than that on untreated samples (261.1 mL g -1), while ammonia lignin residue showed a higher cellulase binding strength (402.8 mL g -1) and had more significant inhibition effect on cellulose hydrolysis. Our results demonstrated that the binding strength significantly affected the lignin-derived inhibition on enzymatic hydrolysis of cellulose in the cellulose-lignin mixtures.« less

Effects of organosolv and ammonia pretreatments on lignin properties and its inhibition for enzymatic hydrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoo, Chang Geun; Li, Mi; Meng, Xianzhi

Lignin offers structural support and protection for plant cell walls; but, it also contributes to biomass recalcitrance and the costs of biofuel production via the biological pathway. Organosolv and ammonia pretreatments have been developed to reduce biomass recalcitrance and improve sugar release performance during enzymatic hydrolysis. It is believed that lignin properties are related to its inhibition on enzymatic hydrolysis; therefore, understanding the characteristics of lignin is a key for effective biomass conversion to biofuels. In this study, an organosolv pretreatment using 60% ethanol with 1.25% H 2SO 4 significantly deconstructed poplar lignin and reduced its molecular weights due tomore » the cleavage of lignin inter-unit linkages. The organosolv pretreatment increased the contents of phenolic OH units and the lignin residue showed a high cellulase maximum adsorption capacity. Ammonia pretreatment with 5% ammonium hydroxide was not as effective as organosolv pretreatment on lignin deconstruction. Organosolv lignin residue had lower lignin S/G ratio than the untreated one. Furthermore, when compared to the organosolv lignin residue and untreated lignin, ammonia lignin residue had a higher cellulase adsorption affinity. In addition, the effects of lignin on cellulose hydrolysis was investigated and the results suggested that the presence of lignin with cellulose substrates reduced cellulose hydrolysis, and its inhibitory effect was primarily determined by the lignin properties after each pretreatment. The organosolv pretreatment resulted in a slightly lower cellulase binding strength (249.7 mL g -1) on poplar lignin than that on untreated samples (261.1 mL g -1), while ammonia lignin residue showed a higher cellulase binding strength (402.8 mL g -1) and had more significant inhibition effect on cellulose hydrolysis. Our results demonstrated that the binding strength significantly affected the lignin-derived inhibition on enzymatic hydrolysis of cellulose in the cellulose-lignin mixtures.« less

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

PubMed

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

2014-07-01

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

Reducing sugar production of sweet sorghum bagasse kraft pulp

NASA Astrophysics Data System (ADS)

Solihat, Nissa Nurfajrin; Fajriutami, Triyani; Adi, Deddy Triyono Nugroho; Fatriasari, Widya; Hermiati, Euis

2017-01-01

Kraft pulping of sweet sorghum bagasse (SSB) has been used for effective delignification method for cellulose production. This study was conducted to evaluate the performance pulp kraft of SSB for reducing sugar production. The study intended to investigate the effect of active alkali and sulfidity loading variation of SSB pulp kraft on reducing sugar yield per biomass. The SSB pulp was prepared after pulping using three variations of active alkali (17, 19, and 22%) and sulfidity loading (20, 22, and 24%) at 170°C for 4 h with liquor to wood ratio of 10. A total of 9 pulps were obtained from these pretreatments. Delignification pretreatment has been succesfully removed lignin and hemicellulose more than 90% and 50%, respectively. Increasing active alkali and sulfidity loading has significantly increased lignin removal caused by disruption of the cell wall structure for releasing lignin into black liquor in the cellulose extraction. The enzymatic hydrolysis of pulp was carried out with cellulase loading of 40 FPU per g substrate in the shaking incubator at 50°C and 150 rpm for 78 h. For each 24 h, the reducing sugar yield (DNS assay) has been observed. Even though the lignin and hemicellulose loss occurred along with higher active alkali loading, this condition tends to decrease its yield. The reducing sugar concentration varied between 7-8 g/L. Increasing active alkali and sulfidity was significantly decreased the reducing sugar per biomass. Pulp delignified by 17% active alkali and 20% sulfidity has demonstrated the maximum reducing sugar yield per biomass of 45.57% resulted after 72 h enzymatic hydrolysis. These results indicated that kraft pulping was success to degrade more lignin and hemicellulose content to facilitate the enzyme for breaking down the cellulose into its sugar monomer. A high loss of lignin and hemicellulose are not single factor to improve digestibility of SSB. This sugar has potential for yeast fermented into bioethanol.

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2017-02-08

Lignins isolated from representative hardwood, softwood, and grass materials were effectively hydrocracked to aromatics catalyzed by tungsten carbide over activated carbon (W 2 C/AC). The effects of botanical species and fractionation methods on lignin structure and the activity of W 2 C/AC were studied in detail. Gas permeation chromatography (GPC), FTIR, elemental analysis, and 2 D HSQC NMR showed that all the extracted samples shared the basic skeleton of lignin, whereas the fractionation method significantly affected the structure. The organosolv process provided lignin with a structure more similar to the native lignin, which was labile to be depolymerized by W 2 C/AC. Softwood lignins (i.e., spruce and pine) possessed higher molecular weights than hardwood lignins (i.e., poplar and basswood); whereas corn stalk lignin that has noncanonical subunits and exhibited the lowest molecular weight owing to its shorter growth period. β-O-4 bonds were the major linkages in all lignin samples, whereas softwood lignins contained more resistant linkages of β-5 and less β-β than corn stalk and hardwood lignins; as a result, lowest hydrocracking efficiency was obtained in softwood lignins, followed by corn stalk and hardwood lignins. 2 D HSQC NMR spectra of lignin and the liquid oil as well as the solid residue showed that W 2 C/AC exhibited high activity not only in β-O-4 cleavage, but also in deconstruction of other ether linkages between aromatic units, so that high yield of liquid oil was obtained from lignin. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lignin Valorization: Emerging Approaches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beckham, Gregg T

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)more » 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.« less

Contrasting composition of terrigenous organic matter in the dissolved, particulate and sedimentary organic carbon pools on the outer East Siberian Arctic Shelf

NASA Astrophysics Data System (ADS)

Salvadó, Joan A.; Tesi, Tommaso; Sundbom, Marcus; Karlsson, Emma; Kruså, Martin; Semiletov, Igor P.; Panova, Elena; Gustafsson, Örjan

2016-11-01

Fluvial discharge and coastal erosion of the permafrost-dominated East Siberian Arctic delivers large quantities of terrigenous organic carbon (Terr-OC) to marine waters. The composition and fate of the remobilized Terr-OC needs to be better constrained as it impacts the potential for a climate-carbon feedback. In the present study, the bulk isotope (δ13C and Δ14C) and macromolecular (lignin-derived phenols) composition of the cross-shelf exported organic carbon (OC) in different marine pools is evaluated. For this purpose, as part of the SWERUS-C3 expedition (July-September 2014), sediment organic carbon (SOC) as well as water column (from surface and near-bottom seawater) dissolved organic carbon (DOC) and particulate organic carbon (POC) samples were collected along the outer shelves of the Kara Sea, Laptev Sea and East Siberian Sea. The results show that the Lena River and the DOC may have a preferential role in the transport of Terr-OC to the outer shelf. DOC concentrations (740-3600 µg L-1) were 1 order of magnitude higher than POC (20-360 µg L-1), with higher concentrations towards the Lena River plume. The δ13C signatures in the three carbon pools varied from -23.9 ± 1.9 ‰ in the SOC, -26.1 ± 1.2 ‰ in the DOC and -27.1 ± 1.9 ‰ in the POC. The Δ14C values ranged between -395 ± 83 (SOC), -226 ± 92 (DOC) and -113 ± 122 ‰ (POC). These stable and radiocarbon isotopes were also different between the Laptev Sea and the East Siberian Sea. Both DOC and POC showed a depleted and younger trend off the Lena River plume. Further, the Pacific inflow and the sea-ice coverage, which works as a barrier preventing the input of "young" DOC and POC, seem to have a strong influence in these carbon pools, presenting older and more enriched δ13C signatures under the sea-ice extent. Lignin phenols exhibited higher OC-normalized concentrations in the SOC (0.10-2.34 mg g-1 OC) and DOC (0.08-2.40 mg g-1 OC) than in the POC (0.03-1.14 mg g-1 OC). The good relationship between lignin and Δ14C signatures in the DOC suggests that a significant fraction of the outer-shelf DOC comes from "young" Terr-OC. By contrast, the slightly negative correlation between lignin phenols and Δ14C signatures in POC, with higher lignin concentrations in older POC from near-bottom waters, may reflect the off-shelf transport of OC from remobilized permafrost in the nepheloid layer. Syringyl / vanillyl and cinnamyl / vannillyl phenol ratios presented distinct clustering between DOC, POC and SOC, implying that those pools may be carrying different Terr-OC of partially different origin. Moreover, 3,5-dihydroxybenzoic acid to vanillyl phenol ratios and p-coumaric acid to ferulic acid ratios, used as a diagenetic indicators, enhanced in POC and SOC, suggesting more degradation within these pools. Overall, the key contrast between enhanced lignin yields both in the youngest DOC and the oldest POC samples reflects a significant decoupling of terrestrial OC sources and pathways.

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

PubMed

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

2013-01-01

The enzymatic oxidative polymerization of five technical lignins with different molecular properties, i.e. Soda Grass/Wheat straw Lignin, Organosolv Hardwood Lignin, Soda Wheat straw Lignin, Alkali pretreated Wheat straw Lignin, and Kraft Softwood was studied. All lignins were previously fractionated by acetone/water 50:50 (v/v) and the laccase-catalyzed polymerization of the low molecular weight fractions (Mw < 4000 g/mol) was carried out in the same solvent system. Reactivity of lignin substrates in laccase-catalyzed reactions was determined by monitoring the oxygen consumption. The oxidation reactions in 50% acetone in water mixture proceed with high rate for all tested lignins. Polymerization products were analyzed by size exclusion chromatography, FT-IR, and (31)P-NMR and evidence of important lignin modifications after incubation with laccase. Lignin polymers with higher molecular weight (Mw up to 17500 g/mol) were obtained. The obtained polymers have potential for applications in bioplastics, adhesives and as polymeric dispersants.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.

2016-06-17

Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple “upstream” (i.e., lignin bioengineering, lignin isolation and “early-stage catalytic conversion of lignin”) and “downstream” (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a “beginning-to-end” analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on the improved understanding ofmore » ligninÏs biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.« less

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

DOE PAGES

Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.; ...

2016-06-17

In this study, lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple “upstream” (i.e., lignin bioengineering, lignin isolation and “early-stage catalytic conversion of lignin”) and “downstream” (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a “beginning-to-end” analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on themore » improved understanding of ligninÏs biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.« less

A prototype portable breath acetone analyzer for monitoring fat loss.

PubMed

Toyooka, Tsuguyoshi; Hiyama, Satoshi; Yamada, Yuki

2013-09-01

Acetone contained in our exhaled breath is a metabolic product of the breakdown of body fat and is expected to be a good indicator of fat-burning. Typically, gas chromatography or mass spectrometry are used to measure low-concentration compounds in breath but such large instruments are not suitable for daily use by diet-conscious people. Here, we prototype a portable breath acetone analyzer that has two types of semiconductor-based gas sensors with different sensitivity characteristics, enabling the acetone concentration to be calculated while taking into account the presence of ethanol, hydrogen, and humidity. To investigate the accuracy of our prototype and its application in diet support, experiments were conducted on healthy adult volunteers. Breath acetone concentrations obtained from our prototype and from gas chromatography showed a strong correlation throughout the experiments. Moreover, body fat in subjects with a controlled caloric intake and taking exercise decreased significantly, whereas breath acetone concentrations in those subjects increased significantly. These results prove that our prototype is practical and useful for self-monitoring of fat-burning at home or outside. Our prototype will help to prevent and alleviate obesity and diabetes.

Systematic Parameterization of Lignin for the CHARMM Force Field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vermaas, Joshua; Petridis, Loukas; Beckham, Gregg

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 formore » 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 disparate feedstocks, and guide further lignin engineering efforts.« less

Lignin-carbohydrate complexes from sisal (Agave sisalana) and abaca (Musa textilis): chemical composition and structural modifications during the isolation process.

PubMed

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

2016-05-01

Two types of lignins occurred in different lignin-carbohydrate fractions, a lignin enriched in syringyl units, less condensed, preferentially associated with xylans, and a lignin with more guaiacyl units, more condensed, associated with glucans. Lignin-carbohydrate complexes (LCC) were isolated from the fibers of sisal (Agave sisalana) and abaca (Musa textilis) according to a plant biomass fractionation procedure recently developed and which was termed as "universally" applicable to any type of lignocellulosic material. Two LCC fractions, namely glucan-lignin (GL) and xylan-lignin (XL), were isolated and differed in the content and composition of carbohydrates and lignin. In both cases, GL fractions were enriched in glucans and comparatively depleted in lignin, whereas XL fractions were depleted in glucans, but enriched in xylans and lignin. Analysis by two-dimensional Nuclear Magnetic Resonance (2D-NMR) and Derivatization Followed by Reductive Cleavage (DFRC) indicated that the XL fractions were enriched in syringyl (S)-lignin units and β-O-4' alkyl-aryl ether linkages, whereas GL fractions have more guaiacyl (G)-lignin units and less β-O-4' alkyl-aryl ether linkages per lignin unit. The data suggest that the structural characteristics of the lignin polymers are not homogeneously distributed within the same plant and that two different lignin polymers with different composition and structure might be present. The analyses also suggested that acetates from hemicelluloses and the acyl groups (acetates and p-coumarates) attached to the γ-OH of the lignin side chains were extensively hydrolyzed and removed during the LCC fractionation process. Therefore, caution must be paid when using this fractionation approach for the structural characterization of plants with acylated hemicelluloses and lignins. Finally, several chemical linkages (phenylglycosides and benzyl ethers) could be observed to occur between lignin and xylans in these plants.

Litter decay rates are determined by lignin chemistry

Treesearch

Jennifer M. Talbot; Daniel J. Yelle; James Nowick; Kathleen K. Treseder

2011-01-01

Litter decay rates are often correlated with the initial lignin:N or lignin:cellulose content of litter, suggesting that interactions between lignin and more labile compounds are important controls over litter decomposition. The chemical composition of lignin may influence these interactions, if lignin physically or chemically protects labile components from microbial...

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

PubMed Central

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

2013-01-01

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

Organosolv delignification of Eucalyptus globulus: Kinetic study of autocatalyzed ethanol pulping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oliet, M.; Rodriguez, F.; Santos, A.

2000-01-01

The autocatalyzed delignification of Eucalyptus globulus in 50% ethanol (w/w) was modeled as the irreversible and consecutive dissolution of initial, bulk, and residual lignin. Their respective contributions to total lignin was estimated as 9, 75, and 16%. Isothermal pulping experiments were carried out to evaluate an empirical kinetic model among eight proposals corresponding to different reaction schemes. The calculated activation energy was found to be 96.5, 98.5, and 40.8 kJ/mol for initial, bulk, and residual delignification, respectively. The influence of hydrogen ion concentration was expressed by a power-law function model. The kinetic model developed here was validated using data frommore » nonisothermal pulping runs.« less

Current understanding of the correlation of lignin structure with biomass recalcitrance

DOE PAGES

Li, Mi; Pu, Yunqiao; Ragauskas, Arthur J.

2016-11-18

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

Current understanding of the correlation of lignin structure with biomass recalcitrance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Mi; Pu, Yunqiao; Ragauskas, Arthur J.

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

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

NASA Astrophysics Data System (ADS)

Li, Mi; Pu, Yunqiao; Ragauskas, Arthur

2016-11-01

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

Characterization and analysis of the molecular weight of lignin for biorefining studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolbert, Allison; Akinosho, Hannah; Khunsupat, Ratayakorn

2014-06-04

The molecular weight of lignin is a fundamental property that infl uences the recalcitrance of biomass and the valorization of lignin. The determination of the molecular weight of lignin in native biomass is dependent on the bioresources used and the isolation and purifi cation procedures employed. The three most commonly employed isolation methods are milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and enzymatic mild acidolysis lignin (EMAL). Common characterization techniques for determining the molecular weight of lignin will be addressed, with an emphasis on gel permeation chromatography (GPC). This review also examines the mechanisms behind several biological, physical, andmore » chemical pre-treatments and their impact on the molecular weight of lignin. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (D) all vary in magnitude depending on the biomass source, pre-treatment conditions, and isolation method. Additionally, there is a growing body of literature that supports changes in the molecular weight of lignin in response to genetic modifi cations in the lignin biosynthetic pathways. This review summarizes different procedures for obtaining the molecular weight of lignin that have been used in recent years and highlight future opportunities for applications of lignin.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Yining; Donohoe, Bryon S

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 wholemore » cell walls from native plant tissue and treated biomass are also discussed.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joshua, C. J.; Simmons, B. A.; Singer, S. W.

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 insoluble aggregates. The soluble lignin moieties exhibited higher ferricyanide reactivity because of increased access of the phenolic hydroxyl groups to the ferricyanide reagents. Ferricyanide reactivity of soluble lignin moieties correlated inversely with the molecular weightmore » distributions of the molecules, probably due to the involvement of phenolic hydroxyl groups in bond formation. The insoluble lignin aggregates exhibited low ferricyanide reactivity due to sequestration of the phenolic hydroxyl groups within the solid matrix. The study also highlighted the sequestration of polydispersed water-soluble lignin moieties by insoluble aggregates. The sequestered moieties were released by treatment with 0.01 M NaOH at 37 °C for 180 min. The redox assay was effective on different types of lignin extracts such as Klason lignin from switchgrass, ionic-liquid derived lignin from Eucalyptus and alkali lignin extracts. The assay generated a distinct profile for each lignin sample that was highly reproducible. The assay was also used to monitor consumption of syringic acid by Sphingobium sp. SYK-6. The simplicity and reproducibility of this assay makes it an excellent and versatile tool for qualitative and semi-quantitative characterization and comparative profiling of aqueous lignin samples.« less

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

DOE PAGES

Joshua, C. J.; Simmons, B. A.; Singer, S. W.

2016-06-02

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 insoluble aggregates. The soluble lignin moieties exhibited higher ferricyanide reactivity because of increased access of the phenolic hydroxyl groups to the ferricyanide reagents. Ferricyanide reactivity of soluble lignin moieties correlated inversely with the molecular weightmore » distributions of the molecules, probably due to the involvement of phenolic hydroxyl groups in bond formation. The insoluble lignin aggregates exhibited low ferricyanide reactivity due to sequestration of the phenolic hydroxyl groups within the solid matrix. The study also highlighted the sequestration of polydispersed water-soluble lignin moieties by insoluble aggregates. The sequestered moieties were released by treatment with 0.01 M NaOH at 37 °C for 180 min. The redox assay was effective on different types of lignin extracts such as Klason lignin from switchgrass, ionic-liquid derived lignin from Eucalyptus and alkali lignin extracts. The assay generated a distinct profile for each lignin sample that was highly reproducible. The assay was also used to monitor consumption of syringic acid by Sphingobium sp. SYK-6. The simplicity and reproducibility of this assay makes it an excellent and versatile tool for qualitative and semi-quantitative characterization and comparative profiling of aqueous lignin samples.« less

Lignin-assisted exfoliation of molybdenum disulfide in aqueous media and its application in lithium ion batteries

NASA Astrophysics Data System (ADS)

Liu, Wanshuang; Zhao, Chenyang; Zhou, Rui; Zhou, Dan; Liu, Zhaolin; Lu, Xuehong

2015-05-01

In this article, alkali lignin (AL)-assisted direct exfoliation of MoS2 mineral into single-layer and few-layer nanosheets in water is reported for the first time. Under optimized conditions, the concentration of MoS2 nanosheets in the obtained dispersion can be as high as 1.75 +/- 0.08 mg mL-1, which is much higher than the typical reported concentrations (<1.0 mg mL-1) using synthetic polymers or compounds as surfactants. The stabilizing mechanism primarily lies in the electrostatic repulsion between negative charged AL, as suggested by zeta-potential measurements. When the exfoliated MoS2 nanosheets are applied as electrode materials for lithium ion batteries, they show much improved electrochemical performance compared with the pristine MoS2 mineral because of the enhanced ion and electron transfer kinetics. This facile, scalable and eco-friendly aqueous-based process in combination with renewable and ultra-low-cost lignin opens up possibilities for large-scale fabrication of MoS2-based nanocomposites and devices. Moreover, herein we demonstrate that AL is also an excellent surfactant for exfoliation of many other types of layered materials, including graphene, tungsten disulfide and boron nitride, in water, providing rich opportunities for a wider range of applications.In this article, alkali lignin (AL)-assisted direct exfoliation of MoS2 mineral into single-layer and few-layer nanosheets in water is reported for the first time. Under optimized conditions, the concentration of MoS2 nanosheets in the obtained dispersion can be as high as 1.75 +/- 0.08 mg mL-1, which is much higher than the typical reported concentrations (<1.0 mg mL-1) using synthetic polymers or compounds as surfactants. The stabilizing mechanism primarily lies in the electrostatic repulsion between negative charged AL, as suggested by zeta-potential measurements. When the exfoliated MoS2 nanosheets are applied as electrode materials for lithium ion batteries, they show much improved electrochemical performance compared with the pristine MoS2 mineral because of the enhanced ion and electron transfer kinetics. This facile, scalable and eco-friendly aqueous-based process in combination with renewable and ultra-low-cost lignin opens up possibilities for large-scale fabrication of MoS2-based nanocomposites and devices. Moreover, herein we demonstrate that AL is also an excellent surfactant for exfoliation of many other types of layered materials, including graphene, tungsten disulfide and boron nitride, in water, providing rich opportunities for a wider range of applications. Electronic supplementary information (ESI) available: CV of the bulk MoS2 between 1-3 V, electrochemical performances of the exfoliated MoS2 nanosheets between 1-3 V with 10 wt% carbon black, referenced table of exfoliation of MoS2 in aqueous media. See DOI: 10.1039/c5nr01891a

Pathways for degradation of lignin in bacteria and fungi.

PubMed

Bugg, Timothy D H; Ahmad, Mark; Hardiman, Elizabeth M; Rahmanpour, Rahman

2011-11-01

Lignin is a heterogeneous aromatic polymer found as 10-35% of lignocellulose, found in plant cell walls. The bio-conversion of plant lignocellulose to glucose is an important part of second generation biofuel production, but the resistance of lignin to breakdown is a major obstacle in this process, hence there is considerable interest in the microbial breakdown of lignin. White-rot fungi are known to break down lignin with the aid of extracellular peroxidase and laccase enzymes. There are also reports of bacteria that can degrade lignin, and recent work indicates that bacterial lignin breakdown may be more significant than previously thought. The review will discuss the enzymes for lignin breakdown in fungi and bacteria, and the catabolic pathways for breakdown of the β-aryl ether, biphenyl and other components of lignin in bacteria and fungi. The review will also discuss small molecule phenolic breakdown products from lignin that have been identified from lignin-degrading microbes, and includes a bioinformatic analysis of the occurrence of known lignin-degradation pathways in Gram-positive and Gram-negative bacteria.

Coniferyl alcohol hinders the growth of tobacco BY-2 cells and Nicotiana benthamiana seedlings.

PubMed

Väisänen, Enni E; Smeds, Annika I; Fagerstedt, Kurt V; Teeri, Teemu H; Willför, Stefan M; Kärkönen, Anna

2015-09-01

Externally added coniferyl alcohol at high concentrations reduces the growth of Nicotiana cells and seedlings. Coniferyl alcohol is metabolized by BY-2 cells to several compounds. Coniferyl alcohol (CA) is a common monolignol and a building block of lignin. The toxicity of monolignol alcohols has been stated in the literature, but there are only few studies suggesting that this is true. We investigated the physiological effects of CA on living plant cells in more detail. Tobacco (Nicotiana tabacum) Bright yellow-2 cells (BY-2) and Nicotiana benthamiana seedlings both showed concentration-dependent growth retardation in response to 0.5-5 mM CA treatment. In some cases, CA addition caused cell death in BY-2 cultures, but this response was dependent on the growth stage of the cells. Based on LC-MS/MS analysis, BY-2 cells did not accumulate the externally supplemented CA, but metabolized it to ferulic acid, ferulic acid glycoside, coniferin, and to some other phenolic compounds. In addition to growth inhibition, CA caused the formation of a lignin-like compound detected by phloroglucinol staining in N. benthamiana roots and occasionally in BY-2 cells. To prevent this, we added potassium iodide (KI, at 5 mM) to overcome the peroxidase-mediated CA polymerization to lignin. KI had, however, toxic effects on its own: in N. benthamiana seedlings, it caused reduction in growth; in BY-2 cells, reduction in growth and cell viability. Surprisingly, CA restored the growth of KI-treated BY-2 cells and N. benthamiana seedlings. Our results suggest that CA at high concentrations is toxic to plant cells.

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

PubMed

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

2016-09-01

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

The effect of seaweed Ecklonia maxima extract and mineral nitrogen on fodder grass chemical composition.

PubMed

Ciepiela, Grażyna Anna; Godlewska, Agnieszka; Jankowska, Jolanta

2016-02-01

The objective of this study was to determine the effect of the biostimulant Kelpak and different nitrogen rates on cellulose, hemicellulose and lignin contents as well as non-structural carbohydrates in orchard grass and Braun's festulolium. The experiment was a split-plot arrangement with three replicates. It was set up at the experimental facility of the University of Natural Sciences and Humanities, Siedlce, in late April 2009. The following factors were examined: biostimulant with the trade name Kelpak SL applied at 2 dm(3) ha(-1) and a control-no biostimulant; nitrogen application rates 50 and 150 kg ha(-1) and a control (0 kg ha(-1)); pure stands of grass species grown in monoculture--orchard grass (Dactylis glomerata), cv. Amila,-Braun's festulolium (Festulolium braunii), cv. Felopa. Kelpak significantly increased non-structural carbohydrates, and increasing nitrogen rates reduced the concentration of these components in plants. Increasing nitrogen rates significantly decreased cellulose, hemicellulose, lignin and non-structural carbohydrate contents. Compared with orchard grass, Braun's festulolium proved to be of a higher nutritional value due to lower cellulose, hemicellulose and lignin contents and more non-structural carbohydrates. The aforementioned contents in the grasses differed significantly depending on the cut. Most cellulose and non-structural carbohydrates were determined in second-cut grass whereas most hemicellulose and lignin in second-cut grass.

Novel Bioactive Antimicrobial Lignin Containing Coatings on Titanium Obtained by Electrophoretic Deposition

PubMed Central

Erakovic, Sanja; Jankovic, Ana; Tsui, Gary C. P.; Tang, Chak-Yin; Miskovic-Stankovic, Vesna; Stevanovic, Tatjana

2014-01-01

Hydroxyapatite (HAP) is the most suitable biocompatible material for bone implant coatings; its brittleness, however, is a major obstacle, and the reason why research focuses on creating composites with biopolymers. Organosolv lignin (Lig) is used for the production of composite coatings, and these composites were examined in this study. Titanium substrate is a key biomedical material due to its well-known properties, but infections of the implantation site still impose a serious threat. One approach to prevent infection is to improve antimicrobial properties of the coating material. Silver doped hydroxyapatite (Ag/HAP) and HAP coatings on titanium were obtained by an electrophoretic deposition method in order to control deposited coating mass and morphology by varying applied voltage and deposition time. The effect of lignin on microstructure, morphology and thermal behavior of biocomposite coatings was investigated. The results showed that higher lignin concentrations protect the HAP lattice during sintering, improving coating stability. The corrosion stability was evaluated in simulated body fluid (SBF) at 37 °C. Newly formed plate-shaped carbonate-HAP was detected, indicating enhanced bioactive performance. The antimicrobial efficiency of Ag/HAP/Lig was confirmed by its higher reduction of bacteria Staphylococcus aureus TL (S. aureus TL) than of HAP/Lig coating. Cytotoxicity assay revealed that both coatings can be classified as non-toxic against healthy immunocompetent peripheral blood mononuclear cells (PBMC). PMID:25019343

Novel bioactive antimicrobial lignin containing coatings on titanium obtained by electrophoretic deposition.

PubMed

Erakovic, Sanja; Jankovic, Ana; Tsui, Gary C P; Tang, Chak-Yin; Miskovic-Stankovic, Vesna; Stevanovic, Tatjana

2014-07-11

Hydroxyapatite (HAP) is the most suitable biocompatible material for bone implant coatings; its brittleness, however, is a major obstacle, and the reason why research focuses on creating composites with biopolymers. Organosolv lignin (Lig) is used for the production of composite coatings, and these composites were examined in this study. Titanium substrate is a key biomedical material due to its well-known properties, but infections of the implantation site still impose a serious threat. One approach to prevent infection is to improve antimicrobial properties of the coating material. Silver doped hydroxyapatite (Ag/HAP) and HAP coatings on titanium were obtained by an electrophoretic deposition method in order to control deposited coating mass and morphology by varying applied voltage and deposition time. The effect of lignin on microstructure, morphology and thermal behavior of biocomposite coatings was investigated. The results showed that higher lignin concentrations protect the HAP lattice during sintering, improving coating stability. The corrosion stability was evaluated in simulated body fluid (SBF) at 37 °C. Newly formed plate-shaped carbonate-HAP was detected, indicating enhanced bioactive performance. The antimicrobial efficiency of Ag/HAP/Lig was confirmed by its higher reduction of bacteria Staphylococcus aureus TL (S. aureus TL) than of HAP/Lig coating. Cytotoxicity assay revealed that both coatings can be classified as non-toxic against healthy immunocompetent peripheral blood mononuclear cells (PBMC).

Variability in Lignin Composition and Structure in Cell Walls of Different Parts of Macaúba (Acrocomia aculeata) Palm Fruit.

PubMed

Rencoret, Jorge; Kim, Hoon; Evaristo, Anderson B; Gutiérrez, Ana; Ralph, John; Del Río, José C

2018-01-10

The lignins from different anatomical parts of macaúba (Acrocomia aculeata) palm fruit, namely stalks, epicarp, and endocarp, were studied. The lignin from stalks was enriched in S-lignin units (S/G 1.2) and β-ether linkages (84% of the total) and was partially acylated at the γ-OH of the lignin side-chains (26% lignin acylation), predominantly with p-hydroxybenzoates and acetates. The epicarp lignin was highly enriched in G-lignin units (S/G 0.2) and consequently depleted in β-ethers (65%) and enriched in condensed structures such as phenylcoumarans (24%) and dibenzodioxocins (3%). The endocarp lignin was strikingly different from the rest and presented large amounts of piceatannol units incorporated into the polymer. This resulted in a lignin polymer depleted in β-ethers but enriched in condensed structures and linked piceatannol moieties. The incorporation of piceatannol into the lignin polymer seems to have a role in seed protection.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

da Costa Sousa, Leonardo; Foston, Marcus; Bokade, Vijay

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

The controlled release of bioactive compounds from lignin and lignin-based biopolymer matrices.

PubMed

Chowdhury, Mohammad A

2014-04-01

This article presents the perspectives on the lignin-based controlled release (CR) of bioactive materials which are based on the researches that took place over the last three decades. It encompasses three broad spectra of observations: CR formulations with mixed-matrix of lignin; CR formulations with modified lignin; and the lignin-based CR formulation modelling. The article covers a range of bioactive materials aimed for agricultural utilisations viz. herbicides, pesticides, insecticides and fertilisers for their controlled release studies, which were formulated either with lignin or lignin-based biopolymers. The inherent complexities, structural heterogeneities, and the presence of myriad range of functionalities in the lignin structure make it difficult to understand and explaining the underlying CR behaviour and process. In conjunction to this issue, the fundamental aspects of the synthetic and biocompatible polymer-based drug controlled release process are presented, and correlated with the lignin-based CR research. The articulation of this correlation and the overview presented in this article may be complemented of the future lignin-based CR research gaining better insights, reflections, and understanding. A recommended approach on the lignin depolymerisation is suggested to fragmenting the lignin, which may be tailored further using the re-polymerisation or other synthetic approaches. Thus it may allow more control with flexibilities and improved properties of the modified lignin materials, and help achieve the desired CR outcomes. Copyright © 2014 Elsevier B.V. All rights reserved.

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

PubMed

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.

Physiology and biochemistry of a lignin degrading bacterium Erwinia sp. Cu 3614

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajan, J.S.

1992-01-01

Previous researchers have reported the isolation of a diphenylether cleaving organism, Erwinia sp., using an enrichment medium containing lignin. A copper and dinitrophenol resistant mutant of this organism, Erwinia sp. Cu3614, has also been reported. To assess the effect of copper on the growth and biochemistry of this organism, continuous cultivation was used employing an apparently optimized medium containing ethanol as carbon source. Upon increasing the concentration of copper sulfate in the medium from 5 [mu]g/ml to 10 [mu]g/ml increases in maximum specific growth rate and growth yield were seen. Also decrease in the values for doubling time and themore » coefficient for maintenance energy were seen. At higher levels of copper sulfate a [open quotes]non competitive[close quotes] inhibition of growth was seen as indicated by the values calculated for substrate affinity constant, and inhibition constant. To assess this organism's ligninolytic ability, an assay for residual lignin was developed. The assay measured a reaction between diazotized sulfanilic acid and lignin in alkaline solution by spectrophotometric monitoring of the resulting adduct. Use of this technique indicated that Erwinia sp. Cu3614 could degrade up to 80% of lignin in batch cultures. Further evidence about the ligninolytic ability of this organism was provided by examination of electron micrographs of lignocellulosic substrates incubated with cell suspensions. An assay for monitoring diphenylether cleaving abilities was also developed using resazurin, a redox dye. In vivo assays with cells obtained from continuous culture studies indicated a linear relationship between the rates of reaction with resazurin and the amount of copper associated with cells. In vitro assays, employing cell free extracts and resazurin, were used to obtain a fraction enriched in diphenylether cleaving activity by a heat treatment procedure.« less

Lignin-modifying enzymes of the white rot basidiomycete Ganoderma lucidum

DOE Office of Scientific and Technical Information (OSTI.GOV)

D /Souza, T.M.; Merritt, C.S.; Reddy, C.A.

1999-12-01

Ganoderma lucidum, a white rot basidiomycete widely distributed worldwide, was studied for the production of the lignin-modifying enzymes laccase, manganese-dependent peroxidase (MnP), and lignin peroxidase (LiP). Laccase levels observed in high-nitrogen shaken cultures were much greater than those seen in low-nitrogen, malt extract, or wool-grown cultures and those reported for most other white rot fungi to date. Laccase production was readily seen in cultures grown with pine or poplar as the sole carbon and energy source. Cultures containing both pine and poplar showed 5- to 10-fold-higher levels of laccase than cultures containing pine or poplar alone. Since syringyl units aremore » structural components important in poplar lignin and other hardwoods but much less so in pine lignin and other softwoods, pine cultures were supplemented with syringic acid, and this resulted in laccase levels comparable to those seen in pine-plus-poplar cultures. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis of concentrated extracellular culture fluid from HM cultures showed two laccase activity bands, where as isoelectric focusing revealed five major laccase activity bands with estimated pIs of 3.0, 4.25, 4.5, and 5.1. Low levels of MnP activity were detected in poplar-grown cultures but not in cultures grown with pine, with pine plus syringic acid, or in HN medium. No LiP activity was seen in any of the media tested; however, probing the genomic DNA with the LiP cDNA (CLG4) from the white rot fungus Phanerochaete chrysosporium showed distinct hybridization bands suggesting the presence of lip-like sequences in G. lucidum.« less

Bacterial extracellular lignin peroxidase

DOEpatents

Crawford, Donald L.; Ramachandra, Muralidhara

1993-01-01

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

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

PubMed

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

2006-08-09

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1986-01-01

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

Effects of lignin structure on hydrodeoxygenation reactivity of pine wood lignin to valuable chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongliang; Ben, Haoxi; Southeast Univ., Nanjing

Hydrodeoxygenation (HDO) of two dilute acid flow through pretreated softwood lignin samples, including residual lignin in pretreated solid residues (ReL) and recovered insoluble lignin in pretreated liquid (RISL), with apparent different physical and chemical structures, was comprehensively studied. A combination of catalysts (HY zeolite and Ru/Al 2O 3) was employed to investigate the effects of lignin structures, especially condensed structures, on the HDO upgrading process. Results indicated that the condensed structure and short side chains in lignin hindered its HDO conversion under different reaction conditions, including catalyst loading and composition, hydrogen pressure, and reaction time. In addition to lignin structure,more » HY zeolite was found crucial for lignin depolymerization, while Ru/Al 2O 3 and relatively high hydrogen pressure (4 MPa) were necessary for upgrading unstable oxy-compounds to cyclohexanes at high selectivity (>95 wt %). Since the lignin structure essentially affects its reactivity during HDO conversion, the yield and selectivity of HDO products can be predicted by detailed characterization of the lignin structure. Furthermore, the insights gained from this study in the fundamental reaction mechanisms based on the lignin structure will facilitate upgrading of lignin to high-value products for applications in the production of both fuels and chemicals.« less

Effects of lignin structure on hydrodeoxygenation reactivity of pine wood lignin to valuable chemicals

DOE PAGES

Wang, Hongliang; Ben, Haoxi; Southeast Univ., Nanjing; ...

2017-01-05

Hydrodeoxygenation (HDO) of two dilute acid flow through pretreated softwood lignin samples, including residual lignin in pretreated solid residues (ReL) and recovered insoluble lignin in pretreated liquid (RISL), with apparent different physical and chemical structures, was comprehensively studied. A combination of catalysts (HY zeolite and Ru/Al 2O 3) was employed to investigate the effects of lignin structures, especially condensed structures, on the HDO upgrading process. Results indicated that the condensed structure and short side chains in lignin hindered its HDO conversion under different reaction conditions, including catalyst loading and composition, hydrogen pressure, and reaction time. In addition to lignin structure,more » HY zeolite was found crucial for lignin depolymerization, while Ru/Al 2O 3 and relatively high hydrogen pressure (4 MPa) were necessary for upgrading unstable oxy-compounds to cyclohexanes at high selectivity (>95 wt %). Since the lignin structure essentially affects its reactivity during HDO conversion, the yield and selectivity of HDO products can be predicted by detailed characterization of the lignin structure. Furthermore, the insights gained from this study in the fundamental reaction mechanisms based on the lignin structure will facilitate upgrading of lignin to high-value products for applications in the production of both fuels and chemicals.« less

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

PubMed

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

2015-01-21

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

Lignin conversion: Opportunities and challenges for the integrated biorefinery

DOE PAGES

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

2016-06-21

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

Lignin conversion: Opportunities and challenges for the integrated biorefinery

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

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

PubMed

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

2013-02-01

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

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

PubMed

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.

Carbon composite lignin-based adsorbents for the adsorption of dyes.

PubMed

Wang, Xiaohong; Jiang, Chenglong; Hou, Bingxia; Wang, Yingying; Hao, Chen; Wu, Jingbo

2018-05-10

Carbon composite lignin-based adsorbent were prepared through hydrothermal method with glucose as carbon source, calcium lignosulfonate and triethylene tetramine as raw materials, respectively. The optimum synthesis conditions were determined by investigating the addition of carbon and triethylene tetramine. The adsorbent was used for the adsorption of azo dyes Congo red and Eriochrome blue black R, and the five factors affecting the adsorption were discussed, including pH of dyes, initial concentration, adsorption time, adsorption temperature and adsorbent dosage. The corresponding adsorption mechanism such as pseudo first order kinetics, pseudo second order kinetics, intraparticle diffusion, Langmuir adsorption isotherm, Freundlich isotherm, Temkin isotherm, Dubinin-Radushkevich adsorption isotherm, thermodynamics were also studied. When the dye concentration is 40 mg L -1 , Congo red and Eriochrome blue black R dye removal rates reach 99%. Moreover, the adsorption process of two kinds of dyes follow the pseudo second order kinetics and the Langmuir adsorption isotherm. Copyright © 2018 Elsevier Ltd. All rights reserved.

Signatures of Biomass Burning Aerosols during a Smoke Plume Event from a Saltmarsh Wildfire in South Texas

NASA Astrophysics Data System (ADS)

Louchouarn, P.; Griffin, R. J.; Norwood, M. J.; Sterne, A. M. E.; Karakurt Cevik, B.

2014-12-01

The most conventional and abundant tracers of biomass combustion in aerosol particles include potassium and biomarkers derived from thermally altered cellulose/hemicellulose (anhydrosugars) and lignin (methoxyphenols). However, little is known of the role of biomass combustion as a particulate source of major plant polymers to the atmosphere. Here, concentrations of "free" (solvent-extractable) anhydrosugars and methoxyphenols are compared to the yields of polymeric lignin oxidation products (LOPs) during a smoke plume event in Houston, Texas. Downwind aerosol samples (PM2.5) were collected prior to, during, and following a two-day wildfire event that burned ~5,000 acres of a spartina saltmarsh ecosystem in the McFaddin National Wildlife Refuge, 125 km southeast of Houston. In addition, charcoals of the burned plants were collected within a week of the fire at the wildfire site. HYSPLIT modeling shows that Houston was directly downwind of this wildfire during the peak of the burn, with an approximate travel time from source to aerosol sampling site of 12-16 hrs. Concentrations of all organic markers, K+, and Ca2+ jumped by a factor of 2-13 within 1-2 days of the start of the fire and dropped to pre-fire levels three days after the peak event. Source signatures of anhydrosugars and free methoxyphenols during the peak of the plume were identical to those of grass charcoals collected from the site, confirming the potential use of charcoals as endmembers for source input reconstruction during atmospheric transport. An enrichment factor of 20 in the anhydrosugar to methoxyphenol ratio of aerosols vs. charcoals can partially be explained by differences in degradation rate constants between the two biomarker groups. Polymeric LOP comprised 73-91% of all lignin material in the aerosols, pointing to fires as major sources of primary biogenic aerosol particles and confirming an earlier study that lignin phenols in atmospheric particles occur predominantly in polymeric form.

Litter Decomposition in a Semiarid Dune Grassland: Neutral Effect of Water Supply and Inhibitory Effect of Nitrogen Addition.

PubMed

Li, Yulin; Ning, Zhiying; Cui, Duo; Mao, Wei; Bi, Jingdong; Zhao, Xueyong

2016-01-01

The decomposition of plant material in arid ecosystems is considered to be substantially controlled by water and N availability. The responses of litter decomposition to external N and water, however, remain controversial, and the interactive effects of supplementary N and water also have been largely unexamined. A 3.5-year field experiment with supplementary nitrogen and water was conducted to assess the effects of N and water addition on mass loss and nitrogen release in leaves and fine roots of three dominant plant species (i.e., Artemisia halondendron, Setaria viridis, and Phragmites australis) with contrasting substrate chemistry (e.g. N concentration, lignin content in this study) in a desertified dune grassland of Inner Mongolia, China. The treatments included N addition, water addition, combination of N and water, and an untreated control. The decomposition rate in both leaves and roots was related to the initial litter N and lignin concentrations of the three species. However, litter quality did not explain the slower mass loss in roots than in leaves in the present study, and thus warrant further research. Nitrogen addition, either alone or in combination with water, significantly inhibited dry mass loss and N release in the leaves and roots of the three species, whereas water input had little effect on the decomposition of leaf litter and fine roots, suggesting that there was no interactive effect of supplementary N and water on litter decomposition in this system. Furthermore, our results clearly indicate that the inhibitory effects of external N on dry mass loss and nitrogen release are relatively strong in high-lignin litter compared with low-lignin litter. These findings suggest that increasing precipitation hardly facilitates ecosystem carbon turnover but atmospheric N deposition can enhance carbon sequestration and nitrogen retention in desertified dune grasslands of northern China. Additionally, litter quality of plant species should be considered when modelling the carbon cycle and nutrient dynamics of this system.

[Effects of Different Residue Part Inputs of Corn Straws on CO2 Efflux and Microbial Biomass in Clay Loam and Sandy Loam Black Soils].

PubMed

Liu, Si-yi; Liang, Ai-zhen; Yang, Xue-ming; Zhang, Xiao-ping; Jia, Shu-xia; Chen, Xue-wen; Zhang, Shi-xiu; Sun, Bing-jie; Chen, Sheng-long

2015-07-01

The decomposed rate of crop residues is a major determinant for carbon balance and nutrient cycling in agroecosystem. In this study, a constant temperature incubation study was conducted to evaluate CO2 emission and microbial biomass based on four different parts of corn straw (roots, lower stem, upper stem and leaves) and two soils with different textures (sandy loam and clay loam) from the black soil region. The relationships between soil CO2 emission, microbial biomass and the ratio of carbon (C) to nitrogen (N) and lignin of corn residues were analyzed by the linear regression. Results showed that the production of CO2 was increased with the addition of different parts of corn straw to soil, with the value of priming effect (PE) ranged from 215. 53 µmol . g-1 to 335. 17 µmol . g -1. Except for corn leaves, the cumulative CO2 production and PE of clay loam soil were significantly higher than those in sandy loam soil. The correlation of PE with lignin/N was obviously more significant than that with lignin concentration, nitrogen concentration and C/N of corn residue. The addition of corn straw to soil increased the contents of MBC and MBN and decreased MBC/MBN, which suggested that more nitrogen rather than carbon was conserved in microbial community. The augmenter of microbial biomass in sandy loam soil was greater than that in clay loam soil, but the total dissolved nitrogen was lower. Our results indicated that the differences in CO2 emission with the addition of residues to soils were primarily ascribe to the different lignin/N ratio in different corn parts; and the corn residues added into the sandy loam soil could enhance carbon sequestration, microbial biomass and nitrogen holding ability relative to clay loam soil.

Litter Decomposition in a Semiarid Dune Grassland: Neutral Effect of Water Supply and Inhibitory Effect of Nitrogen Addition

PubMed Central

Li, Yulin; Ning, Zhiying; Cui, Duo; Mao, Wei; Bi, Jingdong; Zhao, Xueyong

2016-01-01

Background The decomposition of plant material in arid ecosystems is considered to be substantially controlled by water and N availability. The responses of litter decomposition to external N and water, however, remain controversial, and the interactive effects of supplementary N and water also have been largely unexamined. Methodology/Principal Findings A 3.5-year field experiment with supplementary nitrogen and water was conducted to assess the effects of N and water addition on mass loss and nitrogen release in leaves and fine roots of three dominant plant species (i.e., Artemisia halondendron, Setaria viridis, and Phragmites australis) with contrasting substrate chemistry (e.g. N concentration, lignin content in this study) in a desertified dune grassland of Inner Mongolia, China. The treatments included N addition, water addition, combination of N and water, and an untreated control. The decomposition rate in both leaves and roots was related to the initial litter N and lignin concentrations of the three species. However, litter quality did not explain the slower mass loss in roots than in leaves in the present study, and thus warrant further research. Nitrogen addition, either alone or in combination with water, significantly inhibited dry mass loss and N release in the leaves and roots of the three species, whereas water input had little effect on the decomposition of leaf litter and fine roots, suggesting that there was no interactive effect of supplementary N and water on litter decomposition in this system. Furthermore, our results clearly indicate that the inhibitory effects of external N on dry mass loss and nitrogen release are relatively strong in high-lignin litter compared with low-lignin litter. Conclusion/Significance These findings suggest that increasing precipitation hardly facilitates ecosystem carbon turnover but atmospheric N deposition can enhance carbon sequestration and nitrogen retention in desertified dune grasslands of northern China. Additionally, litter quality of plant species should be considered when modelling the carbon cycle and nutrient dynamics of this system. PMID:27617439

Advanced Chemical Design for Efficient Lignin Bioconversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Shangxian; Sun, Qining; Pu, Yunqiao

Here, lignin depolymerization mainly involves redox reactions relying on the effective electron transfer. Even though electron mediators were previously used for delignification of paper pulp, no study has established a bioprocess to fragment and solubilize the lignin with an effective laccase–mediator system, in particular, for subsequent microbial bioconversion. Efficient lignin depolymerization was achieved by screening proper electron mediators with laccase to attain a nearly 6-fold increase of kraft lignin solubility compared to the control kraft lignin without laccase treatment. Chemical analysis suggested the release of a low molecular weight fraction of kraft lignin into the solution phase. Moreover, NMR analysismore » revealed that an efficient enzyme–mediator system can promote the lignin degradation. More importantly, the fundamental mechanisms guided the development of an efficient lignin bioconversion process, where solubilized lignin from laccase–HBT treatment served as a superior substrate for bioconversion by Rhodococcus opacus PD630. The cell growth was increased by 10 6 fold, and the lipid titer reached 1.02 g/L. Overall, the study has manifested that an efficient enzyme–mediator–microbial system can be exploited to establish a bioprocess to solubilize lignin, cleave lignin linkages, modify the structure, and produce substrates amenable to bioconversion.« less

Advanced Chemical Design for Efficient Lignin Bioconversion

DOE PAGES

Xie, Shangxian; Sun, Qining; Pu, Yunqiao; ...

2017-01-30

Here, lignin depolymerization mainly involves redox reactions relying on the effective electron transfer. Even though electron mediators were previously used for delignification of paper pulp, no study has established a bioprocess to fragment and solubilize the lignin with an effective laccase–mediator system, in particular, for subsequent microbial bioconversion. Efficient lignin depolymerization was achieved by screening proper electron mediators with laccase to attain a nearly 6-fold increase of kraft lignin solubility compared to the control kraft lignin without laccase treatment. Chemical analysis suggested the release of a low molecular weight fraction of kraft lignin into the solution phase. Moreover, NMR analysismore » revealed that an efficient enzyme–mediator system can promote the lignin degradation. More importantly, the fundamental mechanisms guided the development of an efficient lignin bioconversion process, where solubilized lignin from laccase–HBT treatment served as a superior substrate for bioconversion by Rhodococcus opacus PD630. The cell growth was increased by 10 6 fold, and the lipid titer reached 1.02 g/L. Overall, the study has manifested that an efficient enzyme–mediator–microbial system can be exploited to establish a bioprocess to solubilize lignin, cleave lignin linkages, modify the structure, and produce substrates amenable to bioconversion.« less

Seedling growth and development on space shuttle

NASA Astrophysics Data System (ADS)

Cowles, J.; Lemay, R.; Jahns, G.

1994-11-01

Young pine seedlings, and mung bean and oat seeds were flown on shuttle flights, STS-3 and STS-51F, in March, 1982 and July/August, 1985, respectively. The plant growth units built to support the two experiments functioned mechanically as anticipated and provided the necessary support data. Pine seedlings exposed to the microgravity environment of the space shuttle for 8 days continued to grow at a rate similar to ground controls. Pine stems in flight seedlings, however, averaged 10 to 12% less lignin than controls. Flight mung beans grew slower than control beans and their stems contained about 25% less lignin than control seedlings. Reduced mung bean growth in microgravity was partly due to slower germination rate. Lignin also was reduced in flight oats as compared to controls. Oats and mung beans exhibited upward growing roots which were not observed in control seedlings. Chlorophll A/B ratios were lower in flight tissues than controls. The sealed PGCs exhibited large variations in atmospheric gas composition but the changes were similar between flight and ground controls. Ethylene was present in low concentrations in all chambers.

Effect of iron salt type and dosing mode on Fenton-based pretreatment of rice straw for enzymatic hydrolysis.

PubMed

Gan, Yu-Yan; Zhou, Si-Li; Dai, Xiao; Wu, Han; Xiong, Zi-Yao; Qin, Yuan-Hang; Ma, Jiayu; Yang, Li; Wu, Zai-Kun; Wang, Tie-Lin; Wang, Wei-Guo; Wang, Cun-Wen

2018-06-15

Fenton-based processes with four different iron salts in two different dosing modes were used to pretreat rice straw (RS) samples to increase their enzymatic digestibility. The composition analysis shows that the RS sample pretreated by the dosing mode of iron salt adding into H 2 O 2 has a much lower hemicellulose content than that pretreated by the dosing mode of H 2 O 2 adding into iron salt, and the RS sample pretreated by the chloride salt-based Fenton process has a much lower lignin content and a slightly lower hemicellulose content than that pretreated by the sulphate salt-based Fenton process. The higher concentration of reducing sugar observed on the RS sample with lower lignin and hemicellulose contents justifies that the Fenton-based process could enhance the enzymic hydrolysis of RS by removing hemicellulose and lignin and increasing its accessibility to cellulase. FeCl 3 ·6H 2 O adding into H 2 O 2 is the most efficient Fenton-based process for RS pretreatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Seedling growth and development on space shuttle

NASA Technical Reports Server (NTRS)

Cowles, J.; Lemay, R.; Jahns, G.

1994-01-01

Young pine seedlings, and mung bean and oat seeds were flown on shuttle flights, STS-3 and STS-51F, in March, 1982 and July/August, 1985, respectively. The plant growth units built to support the two experiments functioned mechanically as anticipated and provided the necessary support data. Pine seedlings exposed to the microgravity environment of the space shuttle for 8 days continued to grow at a rate similar to ground controls. Pine stems in flight seedlings, however, averaged 10 to 12% less lignin than controls. Flight mung beans grew slower than control beans and their stems contained about 25% less lignin than control seedlings. Reduced mung bean growth in microgravity was partly due to slower germination rate. Lignin also was reduced in flight oats as compared to controls. Oats and mung beans exhibited upward growing roots which were not observed in control seedlings. Chlorophyll A/B ratios were lower in flight tissues than controls. The sealed PGCs exhibited large variations in atmospheric gas composition but the changes were similar between flight and ground controls. Ethylene was present in low concentrations in all chambers.

The impact of large river system on the signal of dissolved organic matter: a case study on the Changjiang (Yangtze River), China

NASA Astrophysics Data System (ADS)

xiaona, W.; Bao, H.; Wu, Y.

2013-12-01

As one of the largest river in the world, studying the properties of dissolved organic matter in Changjiang can help us reveal the change of terrestrial organic matter in typical large subtropical river system. Samples collected from mid-lower reaches of Changjiang and its main tributaries/lakes in July 2010 and August 2012 were analysed for dissolved organic carbon (DOC), dissolved lignin phenols and chromophoric dissolved organic carbon (CDOM). Based on the hydrological condition, both of the two cruises are in flood season, while the latter is extremely flood season. The hydrological condition can impact the signal of dissolved lignin phenols as well as DOC. The DOC concentration is similar for both the cruises, with an average of 139×21 μM in 2010 and 130×36 μM in 2012. But the dissolved lignin phenols show obvious difference, the concentration is 13.6×3.4 μg/L and 12.7×5.2 μg/L for the main stream and tributaries/lakes in 2010 respectively, but it decreases to 8.7×2.5 μg/L and 6.5×3.5 μg/L in 2012.The dissolved lignin phenols show positive correlation with DOC in August 2012, but no similar trend is observed in 2010. Excitation-emission matrix fluorescence spectroscopy combined with parallel factor analysis (EEMs-PARAFAC) decomposes the fluorescence matrices of CDOM into three humic-like (H1: 315(250)/400 nm, H2: 350(280)/460 nm, H3: 250/450~485 nm) and two protein-like (P1: 270/315 nm, P2: 285/350 nm) components. Good linear correlations are observed within three humic-like components and two protein-like components, indicating that the same types of components (humic-like or protein-like) have similar origin and geochemical behaviors. However, these two kinds of components show different tendency. The total content of dissolved lignin phenols is correlated with the absorption in 280 nm, indicating the optical property of CDOM is related to its structure. There are many factors impacting the composition of dissolved organic matter in large river system like Changjiang. We find the biomarkers have mutative geochemical behaviors in different hydrological conditions. The variation of biomarkers can reveal the alternation in hydrological factor.

Bacterial enzymes involved in lignin degradation.

PubMed

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

2016-10-20

Lignin forms a large part of plant biomass. It is a highly heterogeneous polymer of 4-hydroxyphenylpropanoid units and is embedded within polysaccharide polymers forming lignocellulose. Lignin provides strength and rigidity to plants and is rather resilient towards degradation. To improve the (bio)processing of lignocellulosic feedstocks, more effective degradation methods of lignin are in demand. Nature has found ways to fully degrade lignin through the production of dedicated ligninolytic enzyme systems. While such enzymes have been well thoroughly studied for ligninolytic fungi, only in recent years biochemical studies on bacterial enzymes capable of lignin modification have intensified. This has revealed several types of enzymes available to bacteria that enable them to act on lignin. Two major classes of bacterial lignin-modifying enzymes are DyP-type peroxidases and laccases. Yet, recently also several other bacterial enzymes have been discovered that seem to play a role in lignin modifications. In the present review, we provide an overview of recent advances in the identification and use of bacterial enzymes acting on lignin or lignin-derived products. Copyright © 2016 The Author(s). Published by Elsevier B.V. All rights reserved.

Alkali-treated kraft lignin as a component in flakeboard eesins

Treesearch

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-...

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

Treesearch

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

2011-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Lan; Yoo, Chang Geun; Meng, Xianzhi

Background: 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).Results: Each lignin fraction had different physicochemical properties. Ethanol-extracted lignin had the lowest weight average molecular weight, while the molecular weightsmore » for the other two lignin fractions were similar. 31P 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 L1 > L3 > L2 for the low recalcitrance poplar and H1 > H2 > H3 for the high recalcitrance poplar.Conclusions: 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 ability. Lignins with more phenolic hydroxyl groups had higher CBH binding strength. It was also found that lignin fractions with more condensed aromatics adsorbed more CBH likely attributed to stronger hydrophobic interactions.« less

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

PubMed

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 ability. Lignins with more phenolic hydroxyl groups had higher CBH binding strength. It was also found that lignin fractions with more condensed aromatics adsorbed more CBH likely attributed to stronger hydrophobic interactions.

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

DOE PAGES

Yao, Lan; Yoo, Chang Geun; Meng, Xianzhi; ...

2018-04-04

Background: 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).Results: Each lignin fraction had different physicochemical properties. Ethanol-extracted lignin had the lowest weight average molecular weight, while the molecular weightsmore » for the other two lignin fractions were similar. 31P 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 L1 > L3 > L2 for the low recalcitrance poplar and H1 > H2 > H3 for the high recalcitrance poplar.Conclusions: 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 ability. Lignins with more phenolic hydroxyl groups had higher CBH binding strength. It was also found that lignin fractions with more condensed aromatics adsorbed more CBH likely attributed to stronger hydrophobic interactions.« less

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

PubMed

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.

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

PubMed

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.

Impact of hydration and temperature history on the structure and dynamics of lignin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vural, Derya; Gainaru, C.; O'Neill, Hugh Michael

The full utilization of plant biomass for the production of energy and novel materials often involves high temperature treatment. Examples include melt spinning of lignin for manufacturing low-cost carbon fiber and the relocalization of lignin to increase the accessibility of cellulose for production of biofuels. These temperature-induced effects arise from poorly understood changes in lignin flexibility. Here, we combine molecular dynamics simulations with neutron scattering and dielectric spectroscopy experiments to probe the dependence of lignin dynamics on hydration and thermal history. We find a dynamical and structural hysteresis: at a given temperature, the lignin molecules are more expanded and theirmore » dynamics faster when the lignin is cooled than when heated. The structural hysteresis is more pronounced for dry lignin. The difference in dynamics, however, follows a different trend, it is found to be more significant at high temperatures and high hydration levels. The simulations also reveal syringyl units to be more dynamic than guiacyl. The results provide an atomic-detailed description of lignin dynamics, important for understanding lignin role in plant cell wall mechanics and for rationally improving lignin processing. The lignin glass transition, at which the polymer softens, is lower when lignin is cooled than when heated, therefore extending the cooling phase of processing and shortening the heating phase may offer ways to lower processing costs.« less

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

PubMed

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

2015-01-01

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

Impact of hydration and temperature history on the structure and dynamics of lignin

DOE PAGES

Vural, Derya; Gainaru, C.; O'Neill, Hugh Michael; ...

2018-03-16

The full utilization of plant biomass for the production of energy and novel materials often involves high temperature treatment. Examples include melt spinning of lignin for manufacturing low-cost carbon fiber and the relocalization of lignin to increase the accessibility of cellulose for production of biofuels. These temperature-induced effects arise from poorly understood changes in lignin flexibility. Here, we combine molecular dynamics simulations with neutron scattering and dielectric spectroscopy experiments to probe the dependence of lignin dynamics on hydration and thermal history. We find a dynamical and structural hysteresis: at a given temperature, the lignin molecules are more expanded and theirmore » dynamics faster when the lignin is cooled than when heated. The structural hysteresis is more pronounced for dry lignin. The difference in dynamics, however, follows a different trend, it is found to be more significant at high temperatures and high hydration levels. The simulations also reveal syringyl units to be more dynamic than guiacyl. The results provide an atomic-detailed description of lignin dynamics, important for understanding lignin role in plant cell wall mechanics and for rationally improving lignin processing. The lignin glass transition, at which the polymer softens, is lower when lignin is cooled than when heated, therefore extending the cooling phase of processing and shortening the heating phase may offer ways to lower processing costs.« less

Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment.

PubMed

Donohoe, Bryon S; Decker, Stephen R; Tucker, Melvin P; Himmel, Michael E; Vinzant, Todd B

2008-12-01

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

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

PubMed

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

2017-10-17

Understanding the mechanisms underlying plant biomass recalcitrance at the molecular level can only be achieved by accurate analyses of both the content and structural features of the molecules involved. Current quantification of lignin is, however, majorly based on unspecific gravimetric analysis after sulfuric acid hydrolysis. Hence, our research aimed at specific lignin quantification with concurrent characterization of its structural features. Hereto, for the first time, a polymeric 13 C lignin was used as internal standard (IS) for lignin quantification via analytical pyrolysis coupled to gas chromatography with mass-spectrometric detection in selected ion monitoring mode (py-GC-SIM-MS). In addition, relative response factors (RRFs) for the various pyrolysis products obtained were determined and applied. First, 12 C and 13 C lignin were isolated from nonlabeled and uniformly 13 C labeled wheat straw, respectively, and characterized by heteronuclear single quantum coherence (HSQC), nuclear magnetic resonance (NMR), and py-GC/MS. The two lignin isolates were found to have identical structures. Second, 13 C-IS based lignin quantification by py-GC-SIM-MS was validated in reconstituted biomass model systems with known contents of the 12 C lignin analogue and was shown to be extremely accurate (>99.9%, R 2 > 0.999) and precise (RSD < 1.5%). Third, 13 C-IS based lignin quantification was applied to four common poaceous biomass sources (wheat straw, barley straw, corn stover, and sugar cane bagasse), and lignin contents were in good agreement with the total gravimetrically determined lignin contents. Our robust method proves to be a promising alternative for the high-throughput quantification of lignin in milled biomass samples directly and simultaneously provides a direct insight into the structural features of lignin.

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

PubMed Central

2017-01-01

Understanding the mechanisms underlying plant biomass recalcitrance at the molecular level can only be achieved by accurate analyses of both the content and structural features of the molecules involved. Current quantification of lignin is, however, majorly based on unspecific gravimetric analysis after sulfuric acid hydrolysis. Hence, our research aimed at specific lignin quantification with concurrent characterization of its structural features. Hereto, for the first time, a polymeric 13C lignin was used as internal standard (IS) for lignin quantification via analytical pyrolysis coupled to gas chromatography with mass-spectrometric detection in selected ion monitoring mode (py-GC-SIM-MS). In addition, relative response factors (RRFs) for the various pyrolysis products obtained were determined and applied. First, 12C and 13C lignin were isolated from nonlabeled and uniformly 13C labeled wheat straw, respectively, and characterized by heteronuclear single quantum coherence (HSQC), nuclear magnetic resonance (NMR), and py-GC/MS. The two lignin isolates were found to have identical structures. Second, 13C-IS based lignin quantification by py-GC-SIM-MS was validated in reconstituted biomass model systems with known contents of the 12C lignin analogue and was shown to be extremely accurate (>99.9%, R2 > 0.999) and precise (RSD < 1.5%). Third, 13C-IS based lignin quantification was applied to four common poaceous biomass sources (wheat straw, barley straw, corn stover, and sugar cane bagasse), and lignin contents were in good agreement with the total gravimetrically determined lignin contents. Our robust method proves to be a promising alternative for the high-throughput quantification of lignin in milled biomass samples directly and simultaneously provides a direct insight into the structural features of lignin. PMID:28926698

Ethanol production from a biomass mixture of furfural residues with green liquor-peroxide saccarified cassava liquid.

PubMed

Ji, Li; Zheng, Tianran; Zhao, Pengxiang; Zhang, Weiming; Jiang, Jianxin

2016-06-01

As the most abundant renewable resources, lignocellulosic materials are ideal candidates as alternative feedstock for bioethanol production. Cassava residues (CR) are byproducts of the cassava starch industry which can be mixed with lignocellulosic materials for ethanol production. The presence of lignin in lignocellulosic substrates can inhibit saccharification by reducing the cellulase activity. Simultaneous saccharification and fermentation (SSF) of furfural residues (FR) pretreated with green liquor and hydrogen peroxide (GL-H2O2) with CR saccharification liquid was investigated. The final ethanol concentration, yield, initial rate, number of live yeast cells, and the dead yeast ratio were compared to evaluate the effectiveness of combining delignificated lignocellulosic substrates and starchy substrates for ethanol production. Our results indicate that 42.0 % of FR lignin removal was achieved on FR using of 0.06 g H2O2/g-substrate and 9 mL GL/g-substrate at 80 °C. The highest overall ethanol yield was 93.6 % of the theoretical. When the ratio of 0.06 g/g-H2O2-GL-pretreated FR to CR was 5:1, the ethanol concentration was the same with that ratio of untreated FR to CR of 1:1. Using 0.06 g/g-H2O2-GL-pretreated FR with CR at a ratio of 2:1 resulted in 51.9 g/L ethanol concentration. Moreover, FR pretreated with GL-H2O2 decreased the concentration of byproducts in SSF compared with that obtained in the previous study. The lignin in FR would inhibit enzyme activity and GL-H2O2 is an advantageous pretreatment method to treat FR and high intensity of FR pretreatment increased the final ethanol concentration. The efficiency of ethanol fermentation of was improved when delignification increased. GL-H2O2 is an advantageous pretreatment method to treat FR. As the pretreatment dosage of GL-H2O2 on FR increased, the proportion of lignocellulosic substrates was enhanced in the SSF of the substrate mixture of CR and FR as compared with untreated FR. Moreover, the final ethanol concentration was increased with a high ethanol yield and lower byproduct concentrations.

Ethanol yields and cell wall properties in divergently bred switchgrass genotypes

USDA-ARS?s Scientific Manuscript database

Genetic modification of herbaceous plant cell walls to increase biofuels yields from harvested biomass is a primary bioenergy research goal. The focus of much of this research has been on cell wall lignin concentration. Using switchgrass genotypes developed by divergent breeding for ruminant diges...

Lignin and etherified ferulates impact digestibility and structural composition of three temperate perennial grasses

USDA-ARS?s Scientific Manuscript database

Breeding grasses for increased digestibility increases their value and profitability in ruminant livestock production systems. Digestibility can be improved in grasses by either increasing the concentration of soluble and readily fermentable carbohydrates or by altering the plant cell wall to create...

Recent advances in oxidative valorization of lignin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Ruoshui; Guo, Mond; Zhang, Xiao

Lignin, an aromatic macromolecule synthesized by all higher plants, is one of the most intriguing natural materials for utilization across a wide range of applications. Depolymerization and fragmentation of lignin into small chemicals constituents which can either replace current market products or be used building blocks for new material synthesis is a focus of current lignin valorization strategies. And among the variety of lignin degradation chemistries, catalytic oxidation of lignin presents an energy efficient means of lignin depolymerization and generating selective reaction products. Our review provides a summary of the recent advancements in oxidative lignin valorization couched in a discussionmore » on how these chemistries may contribute to the degradation of the lignin macromolecule through three major approaches: 1) inter-unit linkages cleavage; 2) propanyl side-chain oxidative modification; and 3) oxidation of the aromatic ring and ring cleavage reactions.« less

Recent advances in oxidative valorization of lignin

DOE PAGES

Ma, Ruoshui; Guo, Mond; Zhang, Xiao

2017-07-21

Lignin, an aromatic macromolecule synthesized by all higher plants, is one of the most intriguing natural materials for utilization across a wide range of applications. Depolymerization and fragmentation of lignin into small chemicals constituents which can either replace current market products or be used building blocks for new material synthesis is a focus of current lignin valorization strategies. And among the variety of lignin degradation chemistries, catalytic oxidation of lignin presents an energy efficient means of lignin depolymerization and generating selective reaction products. Our review provides a summary of the recent advancements in oxidative lignin valorization couched in a discussionmore » on how these chemistries may contribute to the degradation of the lignin macromolecule through three major approaches: 1) inter-unit linkages cleavage; 2) propanyl side-chain oxidative modification; and 3) oxidation of the aromatic ring and ring cleavage reactions.« less

Predicting lignin depolymerization yields from quantifiable properties using fractionated biorefinery lignins

USDA-ARS?s Scientific Manuscript database

Lignin depolymerization to aromatic monomers with high yields and selectivity is essential for the economic feasibility of many lignin-valorization strategies within integrated biorefining processes. Importantly, the quality and properties of the lignin source play an essential role in impacting the...

Dissolution of lignin in green urea aqueous solution

NASA Astrophysics Data System (ADS)

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paul, Ryan; Naskar, Amit; Gallego, Nidia

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

Preparation and Characterization of Modified Soda Lignin with Polyethylene Glycol

PubMed Central

Zhang, Fangda; Lin, Jian; Zhao, Guangjie

2016-01-01

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. PMID:28773943

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

PubMed Central

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

2016-01-01

ABSTRACT Lignin is 1 of the 3 major components of lignocellulose. Its polymeric structure includes aromatic subunits that can be converted into high-value-added products, but this potential cannot yet been fully exploited because lignin is highly recalcitrant to degradation. Different approaches for the depolymerization of lignin have been tested, including pyrolysis, chemical oxidation, and hydrolysis under supercritical conditions. An additional strategy is the use of lignin-degrading enzymes, which imitates the natural degradation process. A versatile set of enzymes for lignin degradation has been identified, and research has focused on the production of recombinant enzymes in sufficient amounts to characterize their structure and reaction mechanisms. Enzymes have been analyzed individually and in combinations using artificial substrates, lignin model compounds, lignin and lignocellulose. Here we consider progress in the production of recombinant lignin-degrading peroxidases, the advantages and disadvantages of different expression hosts, and obstacles that must be overcome before such enzymes can be characterized and used for the industrial processing of lignin. PMID:27295524

Chapter 1: A Brief Introduction to Lignin Structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katahira, Rui; Beckham, Gregg T; Elder, Thomas J.

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

Unraveling the Structural Modifications in Lignin of Arundo donax Linn. during Acid-Enhanced Ionic Liquid Pretreatment.

PubMed

You, Tingting; Zhang, Liming; Guo, Siqin; Shao, Lupeng; Xu, Feng

2015-12-23

Solid acid-enhanced ionic liquid (IL) pretreatment is of paramount importance for boosting the yield of sugars from biomass cost-effectively and environmentally friendly. To unravel the chemical and supramolecular structural changes of lignin after pretreatment, IL-acid lignin (ILAL) and subsequent residual cellulolytic enzyme lignin (RCEL) were isolated from Arundo donax Linn. The structural features were compared with those of the corresponding milled wood lignin (MWL). Results indicated that the pretreatment caused loss of β-O-4', β-β', β-1' linkages and formation of condensed structures in lignin. A preferential breakdown of G-type lignin may have occurred, evidenced by an increased S/G ratio revealed by 2D HSQC NMR analysis. It was determined that the depolymerization of β-O-4' linkage, lignin recondensation, and cleavage of ferulate-lignin ether linkages took place. Moreover, a simulation module was first developed to define morphological changes in lignin based on AFM and TEM analyses. Briefly, tree branch like aggregates was destroyed to monodisperse particles.

Tropospheric ozone effects on chemical composition and decomposition rate of Quercus ilex L. leaves.

PubMed

Baldantoni, Daniela; Fagnano, Massimo; Alfani, Anna

2011-02-01

We determined the effects of tropospheric ozone on the chemical composition of Quercus ilex L. leaves and their decomposition, with a view to assessing the influence of ozone on nutrient cycling and the sustainability of Mediterranean holm oak forests. Forming one of the most widespread thermophilous vegetation communities in the area, Q. ilex is a dominant and widespread evergreen oak in the Mediterranean, where concentrations of tropospheric ozone are particularly high. The dynamics of carbon, nitrogen, lignin and cellulose concentrations were monitored for six months during the decomposition of leaves from plants subjected to controlled ozone exposure in open-top chambers. Ozone-exposed leaves, compared to unexposed leaves, showed no significant differences in C, N, lignin and cellulose concentrations prior to the incubation in mesocosms. However, during decomposition, leaves from plants exposed to ozone lost C significantly more slowly and showed a higher C/N ratio than unexposed leaves. Ozone exposure significantly slowed down the decomposition rate, indicating a negative effect of tropospheric ozone on nutrient cycling, which may reduce long-term sustainability of the holm oak forest. Copyright © 2010 Elsevier B.V. All rights reserved.

High Titer and Yields Achieved with Novel, Low-Severity Pretreatment Strategy

DOE Office of Scientific and Technical Information (OSTI.GOV)

NREL researchers obtained high concentration sugar syrups in enzymatic hydrolysis that are fermentable to ethanol and other advanced biofuels and intermediate products at high yields. The novel DMR process is simpler and bypasses all severe pretreatment methods, thus reducing the environmental impact. The results are unprecedented. Researchers achieved a high concentration of sugars (230g/L of monomeric sugar and 270 g/L total sugar) and this low toxicity, highly fermentable syrup yielded 86 g/L ethanol (> 90 percent conversion). In addition, the lignin streams from this process can readily be converted to jet or renewable diesel blendstocks through a hydrodeoxygenation step. Themore » NREL-developed, low severity DMR process may potentially replace higher severity chemical pretreatments and associated expensive reactors constructed of exotic alloys with a simpler process, using commercial-scale equipment commonly associated with the pulp and paper industry, to produce high concentration, low toxicity sugar streams and highly reactive lignin streams from non-food renewable biomass for biological and catalytic upgrading to advanced biofuels and chemicals. The simpler DMR process with black liquor recycling could reduce environmental and life-cycle impacts, and repurpose shuttered pulp and paper mills to help revitalize rural economies.« less

Discovery of 12-mer peptides that bind to wood lignin

PubMed Central

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

2016-01-01

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

Quantitative analysis of detailed lignin monomer composition by pyrolysis-gas chromatography combined with preliminary acetylation of the samples.

PubMed

Sonoda, T; Ona, T; Yokoi, H; Ishida, Y; Ohtani, H; Tsuge, S

2001-11-15

Detailed quantitative analysis of lignin monomer composition comprising p-coumaryl, coniferyl, and sinapyl alcohol and p-coumaraldehyde, coniferaldehyde, and sinapaldehyde in plant has not been studied from every point mainly because of artifact formation during the lignin isolation procedure, partial loss of the lignin components inherent in the chemical degradative methods, and difficulty in the explanation of the complex spectra generally observed for the lignin components. Here we propose a new method to quantify lignin monomer composition in detail by pyrolysis-gas chromatography (Py-GC) using acetylated lignin samples. The lignin acetylation procedure would contribute to prevent secondary formation of cinnamaldehydes from the corresponding alcohol forms during pyrolysis, which are otherwise unavoidable in conventional Py-GC process to some extent. On the basis of the characteristic peaks on the pyrograms of the acetylated sample, lignin monomer compositions in various dehydrogenative polymers (DHP) as lignin model compounds were determined, taking even minor components such as cinnamaldehydes into consideration. The observed compositions by Py-GC were in good agreement with the supplied lignin monomer contents on DHP synthesis. The new Py-GC method combined with sample preacetylation allowed us an accurate quantitative analysis of detailed lignin monomer composition using a microgram order of extractive-free plant samples.

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

PubMed

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

2017-06-01

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

Enzymatic Processes to Unlock the Lignin Value

PubMed Central

Hämäläinen, Veera; Grönroos, Toni; Suonpää, Anu; Heikkilä, Matti Wilhem; Romein, Bastiaan; Ihalainen, Petri; Malandra, Sara; Birikh, Klara R.

2018-01-01

Main hurdles of lignin valorization are its diverse chemical composition, recalcitrance, and poor solubility due to high-molecular weight and branched structure. Controlled fragmentation of lignin could lead to its use in higher value products such as binders, coatings, fillers, etc. Oxidative enzymes (i.e., laccases and peroxidases) have long been proposed as a potentially promising tool in lignin depolymerization. However, their application was limited to ambient pH, where lignin is poorly soluble in water. A Finnish biotechnology company, MetGen Oy, that designs and supplies industrial enzymes, has developed and brought to market several lignin oxidizing enzymes, including an extremely alkaline lignin oxidase MetZyme® LIGNO™, a genetically engineered laccase of bacterial origin. This enzyme can function at pH values as high as 10–11 and at elevated temperatures, addressing lignin at its soluble state. In this article, main characteristics of this enzyme as well as its action on bulk lignin coming from an industrial process are demonstrated. Lignin modification by MetZyme® LIGNO™ was characterized by size exclusion chromatography, UV spectroscopy, and dynamic light scattering for monitoring particle size of solubilized lignin. Under highly alkaline conditions, laccase treatment not only decreased molecular weight of lignin but also increased its solubility in water and altered its dispersion properties. Importantly, organic solvent-free soluble lignin fragmentation allowed for robust industrially relevant membrane separation technologies to be applicable for product fractionation. These enzyme-based solutions open new opportunities for biorefinery lignin valorization thus paving the way for economically viable biorefinery business. PMID:29623274

Characterization of Lignin Streams during Bionic Liquid-Based Pretreatment from Grass, Hardwood, and Softwood

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Tanmoy; Papa, Gabriella; Wang, Eileen

Delignification as a function of ionic liquid (IL) pretreatment has potential in terms of recovering and converting the fractionated lignin streams to renewable products. Renewable biogenic ionic liquids, or bionic liquids (eg. cholinium lysinate, ([Ch][Lys])), provide opportunities in terms of effective, economic and sustainable lignocellulosic biomass pretreatment. We have evaluated [Ch][Lys] pretreatment in terms of sugar and lignin yields for three different feedstocks: switchgrass, eucalyptus, and pine. Four lignin streams isolated during [Ch][Lys] pretreatment and enzymatic hydrolysis were comprehensively analyzed, tracking their changes in physical-chemical structures. We observed changes in major lignin linkages and lignin aromatics units (p-hydroxyphenyl (H), guaiacylmore » (G), and syringil (S)) that occurred during pretreatment. A compositional analysis of the different process streams and a comprehensive mass balance in conjunction with multiple analytical techniques (Nuclear Magnetic Resonance (NMR), Mass Spectroscopy, Fourier Transform Infrared Spectroscopy (FT-IR), Gel Permeation Chromatography (GPC)) is presented. Qualitative and quantitative analyses indicates that there are significantly more lignin-carbohydrate interactions for G-rich lignin in pine. The lignin removal and extent of lignin depolymerization for switchgrass and eucalyptus were higher than pine, and follows the order of switchgrass > eucalyptus > pine. The recovered lignin from pretreated liquid contained a lower relative amount of carbohydrate signals than raw biomass, indicating a high degree of dissociation of lignin carbohydrate complex (LCC) linkages for all samples analyzed. The insights gained from this work contribute to better understanding of physiochemical properties of lignin streams generated during [Ch][Lys] pretreatment, offering a starting point for lignin valorization strategies.« less

Comparative bacterial degradation and detoxification of model and kraft lignin from pulp paper wastewater and its metabolites

NASA Astrophysics Data System (ADS)

Abhishek, Amar; Dwivedi, Ashish; Tandan, Neeraj; Kumar, Urwashi

2017-05-01

Continuous discharge of lignin containing colored wastewater from pulp paper mill into the environment has resulted in building up their high level in various aquatic systems. In this study, the chemical texture of kraft lignin in terms of pollution parameters (COD, TOC, BOD, etc.) was quite different and approximately twofold higher as compared to model lignin at same optical density (OD 3.7 at 465 nm) and lignin content (2000 mg/L). For comparative bacterial degradation and detoxification of model and kraft lignin two bacteria Citrobacter freundii and Serratia marcescens were isolated, screened and applied in axenic and mixed condition. Bacterial mixed culture was found to decolorize 87 and 70 % model and kraft lignin (2000 mg/L), respectively; whereas, axenic culture Citrobacter freundii and Serratia marcescens decolorized 64, 60 % model and 50, 55 % kraft lignin, respectively, at optimized condition (34 °C, pH 8.2, 140 rpm). In addition, the mixed bacterial culture also showed the removal of 76, 61 % TOC; 80, 67 % COD and 87, 65 % lignin from model and kraft lignin, respectively. High pollution parameters (like TOC, COD, BOD, sulphate) and toxic chemicals slow down the degradation of kraft lignin as compared to model lignin. The comparative GC-MS analysis has suggested that the interspecies collaboration, i.e., each bacterial strain in culture medium has cumulative enhancing effect on growth, and degradation of lignin rather than inhibition. Furthermore, toxicity evaluation on human keratinocyte cell line after bacterial treatment has supported the degradation and detoxification of model and kraft lignin.

Nonimaging light concentration using total internal reflection films.

PubMed

Ouellette, G; Waltham, C E; Drees, R M; Poon, A; Schubank, R; Whitehead, L A

1992-05-01

We present a method of fabricating nonimaging light concentrators from total internal reflection film. A prototype has been made and tested and found to operate in agreement with predictions of ray-tracing codes. The performance of the prototype is comparable with that of concentrators made from specular reflecting materials.

Cellobiose Dehydrogenase Inhibition of Polymerization of Phenolic Compounds and Enhancing Lignin Degradation by Lignina.

PubMed

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.

Lignin-degrading Peroxidases from Genome of Selective Ligninolytic Fungus Ceriporiopsis subverispora

Treesearch

Elena Fernandez-Fueyo; Francisco J. Ruiz-Duenas; Yuta Miki; Marta Jesus Martinez; Kenneth E. Hammel; Angel T. Martinez

2012-01-01

Background: The first genome of a selective lignin degrader is available. Results: Its screening shows 26 peroxidase genes, and 5 genes were heterologously expressed and the catalytic properties investigated. Conclusion: Two new peroxidases oxidize simple and dimeric lignin models and efficiently depolymerize lignin. Significance: Although lignin peroxidase and...

Techniques for characterizing lignin

Treesearch

Nicole M. Stark; Daniel J. Yelle; Umesh P. Agarwal

2016-01-01

Many techniques are available to characterize lignin. The techniques presented in this chapter are considered nondegradative, which are commonly applied to lignin. A brief discussion of lignin structure is included with this chapter to aid the reader in understanding why the discussed characterization techniques are appropriate for the study of lignin. Because the...

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

PubMed

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.

Adsorption of cellobiohydrolases I onto lignin fractions from dilute acid pretreated Broussonetia papyrifera

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Lan; Yang, Haitao; Yoo, Chang Geun

Broussonetia papyrifera, known as paper mulberry, is a potential feed stock for bioethanol production because of its cellulose-rich composition. Lignin in dilute acid pretreated Broussonetia papyrifera was fractionated to three different fractions, and their physiochemical properties were determined by FT-IR, GPC and NMR analyses. Different structural characteristics were observed from each lignin fraction. Cellobiohydrolases I (CBH) adsorption to each lignin was understood by the lignin properties. The results showed that aliphatic hydroxyl groups in lignin showed positive correlations with the maximum binding ability of CBH onto lignin samples. Also, the contents of phenolic compounds such as p-hydroxyphenyl benzoate (PB), syringylmore » (S) and guaiacyl (G) units in the lignin influenced their CBH binding.« less

Adsorption of cellobiohydrolases I onto lignin fractions from dilute acid pretreated Broussonetia papyrifera

DOE PAGES

Yao, Lan; Yang, Haitao; Yoo, Chang Geun; ...

2017-11-01

Broussonetia papyrifera, known as paper mulberry, is a potential feed stock for bioethanol production because of its cellulose-rich composition. Lignin in dilute acid pretreated Broussonetia papyrifera was fractionated to three different fractions, and their physiochemical properties were determined by FT-IR, GPC and NMR analyses. Different structural characteristics were observed from each lignin fraction. Cellobiohydrolases I (CBH) adsorption to each lignin was understood by the lignin properties. The results showed that aliphatic hydroxyl groups in lignin showed positive correlations with the maximum binding ability of CBH onto lignin samples. Also, the contents of phenolic compounds such as p-hydroxyphenyl benzoate (PB), syringylmore » (S) and guaiacyl (G) units in the lignin influenced their CBH binding.« less

Lignin biodegradation by the ascomycete Chrysonilia sitophila.

PubMed

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

1997-01-01

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

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

PubMed

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.

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

DOEpatents

Schroeder, Herbert A.

1991-01-01

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

Comparative study of organosolv lignin extracted from prairie cordgrass, switchgrass and corn stover.

PubMed

Cybulska, Iwona; Brudecki, Grzegorz; Rosentrater, Kurt; Julson, James L; Lei, Hanwu

2012-08-01

Lignin extracted from prairie cordgrass, switchgrass, and corn stover (using ethyl acetate-ethanol-water organosolv pretreatment) was analyzed and characterized using several methods. These methods included analysis of purity (by determination of Klason lignin, carbohydrate, and ash contents), solubility (with several organic solvents), phenolic group analysis (ultraviolet ionization difference spectra, and nitrobenzene oxidation), and general functional group analysis (by (1)H NMR). Results showed that all the examined lignin samples were relatively pure (contained over 50% Klason lignin, less than 5% carbohydrate contamination, and less than 3% ash), but switchgrass-derived lignin was observed to be the purest. All the lignins were found to contain high amounts of phenolic groups, while switchgrass-derived lignin was the most phenolic, according to the ionization difference spectra. Nitrobenzene oxidation revealed that all the lignin samples contained available guaiacyl units in high amounts. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

DOEpatents

Schroeder, Herbert A.

1991-01-01

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

Lignin and veratryl alcohol are not inducers of the ligninolytic system of Phanerochaete chrysosporium.

PubMed Central

Cancel, A M; Orth, A B; Tien, M

1993-01-01

Phanerochaete chrysosporium is a white rot fungus which secretes a family of lignin-degrading enzymes under nutrient limitation. In this work, we investigated the roles of veratryl alcohol and lignin in the ligninolytic system of P. chrysosporium BKM-F-1767 cultures grown under nitrogen-limited conditions. Cultures supplemented with 0.4 to 2 mM veratryl alcohol showed increased lignin peroxidase activity. Addition of veratryl alcohol had no effect on Mn-dependent peroxidase activity and inhibited glyoxal oxidase activity. Azure-casein analysis of acidic proteases in the extracellular fluid showed that protease activity decreased during the early stages of secondary metabolism while lignin peroxidase activity was at its peak, suggesting that proteolysis was not involved in the regulation of lignin peroxidase activity during early secondary metabolism. In cultures supplemented with lignin or veratryl alcohol, no induction of mRNA coding for lignin peroxidase H2 or H8 was observed. Veratryl alcohol protected lignin peroxidase isozymes H2 and H8 from inactivation by H2O2. We conclude that veratryl alcohol acts as a stabilizer of lignin peroxidase activity and not as an inducer of lignin peroxidase synthesis. Images PMID:8215363

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

PubMed

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

2016-07-25

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Ruoshui; Guo, Mond; Lin, Kuan-ting

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) includingmore » 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.« less

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2013-01-01

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

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

NASA Astrophysics Data System (ADS)

Hall, S. J.; Hammel, K.

2017-12-01

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

The role of condensed tannins in the nutritional value of Lotus pedunculatus for sheep. 4. Sites of carbohydrate and protein digestion as influenced by dietary reactive tannin concentration.

PubMed

Barry, T N; Manley, T R; Duncan, S J

1986-01-01

1. Vegetative secondary growth Lotus pedunculatus was cut daily, and fed fresh at hourly intervals (600 g dry matter (DM)/d) to three groups each of three sheep fitted with permanent cannulas into the rumen and duodenum. Lotus fed to two of the groups was sprayed with low and high rates of polyethylene glycol (PEG; molecular weight 3350), which specifically binds the condensed tannins (CT). Nutrient intake and faecal excretion were measured directly, duodenal flows estimated from continuous intraruminal infusion of inert ruthenium phenanthroline (Ru-P) and CrEDTA markers, and rumen pool sizes measured at slaughter. 2. Dietary concentrations of total reactive CT (i.e. that not bound to PEG) were 95, 45 and 14 g/kg DM, whilst the corresponding values for free CT were 15, 5 and 2 g/kg DM. 3. Increasing dietary reactive CT concentration linearly increased duodenal flows of non-ammonia nitrogen, but linearly decreased the apparent digestibility of energy and organic matter, and rumen digestion of hemicellulose but not of cellulose. Rumen digestion as a proportion of total digestion was increased by the higher PEG rate for organic matter, energy, pectin and lignin. 4. High dietary CT concentration was associated with increased N retention. Rumen ammonia concentration and pool size showed only a slight decline on this diet, indicating that there must have been increased recycling of N into the rumen. 5. Increasing dietary reactive CT concentration had no effect on the rate at which carbohydrate constituents were degraded in the rumen per unit time (FDR), but increased the rate at which their undegraded residues (FOR) left the rumen per unit time. The latter appeared to be the principal mechanism by which rumen digestion as a proportion of total digestion was reduced at high dietary CT concentrations. From a comparison of FDR and FOR of carbohydrate components in lotus and Brassica oleracea diets, it was concluded that hemicellulose digestion was rate-limiting for rumen cell-wall digestion, probably due to bonding with lignin. However, the considerable post-rumen digestion of hemicellulose was not associated with post-rumen lignin digestion. 6. It was concluded that a desired concentration of CT in Lotus sp. should represent a balance between the positive effect of CT in improving the efficiency of N digestion and their negative effect in depressing rumen carbohydrate digestion. A recommended concentration is 30-40 g/kg DM.

Quantitative and Qualitative Prediction of Light Absorption by Colored Dissolved Organic Matter in the Coastal Zone

DTIC Science & Technology

2006-09-30

photochemical reactivity of CDOM, affecting its concentration and characteristics. The sampling strategy is coordinated with the Danish National...and DOP), stable isotopic composition of DOM, and lignin content (Osburn et al 2001). (Responsible project partner: NRL) This work package will

Lignin Sensor Based On Flash-Pyrolysis Mass Spectrometry

NASA Technical Reports Server (NTRS)

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

1990-01-01

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

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

PubMed

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

2016-07-20

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

Raman spectra of lignin model compounds

Treesearch

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

2005-01-01

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

Carboxymethylated lignins with low surface tension toward low viscosity and highly stable emulsions of crude bitumen and refined oils.

PubMed

Li, Shuai; Ogunkoya, Dolanimi; Fang, Tiegang; Willoughby, Julie; Rojas, Orlando J

2016-11-15

Kraft and organosolv lignins were subjected to carboxymethylation to produce fractions that were soluble in water, displayed a minimum surface tension as low as 34mN/m (25°C) and a critical aggregation concentration of ∼1.5wt%. The carboxymethylated lignins (CML), which were characterized in terms of their degree of substitution ((31)P NMR), elemental composition, and molecular weight (GPC), were found suitable in the formulation of emulsions with bitumens of ultra-high viscosity, such as those from the Canadian oil sands. Remarkably, the interfacial features of the CML enabled fuel emulsions that were synthesized in a very broad range of internal phase content (30-70%). Cryo-replica transmission electron microscopy, which was used here the first time to assess the morphology of the lignin-based emulsions, revealed the droplets of the emulsion stabilized with the modified lignin. The observed drop size (diameters<2μm) was confirmed by light scattering, which revealed a normal size distribution. Such characteristics led to stable emulsified systems that are amenable for a wide range of applications. Emulsification with CML afforded bitumen emulsions with very high colloidal stability (no change was noted for over one month) and with a strong shear thinning behavior. Both features indicate excellent prospects for storage, transport and spraying, which are relevant in operations for power generation, which also take advantage of the high heating value of the emulsion components. The ability of CML to stabilize emulsions and to contribute in their combustion was tested with light fuels (kerosene, diesel, and jet fuel) after formulation of high internal phase systems (70% oil) that enabled operation of a fuel engine. A significant finding is that under certain conditions and compared to the respective pure fuel, combustion of the O/W emulsions stabilized by CML presented lower NOx and CO emissions and maintained a relatively high combustion efficiency. The results highlight the possibilities in high volume application for lignin biomacromolecules. Copyright © 2016 Elsevier Inc. All rights reserved.

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

DOE PAGES

Yao, Lan; Yang, Haitao; Yoo, Chang Geun; ...

2018-02-06

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 acidmore » (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.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Lan; Yang, Haitao; Yoo, Chang Geun

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 acidmore » (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.« less

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

NASA Astrophysics Data System (ADS)

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

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

Selective electrochemical detection of 2,4,6-trinitrotoluene (TNT) in water based on poly(styrene-co-acrylic acid) PSA/SiO2/Fe3O4/AuNPs/lignin-modified glassy carbon electrode.

PubMed

Mahmoud, Khaled A; Abdel-Wahab, Ahmed; Zourob, Mohammed

2015-01-01

A new versatile electrochemical sensor based on poly(styrene-co-acrylic acid) PSA/SiO2/Fe3O4/AuNPs/lignin (L-MMS) modified glassy carbon electrode (GCE) was developed for the selective detection of trace trinitrotoluene (TNT) from aqueous media with high sensitivity. The fabricated magnetic microspheres were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). L-MMS films were cast on the GCE surface to fabricate the TNT sensing electrode. The limit of detection (LOD) of TNT determined by the amperometric i-t curve reached 35 pM. The lignin film and well packed Fe3O4/AuNPs facilitated the pre-concentration of trace TNT on the electrode surface resulting in a fast amperometric response of 3 seconds near the detection limit. The high sensitivity and excellent catalytic activity of the modified electrode could be attributed to the lignin layer and highly packed Fe3O4/AuNPs on the electrode surface. The total recovery of TNT from tapwater and seawater matrices was 98% and 96%, respectively. The electrode film was highly stable after five repeated adsorption/desorption cycles. The new electrochemical sensing scheme provides a highly selective, sensitive and versatile assay for the in-situ detection of TNT in complex water media.

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

PubMed

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.

Phenolic compounds in ectomycorrhizal interaction of lignin modified silver birch

PubMed Central

Sutela, Suvi; Niemi, Karoliina; Edesi, Jaanika; Laakso, Tapio; Saranpää, Pekka; Vuosku, Jaana; Mäkelä, Riina; Tiimonen, Heidi; Chiang, Vincent L; Koskimäki, Janne; Suorsa, Marja; Julkunen-Tiitto, Riitta; Häggman, Hely

2009-01-01

Background The monolignol biosynthetic pathway interconnects with the biosynthesis of other secondary phenolic metabolites, such as cinnamic acid derivatives, flavonoids and condensed tannins. The objective of this study is to evaluate whether genetic modification of the monolignol pathway in silver birch (Betula pendula Roth.) would alter the metabolism of these phenolic compounds and how such alterations, if exist, would affect the ectomycorrhizal symbiosis. Results Silver birch lines expressing quaking aspen (Populus tremuloides L.) caffeate/5-hydroxyferulate O-methyltransferase (PtCOMT) under the 35S cauliflower mosaic virus (CaMV) promoter showed a reduction in the relative expression of a putative silver birch COMT (BpCOMT) gene and, consequently, a decrease in the lignin syringyl/guaiacyl composition ratio. Alterations were also detected in concentrations of certain phenolic compounds. All PtCOMT silver birch lines produced normal ectomycorrhizas with the ectomycorrhizal fungus Paxillus involutus (Batsch: Fr.), and the formation of symbiosis enhanced the growth of the transgenic plants. Conclusion The down-regulation of BpCOMT in the 35S-PtCOMT lines caused a reduction in the syringyl/guaiacyl ratio of lignin, but no significant effect was seen in the composition or quantity of phenolic compounds that would have been caused by the expression of PtCOMT under the 35S or UbB1 promoter. Moreover, the detected alterations in the composition of lignin and secondary phenolic compounds had no effect on the interaction between silver birch and P. involutus. PMID:19788757

Genetic Linkage of Soil Carbon Pools and Microbial Functions in Subtropical Freshwater Wetlands in Response to Experimental Warming

PubMed Central

Wang, Hang; He, Zhili; Lu, Zhenmei; Zhou, Jizhong; Van Nostrand, Joy D.; Xu, Xinhua

2012-01-01

Rising climate temperatures in the future are predicted to accelerate the microbial decomposition of soil organic matter. A field microcosm experiment was carried out to examine the impact of soil warming in freshwater wetlands on different organic carbon (C) pools and associated microbial functional responses. GeoChip 4.0, a functional gene microarray, was used to determine microbial gene diversity and functional potential for C degradation. Experimental warming significantly increased soil pore water dissolved organic C and phosphorus (P) concentrations, leading to a higher potential for C emission and P export. Such losses of total organic C stored in soil could be traced back to the decomposition of recalcitrant organic C. Warming preferentially stimulated genes for degrading recalcitrant C over labile C. This was especially true for genes encoding cellobiase and mnp for cellulose and lignin degradation, respectively. We confirmed this with warming-enhanced polyphenol oxidase and peroxidase activities for recalcitrant C acquisition and greater increases in recalcitrant C use efficiency than in labile C use efficiency (average percentage increases of 48% versus 28%, respectively). The relative abundance of lignin-degrading genes increased by 15% under warming; meanwhile, soil fungi, as the primary decomposers of lignin, were greater in abundance by 27%. This work suggests that future warming may enhance the potential for accelerated fungal decomposition of lignin-like compounds, leading to greater microbially mediated C losses than previously estimated in freshwater wetlands. PMID:22923398

Alternative oxidase (AOX) and phenolic metabolism in methyl jasmonate-treated hairy root cultures of Daucus carota L.

PubMed

Sircar, Debabrata; Cardoso, Hélia G; Mukherjee, Chiranjit; Mitra, Adinpunya; Arnholdt-Schmitt, Birgit

2012-05-01

Methyl-jasmonate (MJ)-treated hairy roots of Daucus carota L. were used to study the influence of alternative oxidase (AOX) in phenylpropanoid metabolism. Phenolic acid accumulation, as well as total flavonoids and lignin content of the MJ-treated hairy roots were decreased by treatment with salicylhydroxamic acid (SHAM), a known inhibitor of AOX. The inhibitory effect of SHAM was concentration dependent. Treatment with propyl gallate (PG), another inhibitor of AOX, also had a similar inhibitory effect on accumulation of phenolic acid, total flavonoids and lignin. The transcript levels of two DcAOX genes (DcAOX2a and DcAOX1a) were monitored at selected post-elicitation time points. A notable rise in the transcript levels of both DcAOX genes was observed preceding the MJ-induced enhanced accumulation of phenolics, flavonoids and lignin. An appreciable increase in phenylalanine ammonia-lyase (PAL) transcript level was also observed prior to enhanced phenolics accumulation. Both DcAOX genes showed differential transcript accumulation patterns after the onset of elicitation. The transcript levels of DcAOX1a and DcAOX2a attained peak at 6hours post elicitation (hpe) and 12hpe, respectively. An increase in the transcript levels of both DcAOX genes preceding the accumulation of phenylpropanoid-derivatives and lignin showed a positive correlation between AOX activity and phenylpropanoid biosynthesis. The results provide important new insight about the influence of AOX in phenylpropanoid biosynthesis. Copyright © 2012 Elsevier GmbH. All rights reserved.

Ozone delignification of pine and eucalyptus kraft pulps. 2: Selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simoes, R.M.S.; Castro, J.A.A.M.

1999-12-01

The selectivity of ozone in the delignification of unbleached pine and eucalyptus kraft pulps is studied at ultralow consistency in a stirred reactor under closely controlled experimental conditions. The effect of several operating variables is analyzed, but special attention is paid to the depolymerization rate of polysaccharides with the particular goal of evaluating the influence of the lignin contents on its kinetics. By using substantially different ozone concentrations in the pulp suspension and different reaction temperatures, it is possible to show that ozone selectivity can only be slightly improved by manipulating these operating variables. Furthermore, for the same type ofmore » material, it was observed that the initial rate of delignification plays the most important role on selectivity. In fact, for a given pulp, selectivity decreases with a decrease of the initial lignin contents, and such results can be well justified by the corresponding reduction of the initial rates of delignification. To further investigate the effect of lignin on pulp degradation, experiments were carried out at 4 C between ozone and holocellulose, which represent the polysaccharides of the unbleached pulps. The results suggest that molecular ozone can be responsible for an important part of the polysaccharides depolymerization during the delignification process. Moreover, the comparison of the kinetic behavior of holocellulose and of the corresponding unbleached pulp also reveals that the presence of lignin in the pulp enhances both the depolymerization and the degradation rates of polysaccharides.« less

Contribution of species-specific chemical signatures to soil organic matter in Kohala, HI.

NASA Astrophysics Data System (ADS)

Stewart, C. E.; Amatangelo, K.; Neff, J. C.

2008-12-01

Soil organic matter (SOM) inherits much of its chemical structure from the dominant vegetation, including phenolic (lignin-derived), aromatic, and aliphatic (cutin and wax-derived) compounds. The Hawaiian fern species Dicranopteris decomposes more slowly than the angiosperm, Cheirodendron due to high concentrations of recalcitrant C compounds. These aliphatic fern leaf waxes are well-preserved and may comprise a large portion of the recalcitrant organic matter in these soils. Our objective was to determine the chemical signature of fern and angiosperm vegetation types and trace the preservation or loss of those compounds into the soil. We collected live tissue, litter, roots, and soil (<53 μm) from five dominant vegetation types including two angiosperms Cheirodendron and Metrosideros, two basal ferns Dicranopteris and Cibotium and a polypod fern Diplazium in Kohala, HI. We characterized them via TMAH-pyrolysis-gas chromatography-mass spectrometry. We found distinct chemical differences between angiosperm and fern vegetation; angiosperm contained more G- and S-derived lignin structures and the fern species contained greater relative abundances of P-derived lignin and tannin-derivatives. There was a general decrease of lignin-derived phenolic compounds from live to litter to soils and an increase in more recalcitrant, aromatic and aliphatic C. Recalcitrant fern-derived cutin and leaf waxes (alkene and alkanes structures) were evident in the soils, but clear species differences were not observed. Although ferns contain distinct lipid and wax-derived compounds, soils developed under fern do not appear to accumulate these compounds in SOM.

Ultrasound-assisted extraction and characterization of hydrolytic and oxidative enzymes produced by solid state fermentation.

PubMed

Szabo, Orsolya Erzsebet; Csiszar, Emilia; Toth, Karolina; Szakacs, George; Koczka, Bela

2015-01-01

Ligninolytic and hydrolytic enzymes were produced with six selected fungi on flax substrate by solid state fermentation (SSF). The extracellular enzyme production of the organisms in two SSF media was evaluated by measuring the soluble protein concentration and the filter paper, endoxylanase, 1,4-β-d-glucosidase, 1,4-β-d-endoglucanase, polygalacturonase, lignin peroxidase, manganese peroxidase and laccase activities of the clear culture solutions produced by conventional extraction from the SSF materials. The SSF material of the best enzyme producer (Trichoderma virens TUB F-498) was further investigated to enhance the enzyme recovery by low frequency ultrasound treatment. Performance of both the original and ultrasound macerated crude enzyme mixtures was evaluated in degradation of the colored lignin-containing and waxy materials of raw linen fabric. Results proved that sonication (at 40%, 60% and 80% amplitudes, for 60min) did not result in reduction in the filter paper, lignin peroxidase and laccase activities of the crude enzyme solution, but has a significant positive effect on the efficiency of enzyme extraction from the SSF material. Depending on the parameters of sonication, the enzyme activities in the extracts obtained can be increased up to 129-413% of the original activities measured in the control extracts recovered by a common magnetic stirrer. Sonication also has an effect on both the enzymatic removal of the lignin-containing color materials and hydrophobic surface layer from the raw linen. Copyright © 2014 Elsevier B.V. All rights reserved.

Difference analysis of the enzymatic hydrolysis performance of acid-catalyzed steam-exploded corn stover before and after washing with water.

PubMed

Zhu, Junjun; Shi, Linli; Zhang, Lingling; Xu, Yong; Yong, Qiang; Ouyang, Jia; Yu, Shiyuan

2016-10-01

The difference in the enzymatic hydrolysis yield of acid-catalyzed steam-exploded corn stover (ASC) before and after washing with water reached approximately 15 % under the same conditions. The reasons for the difference in the yield between ASC and washed ASC (wASC) were determined through the analysis of the composition of ASC prehydrolyzate and sugar concentration of enzymatic hydrolyzate. Salts produced by neutralization (CaSO4, Na2SO4, K2SO4, and (NH4)2SO4), sugars (polysaccharides, oligosaccharides, and monosaccharides), sugar-degradation products (weak acids and furans), and lignin-degradation products (ethyl acetate extracts and nine main lignin-degradation products) were back-added to wASC. Results showed that these products, except furans, exerted negative effect on enzymatic hydrolysis. According to the characteristics of acid-catalyzed steam explosion pretreatment, the five sugar-degradation products' mixture and salts [Na2SO4, (NH4)2SO4] showed minimal negative inhibition effect on enzymatic hydrolysis. By contrast, furans demonstrated a promotion effect. Moreover, soluble sugars, such as 13 g/L xylose (decreased by 6.38 %), 5 g/L cellobiose (5.36 %), 10 g/L glucose (3.67 %), as well as lignin-degradation products, and ethyl acetate extracts (4.87 %), exhibited evident inhibition effect on enzymatic hydrolysis. Therefore, removal of soluble sugars and lignin-degradation products could effectively promote the enzymatic hydrolysis performance.

Lignin depolymerization by fungal secretomes and a microbial sink

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salvachúa, Davinia; Katahira, Rui; Cleveland, Nicholas S.

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

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

PubMed Central

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 themore » 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.« less

Lignin depolymerization by fungal secretomes and a microbial sink

DOE PAGES

Salvachua, Davinia; Katahira, Rui; Cleveland, Nicholas S.; ...

2016-08-25

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

Lignin depolymerization by fungal secretomes and a microbial sink

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salvachua, Davinia; Katahira, Rui; Cleveland, Nicholas S.

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

Lignin-Derived Advanced Carbon Materials

DOE PAGES

Chatterjee, Sabornie; Saito, Tomonori

2015-11-16

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

Lignin-Derived Advanced Carbon Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, Sabornie; Saito, Tomonori

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

Abnormal lignin in a loblolly pine mutant.

PubMed

Ralph, J; MacKay, J J; Hatfield, R D; O'Malley, D M; Whetten, R W; Sederoff, R R

1997-07-11

Novel lignin is formed in a mutant loblolly pine (Pinus taeda L.) severely depleted in cinnamyl alcohol dehydrogenase (E.C. 1.1.1.195), which converts coniferaldehyde to coniferyl alcohol, the primary lignin precursor in pines. Dihydroconiferyl alcohol, a monomer not normally associated with the lignin biosynthetic pathway, is the major component of the mutant's lignin, accounting for approximately 30 percent (versus approximately 3 percent in normal pine) of the units. The level of aldehydes, including new 2-methoxybenzaldehydes, is also increased. The mutant pines grew normally indicating that, even within a species, extensive variations in lignin composition need not disrupt the essential functions of lignin.

Fate and transport of lignin in the soil-water continuum

NASA Astrophysics Data System (ADS)

Williams, J. S.; Dungait, J.; Bol, R.; Abbott, G. D.

2011-12-01

Soils have been identified as having the potential to store greater amounts of carbon (C) in soil organic matter (SOM) through appropriate land uses and management practices to increase the input of recalcitrant components of organic matter, such as lignin. Lignin is allocated to the 'slow' soil C pools with residence times between 15 - 100 yrs. Lignin is 30% of the C fixed by plants and is an important C input to soils. However, Recent research has shown that the configuration of lignin monomers within the lignin macromolecule is not random [1], that lignin degradation is monomer specific [2], and that lignin is preferentially degraded relative to the bulk SOM [3], thereby questioning the role of lignin in C sequestration. Although guaiacyl (G) and syringyl (S) lignin monomers have been identified in fresh, estuarine, and marine waters [4], the initial forms to which lignin is degraded into water-transportable products and lost from the soil C reservoir are not known. The aims of this project are to (i) identify and quantify the lignin-derived products entering the soluble phase in soils, and (ii) determine the rate of lignin degradation into water-soluble components, and their rate of transport through soil. In experiment 1 we tested the best approach to extract and analyse dissolved lignin from outflows from grassland and woodland sites. C18 solid phase extraction (SPE) or freeze-drying (FD) was used to isolate water-borne lignin monomers. Gas chromatography-mass spectrometry (GC-MS) of trimethylsilyl (TMS) derivatives or tetramethylammonium hydroxide (TMAH) thermochemolysis was used to analyse the samples. In a subsequent experiment, we allowed leaves from different vegetation types (Lolium perenne, Ranunculus repens, Fraxinus excelsior, Quercus robur), corresponding to the vegetation at our initial sites in Experiment 1, to degrade in soil lysimeters for 1.5 years to determine the rates of decomposition of different plant material and dominant form of lignin moving into the aqueous phase in each case. Our results showed that C18 silica-based SPE recovered a greater proportion of detectable dissolved lignin than FD both in terms of number of compounds identified as well as total mass of lignin. More lignin-derived compounds were identified using TMAH/GC-MS than GC-MS of TMS derivatives. The lysimeter experiment showed that Ranunculus repens and Lolium perenne decomposition was most rapid and generated the highest leachate TOC values. TMAH/GC/MS analysis identified G, S, and p-hydroxyphenyl (P) units in the vegetation leachates with side-chains ranging from one to three carbons, with varying degrees of oxidation. This research provides new insight into the complexity of lignin breakdown and movement through soils.

Characterization of Trapped Lignin-Degrading Microbes in Tropical Forest Soil

PubMed Central

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

2011-01-01

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. PMID:21559391

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

PubMed

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

2017-12-01

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

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

PubMed

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

2018-02-26

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

Stimulation and inhibition of enzymatic hydrolysis by organosolv lignins as determined by zeta potential and hydrophobicity.

PubMed

Huang, Yang; Sun, Shaolong; Huang, Chen; Yong, Qiang; Elder, Thomas; Tu, Maobing

2017-01-01

Lignin typically inhibits enzymatic hydrolysis of cellulosic biomass, but certain organosolv lignins or lignosulfonates enhance enzymatic hydrolysis. The hydrophobic and electrostatic interactions between lignin and cellulases play critical roles in the enzymatic hydrolysis process. However, how to incorporate these two interactions into the consideration of lignin effects has not been investigated. We examined the physicochemical properties and the structures of ethanol organosolv lignins (EOL) from hardwood and softwood and ascertained the association between lignin properties and their inhibitory and stimulatory effects on enzymatic hydrolysis. The zeta potential and hydrophobicity of EOL lignin samples, isolated from organosolv pretreatment of cottonwood (CW), black willow (BW), aspen (AS), eucalyptus (EH), and loblolly pine (LP), were determined and correlated with their effects on enzymatic hydrolysis of Avicel. EOLs from CW, BW, and AS improved the 72 h hydrolysis yield by 8-12%, while EOLs from EH and LP decreased the 72 h hydrolysis yield by 6 and 16%, respectively. The results showed a strong correlation between the 72 h hydrolysis yield with hydrophobicity and zeta potential. The correlation indicated that the hydrophobicity of EOL had a negative effect and the negative zeta potential of EOL had a positive effect. HSQC NMR spectra showed that β- O -4 linkages in lignin react with ethanol to form an α -ethoxylated β- O -4' substructure (A') during organosolv pretreatment. Considerable amounts of C 2,6 -H 2,6 correlation in p -hydroxybenzoate (PB) units were observed for EOL-CW, EOL-BW, and EOL-AS, but not for EOL-EH and EOL-LP. This study revealed that the effect of lignin on enzymatic hydrolysis is a function of both hydrophobic interactions and electrostatic repulsions. The lignin inhibition is controlled by lignin hydrophobicity and the lignin stimulation is governed by the negative zeta potential. The net effect of lignin depends on the combined influence of hydrophobicity and zeta potential. This study has potential implications in biomass pretreatment for the reduction of lignin inhibition by increasing lignin negative zeta potential and decreasing hydrophobicity.

Lignin-based Phenol-Formaldehyde Resins from Purified CO2 Precipitated Kraft lignin (PCO2KL)

Treesearch

Yao Chen; Charles R. Frihart; Zhiyong Cai; Linda F. Lorenz; Nicole M. Stark

2013-01-01

To investigate the potential for using purified CO2-precipitated Kraft lignin (PCO2KL) with phenol-formaldehyde (PF) for application as an adhesive in plywood production, two lignin replacement procedures were examined to assess lignin’s effect on bond quality. Methylolation and oxidation with hydrogen peroxide (H

Lignin-based Phenol-Formalehyde Resins from Purified CO2 Precipitated Kraft Lignin (PCO2KL)

Treesearch

Yao Chen; Charles R. Frihart; Zhiyong Cai; Linda F. Lorenz; Nicole M. Stark

2013-01-01

To investigate the potential for using purified CO2-precipitated Kraft lignin (PCO2KL) with phenol-formaldehyde (PF) for application as an adhesive in plywood production, two lignin replacement procedures were examined to assess lignin’s effect on bond quality. Methylolation and oxidation with hydrogen peroxide (H

Standardized performance tests of collectors of solar thermal energy: Prototype moderately concentrating grooved collectors

NASA Technical Reports Server (NTRS)

1976-01-01

Prototypes of moderately concentrating grooved collectors were tested with a solar simulator for varying inlet temperature, flux level, and incident angle. Collector performance is correlated in terms of inlet temperature and flux level.

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

PubMed

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

2014-06-18

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

Biodegradation of kraft lignin by newly isolated Klebsiella pneumoniae, Pseudomonas putida, and Ochrobactrum tritici strains.

PubMed

Xu, Zhaoxian; Qin, Ling; Cai, Mufeng; Hua, Wenbo; Jin, Mingjie

2018-05-01

Bacterial systems have drawn an increasing amount of attention on lignin valorization due to their rapid growth and powerful environmental adaptability. In this study, Klebsiella pneumoniae NX-1, Pseudomonas putida NX-1, and Ochrobactrum tritici NX-1 with ligninolytic potential were isolated from leaf mold samples. Their ligninolytic capabilities were determined by measuring (1) the cell growth on kraft lignin as the sole carbon source, (2) the decolorization of kraft lignin and lignin-mimicking dyes, (3) the micro-morphology changes and transformations of chemical groups in kraft lignin, and (4) the ligninolytic enzyme activities of these three isolates. To the best of our knowledge, this is the first report that Ochrobactrum tritici species can depolymerize and metabolize lignin. Moreover, laccase, lignin peroxidase, and Mn-peroxidase showed high activities in P. putida NX-1. Due to their excellent ligninolytic capabilities, these three bacteria are important supplements to ligninolytic bacteria library and could be valuable in lignin valorization.

Enzymatic Synthesis of Lignin-Based Concrete Dispersing Agents.

PubMed

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.

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

PubMed

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.

Lignin dimers: Structures, distribution, and potential geochemical applications

NASA Astrophysics Data System (ADS)

Goñi, Miguel A.; Hedges, John I.

1992-11-01

An extensive suite of thirty lignin-derived phenolic dimers and fourteen additional monomers has been identified among the CuO reaction products of twenty-four different vascular plant tissues. The various lignin dimers are characterized by five different types of linkages between phenolic units, including direct 5,5'-ring-ring bonding, as well as β,1-diketone, α,1-monoketone, α,5-monoketone, and α,2-methyl sidechain-ring couplings. The new lignin-derived monomeric CuO reaction products include vanillyl and syringyl glyoxalic acids and vanillyl phenols with formyl and carboxyl functional groups attached at various ring positions. The distribution of all these novel compounds in twenty-four different vascular plant tissues indicates important differences in the structure and chemical composition of the lignin macromolecule among these sources. The abundances of these compounds in a selected set of sedimentary samples suggest that the lignin dimers and novel lignin monomers can characterize the ultrastructure, sources, and diagenetic state of sedimentary lignin in ways not possible from the routinely utilized lignin monomers alone.

Release of small phenolic compounds from brewer's spent grain and its lignin fractions by human intestinal microbiota in vitro.

PubMed

Aura, Anna-Marja; Niemi, Piritta; Mattila, Ismo; Niemelä, Klaus; Smeds, Annika; Tamminen, Tarja; Faulds, Craig; Buchert, Johanna; Poutanen, Kaisa

2013-10-09

Brewer's spent grain (BSG), the major side-stream from brewing, is rich in protein, lignin, and nonstarch polysaccharides. Lignin is a polyphenolic macromolecule considered resilient toward breakdown and utilization by colon microbiota, although some indications of release of small phenolic components from lignin in animals have been shown. The aim of this study was to investigate if the human intestinal microbiota can release lignans and small phenolic compounds from whole BSG, a lignin-enriched insoluble fraction from BSG and a deferuloylated fraction, in a metabolic in vitro colon model. The formation of short-chain fatty acid (SCFA) was also investigated. More lignin-related monomers and dilignols were detected from the lignin-enriched fraction than from BSG or deferuloylated BSG. SCFA formation was not suppressed by any of the fractions. It was shown that small lignin-like compounds were released from these samples in the in vitro colon model, originating most likely from lignin.

Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics

DOE PAGES

Smith, Micholas Dean; Mostofian, Barmak; Cheng, Xiaolin; ...

2015-10-05

The deconstruction of cellulose is an essential step in the production of ethanol from lignocellulosic biomass. However, the presence of lignin hinders this process. Recently, a novel cosolvent based biomass pretreatment method called CELF (Cosolvent Enhanced Lignocellulosic Fractionation) which employs tetrahydrofuran (THF) in a single phase mixture with water, was found to be highly effective at solubilizing and extracting lignin from lignocellulosic biomass and achieving high yields of fermentable sugars. Here, using all-atom molecular-dynamics simulation, we find that THF preferentially solvates lignin, and in doing so, shifts the equilibrium configurational distribution of the biopolymer from a crumpled globule to coil,more » independent of temperature. Whereas pure water is a bad solvent for lignin, the THF : water cosolvent acts as a "theta" solvent, in which solvent : lignin and lignin : lignin interactions are approximately equivalent in strength. Furthermore, under these conditions, polymers do not aggregate, thus providing a mechanism for the observed lignin solubilization that facilitates unfettered access of celluloytic enzymes to cellulose.« less

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

PubMed

Bi, Ran; Lawoko, Martin; Henriksson, Gunnar

2016-08-01

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

The degradation of wheat straw lignin

NASA Astrophysics Data System (ADS)

Liang, Jiaqi

2017-03-01

Lignin is a kind of formed by polymerization of aromatic alcohol, prices are lower and sources of renewable resources. Using lignin as raw material, through the push to resolve together preparation phenolic high value-added fine chemicals alkanes and aromatic hydrocarbons, such as the high grade biofuels, can partly replace fossil fuels as raw material to the production process, biomass resources is an important part of the comprehensive utilization of effective components. In lignin push solve clustering method, catalytic hydrogenolysis can directly to the lignin into liquid fuels, low oxygen content in the use of biofuels shows great potential. In this paper, through the optimization of the reaction time, reaction temperature, catalyst type and solvent type, dosage of catalyst, etc factors, determines the alcoholysis - hydrogen solution two-step degradation of lignin, the optimal process conditions: lignin alcoholysis under 50% methanol and NaOH catalyst in the solution, the lignin in methanol solution and 50% hydrogen solution under the Pd/C catalyst. In this process, the degradation of lignin yield can reach 42%.

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

PubMed

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

2016-12-16

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

Effect of alkali lignins with different molecular weights from alkali pretreated rice straw hydrolyzate on enzymatic hydrolysis.

PubMed

Li, Yun; Qi, Benkun; Luo, Jianquan; Wan, Yinhua

2016-01-01

This study investigated the effect of alkali lignins with different molecular weights on enzymatic hydrolysis of lignocellulose. Different alkali lignins fractions, which were obtained from cascade ultrafiltration, were added into the dilute acid pretreated (DAP) and alkali pretreated (AP) rice straws respectively during enzymatic hydrolysis. The results showed that the addition of alkali lignins enhanced the hydrolysis and the enhancement for hydrolysis increased with increasing molecular weights of alkali lignins, with maximum enhancement being 28.69% for DAP and 20.05% for AP, respectively. The enhancement was partly attributed to the improved cellulase activity, and filter paper activity increased by 18.03% when adding lignin with highest molecular weight. It was found that the enhancement of enzymatic hydrolysis was correlated with the adsorption affinity of cellulase on alkali lignins, and the difference in surface charge and hydrophobicity of alkali lignins were responsible for the difference in affinity between cellulase and lignins. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Modification of Chitin with Kraft Lignin and Development of New Biosorbents for Removal of Cadmium(II) and Nickel(II) Ions

PubMed Central

Wysokowski, Marcin; Klapiszewski, Łukasz; Moszyński, Dariusz; Bartczak, Przemysław; Szatkowski, Tomasz; Majchrzak, Izabela; Siwińska-Stefańska, Katarzyna; Bazhenov, Vasilii V.; Jesionowski, Teofil

2014-01-01

Novel, functional materials based on chitin of marine origin and lignin were prepared. The synthesized materials were subjected to physicochemical, dispersive-morphological and electrokinetic analysis. The results confirm the effectiveness of the proposed method of synthesis of functional chitin/lignin materials. Mechanism of chitin modification by lignin is based on formation of hydrogen bonds between chitin and lignin. Additionally, the chitin/lignin materials were studied from the perspective of waste water treatment. The synthetic method presented in this work shows an attractive and facile route for producing low-cost chitin/lignin biosorbents with high efficiency of nickel and cadmium adsorption (88.0% and 98.4%, respectively). The discovery of this facile method of synthesis of functional chitin/lignin materials will also have a significant impact on the problematic issue of the utilization of chitinous waste from the seafood industry, as well as lignin by-products from the pulp and paper industry. PMID:24727394

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

PubMed

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chmely, S. C.; McKinney, K. A.; Lawrence, K. R.

2013-01-01

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

Separation and characterization of lignin from bio-ethanol production residue.

PubMed

Guo, Guowan; Li, Shujun; Wang, Lu; Ren, Shixue; Fang, Guizhen

2013-05-01

In order to develop an adequate method to separate lignin from bio-ethanol production residue, solvent extraction was conducted by using benzyl alcohol, dioxane and ethanol. Compared to the conventional alkali-solution and acid-isolation method, benzyl alcohol and dioxane extraction could reach higher lignin yield of 71.55% and 74.14% respectively. FTIR and XRD analysis results indicate that sodium hydroxide solution dissolved most of the lignin in the raw material. However, the low lignin yield by this method may be attributed to the products loss during the complex separation process. GPC and (1)H NMR results revealed that the dioxane-lignin had closer molecular weight with alkali-lignin, lower S/G ratio (0.22) and higher OHPh/OHAl ratio (0.45) with respect to benzyl alcohol-lignin. The results divulge that the lignin products separated from bio-ethanol production residue by dioxane extraction had fairly potential application with better chemical activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Investigation on the structural effect of lignin during the hydrogenolysis process.

PubMed

Shu, Riyang; Long, Jinxing; Xu, Ying; Ma, Longlong; Zhang, Qi; Wang, Tiejun; Wang, Chenguang; Yuan, Zhengqiu; Wu, Qingyun

2016-01-01

Structure has a significant effect on the lignin degradation, so the investigation of structural effect on the lignin depolymerization is important and imperative. In this study, hydrogenolysis of three typical lignins with different structures, dealkaline lignin, sodium lignosulfonate and organosolv lignin, was intensively compared over the synergistic catalyst of CrCl3 and Pd/C. The effects of reaction temperature, time, hydrogen pressure and catalyst dosage on the catalytic performance of lignin species were investigated. The structure evolution of lignins during the hydrogenolysis process was also compared. The results showed that organosolv lignin was more sensitive for hydrogenolysis than others due to its high unsaturation degree and low molecular weight. Further analysis indicated that the hydrogenolysis, hydrodeoxygenation and repolymerization reactions took place and competed intensely. Wherein, the depolymerization products with unsaturated carbonyl groups were prone to repolymerize. And the methylation was helpful to stabilize the depolymerization products and suppress the further repolymerization. Copyright © 2015 Elsevier Ltd. All rights reserved.

Degradation of Lignin by Cyathus Species

PubMed Central

Abbott, Thomas P.; Wicklow, Donald T.

1984-01-01

The ability of 12 Cyathus species to degrade 14C-labeled lignin in kenaf was studied. The sum of 14C released into solution plus 14C released into the gas phase over a 32-day fermentation period was used to determine average daily rates of lignin biodegradation. Cyathus pallidus. C. africanus, and C. berkeleyanus delignified kenaf most rapidly. C. canna showed the greatest preference for lignin degradation over other plant components, and its rate of lignin degradation was only slightly lower than the three most active species. The apparent ability of fungi to metabolize low-molecular-weight lignin breakdown products correlated well with their overall delignification rates. C. stercoreus metabolized degradation products of lignin from wheat straw better than those from kenaf lignin, based on the amount of low-molecular-weight products left in solution. PMID:16346497

Modeling Lignin Polymerization. I. Simulation Model of Dehydrogenation Polymers1[OA

PubMed Central

van Parijs, Frederik R.D.; Morreel, Kris; Ralph, John; Boerjan, Wout; Merks, Roeland M.H.

2010-01-01

Lignin is a heteropolymer that is thought to form in the cell wall by combinatorial radical coupling of monolignols. Here, we present a simulation model of in vitro lignin polymerization, based on the combinatorial coupling theory, which allows us to predict the reaction conditions controlling the primary structure of lignin polymers. Our model predicts two controlling factors for the β-O-4 content of syringyl-guaiacyl lignins: the supply rate of monolignols and the relative amount of supplied sinapyl alcohol monomers. We have analyzed the in silico degradability of the resulting lignin polymers by cutting the resulting lignin polymers at β-O-4 bonds. These are cleaved in analytical methods used to study lignin composition, namely thioacidolysis and derivatization followed by reductive cleavage, under pulping conditions, and in some lignocellulosic biomass pretreatments. PMID:20472753

Formic-acid-induced depolymerization of oxidized lignin to aromatics

NASA Astrophysics Data System (ADS)

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

2014-11-01

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

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

PubMed

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

2014-11-13

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

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

PubMed Central

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

Designer lignins: harnessing the plasticity of lignification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mottiar, Yaseen; Vanholme, Ruben; Boerjan, Wout

Lignin is a complex polyphenolic constituent of plant secondary cell walls. Inspired largely by the recalcitrance of lignin to biomass processing, plant engineering efforts have routinely sought to alter lignin quantity, composition, and structure by exploiting the inherent plasticity of lignin biosynthesis. More recently, researchers are attempting to strategically design plants for increased degradability by incorporating monomers that lead to a lower degree of polymerisation, reduced hydrophobicity, fewer bonds to other cell wall constituents, or novel chemically labile linkages in the polymer backbone. In addition, the incorporation of value-added structures could help valorise lignin. Designer lignins may satisfy the biologicalmore » requirement for lignification in plants while improving the overall efficiency of biomass utilisation.« less

Designer lignins: harnessing the plasticity of lignification

DOE PAGES

Mottiar, Yaseen; Vanholme, Ruben; Boerjan, Wout; ...

2016-01-15

Lignin is a complex polyphenolic constituent of plant secondary cell walls. Inspired largely by the recalcitrance of lignin to biomass processing, plant engineering efforts have routinely sought to alter lignin quantity, composition, and structure by exploiting the inherent plasticity of lignin biosynthesis. More recently, researchers are attempting to strategically design plants for increased degradability by incorporating monomers that lead to a lower degree of polymerisation, reduced hydrophobicity, fewer bonds to other cell wall constituents, or novel chemically labile linkages in the polymer backbone. In addition, the incorporation of value-added structures could help valorise lignin. Designer lignins may satisfy the biologicalmore » requirement for lignification in plants while improving the overall efficiency of biomass utilisation.« less

The Use of Esterified Lignin for Synthesis of Durable Composites

Treesearch

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

2011-01-01

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

Flocculation of wheat straw soda lignin by hemoglobin and chicken blood: Effects of cationic polymer or calcium chloride

USDA-ARS?s Scientific Manuscript database

Flocculation can be used to separate non-sulfonated lignin from base hydrolyzed biomass. In the industrial process, the lignin is isolated by filtration and washed with water. Some of the lignin is lost in the wash water, and flocculation can be used to recover this lignin. Several ways of enhanc...

Structural Transformation of Isolated Poplar and Switchgrass Lignins from Dilute Acid Pretreatment

DOE PAGES

Sun, Qining; Pu, Yunqiao; Meng, Xianzhi; ...

2015-08-27

A key step in conversion of cellulosic biomass into sustainable fuels and chemicals is thermochemical pretreatment to reduce plant cell wall recalcitrance. Obtaining an improved understanding of the fundamental chemistry of lignin, the most recalcitrant component of biomass, during pretreatment is critical to the continued development of renewable biofuel production. To examine the intrinsic chemistry of lignin during dilute acid pretreatment (DAP), lignin was isolated from poplar and switchgrass using a cellulolytic enzyme system and then treated under DAP conditions. These results highlight that lignin is subjected to depolymerization reactions within the first 2 min of dilute acid pretreatment andmore » these changes are accompanied by increased generation of aliphatic and phenolic hydroxyl groups of lignin. This is followed by a competing set of depolymerization and repolymerization reactions that lead to a decrease in the content of guaiacyl lignin units and an increase in condensed lignin units as the reaction residence time is extended beyond 5 min. Finally, we showed that a detailed comparison of changes in functional groups and molecular weights of cellulolytic enzyme lignins with different structural parameters, related to the recalcitrant properties of lignin, could be successfully altered during DAP conditions.« less

The Acetyl Bromide Method Is Faster, Simpler and Presents Best Recovery of Lignin in Different Herbaceous Tissues than Klason and Thioglycolic Acid Methods

PubMed Central

Moreira-Vilar, Flavia Carolina; Siqueira-Soares, Rita de Cássia; Finger-Teixeira, Aline; de Oliveira, Dyoni Matias; Ferro, Ana Paula; da Rocha, George Jackson; Ferrarese, Maria de Lourdes L.; dos Santos, Wanderley Dantas; Ferrarese-Filho, Osvaldo

2014-01-01

We compared the amount of lignin as determined by the three most traditional methods for lignin measurement in three tissues (sugarcane bagasse, soybean roots and soybean seed coat) contrasting for lignin amount and composition. Although all methods presented high reproducibility, major inconsistencies among them were found. The amount of lignin determined by thioglycolic acid method was severely lower than that provided by the other methods (up to 95%) in all tissues analyzed. Klason method was quite similar to acetyl bromide in tissues containing higher amounts of lignin, but presented lower recovery of lignin in the less lignified tissue. To investigate the causes of the inconsistencies observed, we determined the monomer composition of all plant materials, but found no correlation. We found that the low recovery of lignin presented by the thioglycolic acid method were due losses of lignin in the residues disposed throughout the procedures. The production of furfurals by acetyl bromide method does not explain the differences observed. The acetyl bromide method is the simplest and fastest among the methods evaluated presenting similar or best recovery of lignin in all the tissues assessed. PMID:25330077

Structural Variation of Bamboo Lignin before and after Ethanol Organosolv Pretreatment

PubMed Central

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

2013-01-01

In order to make better use of lignocellulosic biomass for the production of renewable fuels and chemicals, it is necessary to disrupt its recalcitrant structure through pretreatment. Specifically, organosolv pretreatment is a feasible method. The main advantage of this method compared to other lignocellulosic pretreatment technologies is the extraction of high-quality lignin for the production of value-added products. In this study, bamboo was treated in a batch reactor with 70% ethanol at 180 °C for 2 h. Lignin fractions were isolated from the hydrolysate by centrifugation and then precipitated as ethanol organosolv lignin. Two types of milled wood lignins (MWLs) were isolated from the raw bamboo and the organosolv pretreated residue separately. After the pretreatment, a decrease of lignin (preferentially guaiacyl unit), hemicelluloses and less ordered cellulose was detected in the bamboo material. It was confirmed that the bamboo MWL is of HGS type (p-hydroxyphenyl (H), vanillin (G), syringaldehyde (S)) associated with a considerable amount of p-coumarate and ferulic esters of lignin. The ethanol organosolv treatment was shown to remove significant amounts of lignin and hemicelluloses without strongly affecting lignin primary structure and its lignin functional groups. PMID:24169436

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Ruoshui; Guo, Mond; Lin, Kuan-ting

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 phenolicmore » 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.« less

Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels.

PubMed

Del Río, José C; Rencoret, Jorge; Gutiérrez, Ana; Kim, Hoon; Ralph, John

2018-05-02

The structure of the phenolic polymer in maize grain fibers, with 5.5% Klason lignin content, has been studied. For this, the milled wood lignin (MWL) and dioxane lignin (DL) preparations were isolated and analyzed. The data indicated that the lignin in maize fibers was syringyl rich, mostly involved in β-aryl ether, resinol, and phenylcoumaran substructures. 2D NMR and derivatization followed by reductive cleavage (DFRC) also revealed the occurrence of associated ferulates together with trace amounts of p-coumarates acylating the γ-OH of lignin side chains, predominantly on S-lignin units. More interesting was the occurrence of diferuloylputrescine, a ferulic acid amide, which was identified by 2D NMR and comparison with a synthesized standard, that was apparently incorporated into this lignin. A phenylcoumaran structure involving a diferuloylputrescine coupled through 8-5' linkages to another diferuloylputrescine (or to a ferulate or a guaiacyl lignin unit) was found, providing compelling evidence for its participation in radical coupling reactions. The occurrence of diferuloylputrescine in cell walls of maize kernels and other cereal grains appears to have been missed in previous works, perhaps due to the alkaline hydrolysis commonly used for composition studies.

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

PubMed

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.

Why genetic modification of lignin leads to low-recalcitrance biomass

DOE PAGES

Carmona, Christopher; Langan, Paul; Smith, Jeremy C.; ...

2014-11-11

Genetic modification of plants via down-regulation of cinnamyl alcohol dehydrogenase leads to incorporation of aldehyde groups in the lignin polymer. Moreover, the resulting lignocellulosic biomass has increased bioethanol yield. However, a molecular-scale explanation of this finding is currently lacking. We perform molecular dynamics simulation of the copolymer with hemicellulose of wild type and the genetically modified lignin, in aqueous solution. We find that the non-covalent association with hemicellulose of lignin containing aldehyde groups is reduced compared to the wild-type. This phase separation may increase the cell wall porosity in the mutant plants, thus explaining their easier deconstruction to biofuels. Themore » thermodynamic origin of the reduced lignin-hemicellulose association is found to be a more favorable self-interaction energy and less favorable interaction with hemicellulose for the mutant lignin. Furthermore, reduced hydration water density fluctuations are found for the mutant lignin, implying a more hydrophobic lignin surface. Our results provide a detailed description of how aldehyde incorporation makes lignin more hydrophobic and reduces its association with hemicellulose, thus suggesting that increased lignin hydrophobicity may be an optimal characteristic required for improved biofuel production.« less

Characterization of Trapped Lignin-Degrading Microbes in Tropical Forest Soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeAngelis, Kristen M.; Allgaier, Martin; Chavarria, Yaucin

2011-04-29

Lignin is often the most difficult portion of plant biomass to degrade, with fungi generally thought to dominate during late stage decomposition. Lignin in feedstock plant material represents a barrier to more efficient plant biomass conversion and can also hinder enzymatic access to cellulose, which is critical for biofuels production. Tropical rain forest soils in Puerto Rico are characterized by frequent anoxic conditions and fluctuating redox, suggesting the presence of lignin-degrading organisms and mechanisms that are different from known fungal decomposers and oxygen-dependent enzyme activities. We explored microbial lignin-degraders by burying bio-traps containing lignin-amended and unamended biosep beads in themore » 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.« less

Characterization of trapped lignin-degrading microbes in tropical forest soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeAngelis, K.M.; Allgaier, M.; Chavarria, Y.

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 themore » 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.« less

Characterization of Trapped Lignin-Degrading Microbes in Tropical Forest Soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeAngelis, Kristen; Allgaier, Martin; Chavarria, Yaucin

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 themore » 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.« less

Lignin Films from Spruce, Eucalyptus, and Wheat Straw Studied with Electroacoustic and Optical Sensors: Effect of Composition and Electrostatic Screening on Enzyme Binding.

PubMed

Pereira, Antonio; Hoeger, Ingrid C; Ferrer, Ana; Rencoret, Jorge; Del Rio, José C; Kruus, Kristiina; Rahikainen, Jenni; Kellock, Miriam; Gutiérrez, Ana; Rojas, Orlando J

2017-04-10

Lignins were isolated from spruce, wheat straw, and eucalyptus by using the milled wood lignin (MWL) method. Functional groups and compositional analyses were assessed via 2D NMR and 31 P NMR to realize their effect on enzyme binding. Films of the lignins were fabricated and ellipsometry, atomic force microscopy, and water contact angle measurements were used for their characterization and to reveal the changes upon enzyme adsorption. Moreover, lignin thin films were deposited on quartz crystal microgravimetry (QCM) and surface plasmon (SPR) resonance sensors and used to gain further insights into the lignin-cellulase interactions. For this purpose, a commercial multicomponent enzyme system and a monocomponent Trichoderma reesei exoglucanase (CBH-I) were considered. Strong enzyme adsorption was observed on the various lignins but compared to the multicomponent cellulases, CBH-I displayed lower surface affinity and higher binding reversibility. This resolved prevalent questions related to the affinity of this enzyme with lignin. Remarkably, a strong correlation between enzyme binding and the syringyl/guaiacyl (S/G) ratio was found for the lignins, which presented a similar hydroxyl group content ( 31 P NMR): higher protein affinity was determined on isolated spruce lignin (99% G units), while the lowest adsorption occurred on isolated eucalyptus lignin (70% S units). The effect of electrostatic interactions in enzyme adsorption was investigated by SPR, which clearly indicated that the screening of charges allowed more extensive protein adsorption. Overall, this work furthers our understanding of lignin-cellulase interactions relevant to biomass that has been subjected to no or little pretreatment and highlights the widely contrasting effects of the nature of lignin, which gives guidance to improve lignocellulosic saccharification and related processes.

Lignin characteristics in soil profiles of different plant communities in a subtropical mixed forest in Central China

NASA Astrophysics Data System (ADS)

Liu, F.; Wang, X.

2016-12-01

Lignin is widely considered as a major source of stable soil carbon, its content and degradation states are important indicators of soil carbon quality and stability. Few studies have explored the effects of plant communities on lignin characteristics in soils, and studies on lignin characteristics across soil depths resulted in contradictory findings. In this study, we investigated the lignin contents, their degradation states in the soil aggregates across three soil depths for four major plant communities in a subtropical mixed forest in central China. We found that lignin content in the litter of two deciduous species (Carpinus fargesii CF and Fagus Lucida FL) are higher than that in the two evergreen species ( Cyclobalanopsis multinervis CM and Schima parviflora SP). These differences maintained in the soil with a diminished scale. Lignin content showed a decreased trend in soil profiles of all plant communities, but no significant differences of degradation states were observed. The distribution of aggregation fractions was significantly different among plant communities, the SP community have higher percent of >2000 μm fraction (50.46%) and lower percent of <0.25 μm fraction (12.87%) than the CF community (40.05%, 21.90% respectively). The lignin content increased with decreasing aggregations size, however, no significant differences of lignin degradation states was observed among the four size aggregations. These results collectively reveal the influence of plant communities on lignin characteristics in soil, probably through litter input. Similar degradation states of lignin across soil profile and different size aggregates emphasized the importance of lignin movements association with soil water. This knowledge of lignin characteristics across soil profile can improve our understanding of soil carbon stability at different depths and how it may respond to changes in soil conditions.

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

PubMed

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

2018-04-01

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

Lignin blockers and uses thereof

DOEpatents

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

2011-01-25

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

Wood properties of Scots pines (Pinus sylvestris) grown at elevated temperature and carbon dioxide concentration.

PubMed

Kilpeläinen, Antti; Peltola, Heli; Ryyppö, Aija; Sauvala, Kari; Laitinen, Kaisa; Kellomäki, Seppo

2003-09-01

Impacts of elevated temperature and carbon dioxide concentration ([CO2]) on wood properties of 15-year-old Scots pines (Pinus sylvestris L.) grown under conditions of low nitrogen supply were investigated in open-top chambers. The treatments consisted of (i) ambient temperature and ambient [CO2] (AT+AC), (ii) ambient temperature and elevated [CO2] (AT+EC), (iii) elevated temperature and ambient [CO2] (ET+AC) and (iv) elevated temperature and elevated [CO2] (ET+EC). Wood properties analyzed for the years 1992-1994 included ring width, early- and latewood width and their proportions, intra-ring wood density (minimum, maximum and mean, as well as early- and latewood densities), mean fiber length and chemical composition of the wood (cellulose, hemicellulose, lignin and acetone extractive concentration). Absolute radial growth over the 3-year period was 54% greater in AT+EC trees and 30 and 25% greater in ET+AC and ET+EC trees, respectively, than in AT+AC trees. Neither elevated temperature nor elevated [CO2] had a statistically significant effect on ring width, early- and latewood widths or their proportions. Both latewood density and maximum intra-ring density were increased by elevated [CO2], whereas fiber length was increased by elevated temperature. Hemicellulose concentration decreased and lignin concentration increased significantly in response to elevated temperature. There were no statistically significant interaction effects of elevated temperature and elevated [CO2] on the wood properties, except on earlywood density.

Silencing CHALCONE SYNTHASE in Maize Impedes the Incorporation of Tricin into Lignin and Increases Lignin Content.

PubMed

Eloy, Nubia B; Voorend, Wannes; Lan, Wu; Saleme, Marina de Lyra Soriano; Cesarino, Igor; Vanholme, Ruben; Smith, Rebecca A; Goeminne, Geert; Pallidis, Andreas; Morreel, Kris; Nicomedes, José; Ralph, John; Boerjan, Wout

2017-02-01

Lignin is a phenolic heteropolymer that is deposited in secondary-thickened cell walls, where it provides mechanical strength. A recent structural characterization of cell walls from monocot species showed that the flavone tricin is part of the native lignin polymer, where it is hypothesized to initiate lignin chains. In this study, we investigated the consequences of altered tricin levels on lignin structure and cell wall recalcitrance by phenolic profiling, nuclear magnetic resonance, and saccharification assays of the naturally silenced maize (Zea mays) C2-Idf (inhibitor diffuse) mutant, defective in the CHALCONE SYNTHASE Colorless2 (C2) gene. We show that the C2-Idf mutant produces highly reduced levels of apigenin- and tricin-related flavonoids, resulting in a strongly reduced incorporation of tricin into the lignin polymer. Moreover, the lignin was enriched in β-β and β-5 units, lending support to the contention that tricin acts to initiate lignin chains and that, in the absence of tricin, more monolignol dimerization reactions occur. In addition, the C2-Idf mutation resulted in strikingly higher Klason lignin levels in the leaves. As a consequence, the leaves of C2-Idf mutants had significantly reduced saccharification efficiencies compared with those of control plants. These findings are instructive for lignin engineering strategies to improve biomass processing and biochemical production. © 2017 American Society of Plant Biologists. All Rights Reserved.

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

PubMed Central

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

2015-01-01

Modifying lignin composition and structure is a key strategy to increase plant cell wall digestibility for biofuel production. Disruption of the genes encoding both cinnamyl alcohol dehydrogenases (CADs), including CADC and CADD, in Arabidopsis thaliana results in the atypical incorporation of hydroxycinnamaldehydes into lignin. Another strategy to change lignin composition is downregulation or overexpression of ferulate 5-hydroxylase (F5H), which results in lignins enriched in guaiacyl or syringyl units, respectively. Here, we combined these approaches to generate plants enriched in coniferaldehyde-derived lignin units or lignins derived primarily from sinapaldehyde. The cadc cadd and ferulic acid hydroxylase1 (fah1) cadc cadd plants are similar in growth to wild-type plants even though their lignin compositions are drastically altered. In contrast, disruption of CAD in the F5H-overexpressing background results in dwarfism. The dwarfed phenotype observed in these plants does not appear to be related to collapsed xylem, a hallmark of many other lignin-deficient dwarf mutants. cadc cadd, fah1 cadc cadd, and cadd F5H-overexpressing plants have increased enzyme-catalyzed cell wall digestibility. Given that these CAD-deficient plants have similar total lignin contents and only differ in the amounts of hydroxycinnamaldehyde monomer incorporation, these results suggest that hydroxycinnamaldehyde content is a more important determinant of digestibility than lignin content. PMID:26265762

Silencing CHALCONE SYNTHASE in Maize Impedes the Incorporation of Tricin into Lignin and Increases Lignin Content

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eloy, Nubia B.; Voorend, Wannes; Lan, Wu

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

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

PubMed Central

2017-01-01

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

Silencing CHALCONE SYNTHASE in Maize Impedes the Incorporation of Tricin into Lignin and Increases Lignin Content

DOE PAGES

Eloy, Nubia B.; Voorend, Wannes; Lan, Wu; ...

2016-12-09

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

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

PubMed

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

2012-02-22

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

Early diagenesis of mangrove leaves in a tropical estuary: Bulk chemical characterization using solid-state 13C NMR and elemental analyses

NASA Astrophysics Data System (ADS)

Benner, Ronald; Hatcher, Patrick G.; Hedges, John I.

1990-07-01

Changes in the chemical composition of mangrove ( Rhizophora mangle) leaves during decomposition in tropical estuarine waters were characterized using solid-state 13C nuclear magnetic resonance (NMR) and elemental (CHNO) analysis. Carbohydrates were the most abundant components of the leaves accounting for about 50 wt% of senescent tissues. Tannins were estimated to account for about 20 wt% of leaf tissues, and lipid components, cutin, and possibly other aliphatic biopolymers in leaf cuticles accounted for about 15 wt%. Carbohydrates were generally less resistant to decomposition than the other constituents and decreased in relative concentration during decomposition. Tannins were of intermediate resistance to decomposition and remained in fairly constant proportion during decomposition. Paraffinic components were very resistant to decomposition and increased in relative concentration as decomposition progressed. Lignin was a minor component of all leaf tissues. Standard methods for the colorimetric determination of tannins (Folin-Dennis reagent) and the gravimetric determination of lignin (Klason lignin) were highly inaccurate when applied to mangrove leaves. The N content of the leaves was particularly dynamic with values ranging from 1.27 wt% in green leaves to 0.65 wt% in senescent yellow leaves attached to trees. During decomposition in the water the N content initially decreased to 0.51 wt% due to leaching, but values steadily increased thereafter to 1.07 wt% in the most degraded leaf samples. The absolute mass of N in the leaves increased during decomposition indicating that N immobilization was occurring as decomposition progressed.

Early diagenesis of mangrove leaves in a tropical estuary: Bulk chemical characterization using solid-state 13C NMR and elemental analyses

USGS Publications Warehouse

Benner, R.; Hatcher, P.G.; Hedges, J.I.

1990-01-01

Changes in the chemical composition of mangrove (Rhizophora mangle) leaves during decomposition in tropical estuarine waters were characterized using solid-state 13C nuclear magnetic resonance (NMR) and elemental (CHNO) analysis. Carbohydrates were the most abundant components of the leaves accounting for about 50 wt% of senescent tissues. Tannins were estimated to account for about 20 wt% of leaf tissues, and lipid components, cutin, and possibly other aliphatic biopolymers in leaf cuticles accounted for about 15 wt%. Carbohydrates were generally less resistant to decomposition than the other constituents and decreased in relative concentration during decomposition. Tannins were of intermediate resistance to decomposition and remained in fairly constant proportion during decomposition. Paraffinic components were very resistant to decomposition and increased in relative concentration as decomposition progressed. Lignin was a minor component of all leaf tissues. Standard methods for the colorimetric determination of tannins (Folin-Dennis reagent) and the gravimetric determination of lignin (Klason lignin) were highly inaccurate when applied to mangrove leaves. The N content of the leaves was particularly dynamic with values ranging from 1.27 wt% in green leaves to 0.65 wt% in senescent yellow leaves attached to trees. During decomposition in the water the N content initially decreased to 0.51 wt% due to leaching, but values steadily increased thereafter to 1.07 wt% in the most degraded leaf samples. The absolute mass of N in the leaves increased during decomposition indicating that N immobilization was occurring as decomposition progressed. ?? 1990.

Sodium hydroxide pretreatment and enzymatic hydrolysis of coastal Bermuda grass.

PubMed

Wang, Ziyu; Keshwani, Deepak R; Redding, Arthur P; Cheng, Jay J

2010-05-01

Coastal Bermuda grass was pretreated with NaOH at concentrations from 0.5% to 3% (w/v) for a residence time from 15 to 90min at 121 degrees C. The pretreatments were evaluated based on total lignin removal and production of total reducing sugars, glucose and xylose from enzymatic hydrolysis of the pretreated biomass. Up to 86% lignin removal was observed. The optimal NaOH pretreatment conditions at 121 degrees C for total reducing sugars production as well as glucose and xylose yields are 15min and 0.75% NaOH. Under these optimal pretreatment conditions, total reducing sugars yield was about 71% of the theoretical maximum, and the overall conversion efficiencies for glucan and xylan were 90.43% and 65.11%, respectively. Copyright 2009 Elsevier Ltd. All rights reserved.

Magnetite nanoparticles conjugated with lignin: A physicochemical and magnetic study

NASA Astrophysics Data System (ADS)

Klapiszewski, Łukasz; Zdarta, Jakub; Antecka, Katarzyna; Synoradzki, Karol; Siwińska-Stefańska, Katarzyna; Moszyński, Dariusz; Jesionowski, Teofil

2017-11-01

Using the by-product biopolymer lignin and nanoparticles of magnetite, well-known for its nontoxicity and magnetic properties, novel nanomagnetite-lignin hybrid materials were synthesized. In the first step, magnetite was produced via a co-precipitation method with hydrothermal treatment, and was found to have a particle size of around 20 nm. Nano-Fe3O4 was then combined with pre-activated lignin to obtain hybrids with various magnetite-lignin ratios, whose physicochemical and magnetic properties were thoroughly analyzed. Thermal analysis showed the hybrids to have higher thermal stability than pure lignin. Based on Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy it was demonstrated that the Fe3O4 and lignin are connected via Fesbnd Osbnd C bonds. Further measurements showed the nanomagnetite-lignin hybrid materials to have good magnetic properties. The results of this study suggest that the synthesized hybrids may find practical applications in many fields of science and industry.

A study of poplar organosolv lignin after melt rheology treatment as carbon fiber precursors

DOE PAGES

Sun, Qining; Khunsupat, Ratayakorn; Akato, Kokouvi; ...

2016-06-16

Lignins from various poplar genotypes were isolated by using organosolv fractionation and subjected to rheological treatment at various temperatures. Physicochemical characterization of the lignin variants shows a broad distribution of glass transition temperatures, melt viscosity, and pyrolysis char residues. Rheological treatment at 170 °C induces lignin repolymerization accompanied with an increase in condensed linkages, molecular weights, and viscosities. In contrast, rheology testing at 190 °C results in the decrease in lignin aliphatic and phenolic hydroxyl groups, β-O-aryl ether linkages, molecular weights, and viscosity values. Lignin under air cooling generates more oxygenated and condensed compounds, but lower amounts of ether linkagesmore » than lignin cooled under nitrogen. Here, lignin with a lower syringyl/guaiacyl ratio tends to form more cross-linkages along with higher viscosity values, higher molecular weight and larger amounts of condensed bonds.« less

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

PubMed

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.

Specific lignin accumulation in granulated juice sacs of Citrus maxima.

PubMed

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

2014-12-17

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

Effective Release of Lignin Fragments from Lignocellulose by Lewis Acid Metal Triflates in the Lignin-First Approach.

PubMed

Huang, Xiaoming; Zhu, Jiadong; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

2016-12-08

Adding value to lignin, the most complex and recalcitrant fraction in lignocellulosic biomass, is highly relevant to costefficient operation of biorefineries. We report the use of homogeneous metal triflates to rapidly release lignin from biomass. Combined with metal-catalyzed hydrogenolysis, the process separates woody biomass into few lignin-derived alkylmethoxyphenols and cellulose under mild conditions. Model compound studies show the unique catalytic properties of metal triflates in cleaving lignin-carbohydrate interlinkages. The lignin fragments can then be disassembled by hydrogenolysis. The tandem process is flexible and allows obtaining good aromatic monomer yields from different woods (36-48 wt %, lignin base). The cellulose-rich residue is an ideal feedstock for established biorefining processes. The highly productive strategy is characterized by short reaction times, low metal triflate catalyst requirement, and leaving cellulose largely untouched. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lignin from Micro- to Nanosize: Applications

PubMed Central

Friedl, Anton

2017-01-01

Micro- and nanosize lignin has recently gained interest due to improved properties compared to standard lignin available today. As the second most abundant biopolymer after cellulose, lignin is readily available but used for rather low-value applications. This review focuses on the application of micro- and nanostructured lignin in final products or processes that all show potential for high added value. The fields of application are ranging from improvement of mechanical properties of polymer nanocomposites, bactericidal and antioxidant properties and impregnations to hollow lignin drug carriers for hydrophobic and hydrophilic substances. Also, a carbonization of lignin nanostructures can lead to high-value applications such as use in supercapacitors for energy storage. The properties of the final product depend on the surface properties of the nanomaterial and, therefore, on factors like the lignin source, extraction method, and production/precipitation methods, as discussed in this review. PMID:29117142

Method for recovering and using lignin in adhesive resins

DOEpatents

Schroeder, Herbert A.

1993-01-01

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

Estimation of Biochemical Constituents From Fresh, Green Leaves By Spectrum Matching Techniques

NASA Technical Reports Server (NTRS)

Goetz, A. F. H.; Gao, B. C.; Wessman, C. A.; Bowman, W. D.

1990-01-01

Estimation of biochemical constituents in vegetation such as lignin, cellulose, starch, sugar and protein by remote sensing methods is an important goal in ecological research. The spectral reflectances of dried leaves exhibit diagnostic absorption features which can be used to estimate the abundance of important constituents. Lignin and nitrogen concentrations have been obtained from canopies by use of imaging spectrometry and multiple linear regression techniques. The difficulty in identifying individual spectra of leaf constituents in the region beyond 1 micrometer is that liquid water contained in the leaf dominates the spectral reflectance of leaves in this region. By use of spectrum matching techniques, originally used to quantify whole column water abundance in the atmosphere and equivalent liquid water thickness in leaves, we have been able to remove the liquid water contribution to the spectrum. The residual spectra resemble spectra for cellulose in the 1.1 micrometer region, lignin in the 1.7 micrometer region, and starch in the 2.0-2.3 micrometer region. In the entire 1.0-2.3 micrometer region each of the major constituents contributes to the spectrum. Quantitative estimates will require using unmixing techniques on the residual spectra.

Optimal experimental condition for hemicellulosic hydrolyzate treatment with activated charcoal for xylitol production.

PubMed

Mussatto, Solange I; Roberto, Inês C

2004-01-01

Rice straw was hydrolyzed into a mixture of sugars using diluted H(2)SO(4). During hydrolysis, a variety of inhibitors was also produced, including acetic acid, furfural, hydroxymethylfurfural, and lignin degradation products (several aromatic and phenolic compounds). To reduce the toxic compounds concentration in the hydrolyzate and to improve the xylitol yield and volumetric productivity, rice straw hemicellulosic hydrolyzate was treated with activated charcoal under different pH values, stirring rates, contact times, and temperatures, employing a 2(4) full-factorial design. Fermentative assays were conducted with treated hydrolyzates containing 90 g/L xylose. The results indicated that temperature, pH, and stirring rate strongly influenced the hydrolyzate treatment, temperature and pH interfering with all of the responses analyzed (removal of color and lignin degradation products, xylitol yield factor, and volumetric productivity). The combination of pH 2.0, 150 rpm, 45 degrees C, and 60 min was considered an optimal condition, providing significant removal rates of color (48.9%) and lignin degradation products (25.8%), as well as a xylitol production of 66 g/L, a volumetric productivity of 0.57 g/L.h, and a yield factor of 0.72 g/g.

Comparative RNA-Sequence Transcriptome Analysis of Phenolic Acid Metabolism in Salvia miltiorrhiza, a Traditional Chinese Medicine Model Plant

PubMed Central

Song, Zhenqiao; Guo, Linlin; Liu, Tian; Lin, Caicai; Wang, Jianhua

2017-01-01

Salvia miltiorrhiza Bunge is an important traditional Chinese medicine (TCM). In this study, two S. miltiorrhiza genotypes (BH18 and ZH23) with different phenolic acid concentrations were used for de novo RNA sequencing (RNA-seq). A total of 170,787 transcripts and 56,216 unigenes were obtained. There were 670 differentially expressed genes (DEGs) identified between BH18 and ZH23, 250 of which were upregulated in ZH23, with genes involved in the phenylpropanoid biosynthesis pathway being the most upregulated genes. Nine genes involved in the lignin biosynthesis pathway were upregulated in BH18 and thus result in higher lignin content in BH18. However, expression profiles of most genes involved in the core common upstream phenylpropanoid biosynthesis pathway were higher in ZH23 than that in BH18. These results indicated that genes involved in the core common upstream phenylpropanoid biosynthesis pathway might play an important role in downstream secondary metabolism and demonstrated that lignin biosynthesis was a putative partially competing pathway with phenolic acid biosynthesis. The results of this study expanded our understanding of the regulation of phenolic acid biosynthesis in S. miltiorrhiza. PMID:28194403

Changes in cinnamyl alcohol dehydrogenase activities from sugarcane cultivars inoculated with Sporisorium scitamineum sporidia.

PubMed

Santiago, Rocío; Alarcón, Borja; de Armas, Roberto; Vicente, Carlos; Legaz, María Estrella

2012-06-01

This study describes a method for determining cinnamyl alcohol dehydrogenase activity in sugarcane stems using reverse phase (RP) high-performance liquid chromatography to elucidate their possible lignin origin. Activity is assayed using the reverse mode, the oxidation of hydroxycinnamyl alcohols into hydroxycinnamyl aldehydes. Appearance of the reaction products, coniferaldehyde and sinapaldehyde is determined by measuring absorbance at 340 and 345 nm, respectively. Disappearance of substrates, coniferyl alcohol and sinapyl alcohol is measured at 263 and 273 nm, respectively. Isocratic elution with acetonitrile:acetic acid through an RP Mediterranea sea C18 column is performed. As case examples, we have examined two different cultivars of sugarcane; My 5514 is resistant to smut, whereas B 42231 is susceptible to the pathogen. Inoculation of sugarcane stems elicits lignification and produces significant increases of coniferyl alcohol dehydrogenase (CAD) and sinapyl alcohol dehydrogenase (SAD). Production of lignin increases about 29% in the resistant cultivar and only 13% in the susceptible cultivar after inoculation compared to uninoculated plants. Our results show that the resistance of My 5514 to smut is likely derived, at least in part, to a marked increase of lignin concentration by the activation of CAD and SAD. Copyright © Physiologia Plantarum 2012.

Multi-time series RNA-seq analysis of Enterobacter lignolyticus SCF1 during growth in lignin-amended medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orellana, Roberto; Chaput, Gina; Markillie, Lye Meng

The production of lignocellulosic-derived biofuels is a highly promising source of alternative energy, but it has been constrained by the lack of a microbial platform capable to efficiently degrade this recalcitrant material and cope with by-products that can be toxic to cells. Species that naturally grow in environments where carbon is mainly available as lignin are promising for finding new ways of removing the lignin that protects cellulose for improved conversion of lignin to fuel precursors. Enterobacter lignolyticus SCF1 is a facultative anaerobic Gammaproteobacteria isolated from tropical rain forest soil collected in El Yunque forest, Puerto Rico under anoxic growthmore » conditions with lignin as sole carbon source. Whole transcriptome analysis of SCF1 during E.lignolyticus SCF1 lignin degradation was conducted on cells grown in the presence (0.1%, w/w) and the absence of lignin, where samples were taken at three different times during growth, beginning of exponential phase, mid-exponential phase and beginning of stationary phase. Lignin-amended cultures achieved twice the cell biomass as unamended cultures over three days, and in this time degraded 60% of lignin. Transcripts in early exponential phase reflected this accelerated growth. A complement of laccases, aryl-alcohol dehydrogenases, and peroxidases were most up-regulated in lignin amended conditions in mid-exponential and early stationary phases compared to unamended growth. The association of hydrogen production by way of the formate hydrogenlyase complex with lignin degradation suggests a possible value added to lignin degradation in the future.« less

Multi-time series RNA-seq analysis of Enterobacter lignolyticus SCF1 during growth in lignin-amended medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orellana, Roberto; Chaput, Gina; Markillie, Lye Meng

The production of lignocellulosic-derived biofuels is a highly promising source of alternative energy, but it has been constrained by the lack of a microbial platform capable to efficiently degrade this recalcitrant material and cope with by-products that can be toxic to cells. Species that naturally grow in environments where carbon is mainly available as lignin are promising for finding new ways of removing the lignin that protects cellulose for improved conversion of lignin to fuel precursors. Enterobacter lignolyticus SCF1 is a facultative anaerobic Gammaproteobacteria isolated from tropical rain forest soil collected in El Yunque forest, Puerto Rico under anoxic growthmore » conditions with lignin as sole carbon source. Whole transcriptome analysis of SCF1 during E.lignolyticus SCF1 lignin degradation was conducted on cells grown in the presence (0.1%, w/w) and the absence of lignin, where samples were taken at three different times during growth, beginning of exponential phase, midexponential phase and beginning of stationary phase. Lignin-amended cultures achieved twice the cell biomass as unamended cultures over three days, and in this time degraded 60% of lignin. Transcripts in early exponential phase reflected this accelerated growth. A complement of laccases, aryl-alcohol dehydrogenases, and peroxidases were most up-regulated in lignin amended conditions in mid-exponential and early stationary phases compared to unamended growth. The association of hydrogen production by way of the formate hydrogenlyase complex with lignin degradation suggests a possible value added to lignin degradation in the future.« less

Multi-time series RNA-seq analysis of Enterobacter lignolyticus SCF1 during growth in lignin-amended medium.

PubMed

Orellana, Roberto; Chaput, Gina; Markillie, Lye Meng; Mitchell, Hugh; Gaffrey, Matt; Orr, Galya; DeAngelis, Kristen M

2017-01-01

The production of lignocellulosic-derived biofuels is a highly promising source of alternative energy, but it has been constrained by the lack of a microbial platform capable to efficiently degrade this recalcitrant material and cope with by-products that can be toxic to cells. Species that naturally grow in environments where carbon is mainly available as lignin are promising for finding new ways of removing the lignin that protects cellulose for improved conversion of lignin to fuel precursors. Enterobacter lignolyticus SCF1 is a facultative anaerobic Gammaproteobacteria isolated from tropical rain forest soil collected in El Yunque forest, Puerto Rico under anoxic growth conditions with lignin as sole carbon source. Whole transcriptome analysis of SCF1 during E.lignolyticus SCF1 lignin degradation was conducted on cells grown in the presence (0.1%, w/w) and the absence of lignin, where samples were taken at three different times during growth, beginning of exponential phase, mid-exponential phase and beginning of stationary phase. Lignin-amended cultures achieved twice the cell biomass as unamended cultures over three days, and in this time degraded 60% of lignin. Transcripts in early exponential phase reflected this accelerated growth. A complement of laccases, aryl-alcohol dehydrogenases, and peroxidases were most up-regulated in lignin amended conditions in mid-exponential and early stationary phases compared to unamended growth. The association of hydrogen production by way of the formate hydrogenlyase complex with lignin degradation suggests a possible value added to lignin degradation in the future.

Synergistic enzymatic and microbial lignin conversion

DOE PAGES

Zhao, Cheng; Xie, Shangxian; Pu, Yunqiao; ...

2015-10-02

We represent the utilization of lignin for fungible fuels and chemicals and it's one of the most imminent challenges in modern biorefineries. However, bioconversion of lignin is highly challenging due to its recalcitrant nature as a phenolic heteropolymer. This study addressed the challenges by revealing the chemical and biological mechanisms for synergistic lignin degradation by a bacterial and enzymatic system, which significantly improved lignin consumption, cell growth and lipid yield. The Rhodococcus opacus cell growth increased exponentially in response to the level of laccase treatment, indicating the synergy between laccase and bacterial cells in lignin degradation. Other treatments like ironmore » and hydrogen peroxide showed limited impact on cell growth. Chemical analysis of lignin under various treatments further confirmed the synergy between laccase and cells at the chemical level. 31P nuclear magnetic resonance (NMR) suggested that laccase, R. opacus cell and Fenton reaction reagents promoted the degradation of different types of lignin functional groups, elucidating the chemical basis for the synergistic effects. 31P NMR further revealed that laccase treatment had the most significant impact for degrading the abundant chemical groups. The results were further confirmed by the molecular weight analysis and lignin quantification by the Prussian blue assay. The cell–laccase fermentation led to a 17-fold increase of lipid production. Overall, the study indicated that laccase and R. opacus can synergize to degrade lignin efficiently, likely through rapid utilization of monomers generated by laccase to promote the reaction toward depolymerization. The study provided a potential path for more efficient lignin conversion and development of consolidated lignin conversion.« less

Multi-time series RNA-seq analysis of Enterobacter lignolyticus SCF1 during growth in lignin-amended medium

PubMed Central

Chaput, Gina; Markillie, Lye Meng; Mitchell, Hugh; Gaffrey, Matt; Orr, Galya; DeAngelis, Kristen M.

2017-01-01

The production of lignocellulosic-derived biofuels is a highly promising source of alternative energy, but it has been constrained by the lack of a microbial platform capable to efficiently degrade this recalcitrant material and cope with by-products that can be toxic to cells. Species that naturally grow in environments where carbon is mainly available as lignin are promising for finding new ways of removing the lignin that protects cellulose for improved conversion of lignin to fuel precursors. Enterobacter lignolyticus SCF1 is a facultative anaerobic Gammaproteobacteria isolated from tropical rain forest soil collected in El Yunque forest, Puerto Rico under anoxic growth conditions with lignin as sole carbon source. Whole transcriptome analysis of SCF1 during E.lignolyticus SCF1 lignin degradation was conducted on cells grown in the presence (0.1%, w/w) and the absence of lignin, where samples were taken at three different times during growth, beginning of exponential phase, mid-exponential phase and beginning of stationary phase. Lignin-amended cultures achieved twice the cell biomass as unamended cultures over three days, and in this time degraded 60% of lignin. Transcripts in early exponential phase reflected this accelerated growth. A complement of laccases, aryl-alcohol dehydrogenases, and peroxidases were most up-regulated in lignin amended conditions in mid-exponential and early stationary phases compared to unamended growth. The association of hydrogen production by way of the formate hydrogenlyase complex with lignin degradation suggests a possible value added to lignin degradation in the future. PMID:29049419

Synergistic enzymatic and microbial lignin conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Cheng; Xie, Shangxian; Pu, Yunqiao

We represent the utilization of lignin for fungible fuels and chemicals and it's one of the most imminent challenges in modern biorefineries. However, bioconversion of lignin is highly challenging due to its recalcitrant nature as a phenolic heteropolymer. This study addressed the challenges by revealing the chemical and biological mechanisms for synergistic lignin degradation by a bacterial and enzymatic system, which significantly improved lignin consumption, cell growth and lipid yield. The Rhodococcus opacus cell growth increased exponentially in response to the level of laccase treatment, indicating the synergy between laccase and bacterial cells in lignin degradation. Other treatments like ironmore » and hydrogen peroxide showed limited impact on cell growth. Chemical analysis of lignin under various treatments further confirmed the synergy between laccase and cells at the chemical level. 31P nuclear magnetic resonance (NMR) suggested that laccase, R. opacus cell and Fenton reaction reagents promoted the degradation of different types of lignin functional groups, elucidating the chemical basis for the synergistic effects. 31P NMR further revealed that laccase treatment had the most significant impact for degrading the abundant chemical groups. The results were further confirmed by the molecular weight analysis and lignin quantification by the Prussian blue assay. The cell–laccase fermentation led to a 17-fold increase of lipid production. Overall, the study indicated that laccase and R. opacus can synergize to degrade lignin efficiently, likely through rapid utilization of monomers generated by laccase to promote the reaction toward depolymerization. The study provided a potential path for more efficient lignin conversion and development of consolidated lignin conversion.« less

Multi-time series RNA-seq analysis of Enterobacter lignolyticus SCF1 during growth in lignin-amended medium

DOE PAGES

Orellana, Roberto; Chaput, Gina; Markillie, Lye Meng; ...

2017-10-19

The production of lignocellulosic-derived biofuels is a highly promising source of alternative energy, but it has been constrained by the lack of a microbial platform capable to efficiently degrade this recalcitrant material and cope with by-products that can be toxic to cells. Species that naturally grow in environments where carbon is mainly available as lignin are promising for finding new ways of removing the lignin that protects cellulose for improved conversion of lignin to fuel precursors. Enterobacter lignolyticus SCF1 is a facultative anaerobic Gammaproteobacteria isolated from tropical rain forest soil collected in El Yunque forest, Puerto Rico under anoxic growthmore » conditions with lignin as sole carbon source. Whole transcriptome analysis of SCF1 during E.lignolyticus SCF1 lignin degradation was conducted on cells grown in the presence (0.1%, w/w) and the absence of lignin, where samples were taken at three different times during growth, beginning of exponential phase, mid-exponential phase and beginning of stationary phase. Lignin-amended cultures achieved twice the cell biomass as unamended cultures over three days, and in this time degraded 60% of lignin. Transcripts in early exponential phase reflected this accelerated growth. A complement of laccases, aryl-alcohol dehydrogenases, and peroxidases were most up-regulated in lignin amended conditions in mid-exponential and early stationary phases compared to unamended growth. The association of hydrogen production by way of the formate hydrogenlyase complex with lignin degradation suggests a possible value added to lignin degradation in the future.« less

Performance of prototype high-flow inhalable dust sampler in a livestock production facility.

PubMed

Anthony, T Renée; Cai, Changjie; Mehaffy, John; Sleeth, Darrah; Volckens, John

2017-05-01

A high-flow inhalable sampler, designed for operational flow rates up to 10 L/min using computer simulations and examined in wind tunnel experiments, was evaluated in the field. This prototype sampler was deployed in collocation with an IOM (the benchmark standard sampler) in a swine farrowing building to examine the sampling performance for assessing concentrations of inhalable particulate mass and endotoxin. Paired samplers were deployed for 24 hr on 19 days over a 3-month period. On each sampling day, the paired samplers were deployed at three fixed locations and data were analyzed to identify agreement and to examine systematic biases between concentrations measured by these samplers. Thirty-six paired gravimetric samples were analyzed; insignificant, unsubstantial differences between concentrations were identified between the two samplers (p = 0.16; mean difference 0.03 mg/m 3 ). Forty-four paired samples were available for endotoxin analysis, and a significant (p = 0.001) difference in endotoxin concentration was identified: the prototype sampler, on average, had 120 EU/m 3 more endotoxin than did the IOM samples. Since the same gravimetric samples were analyzed for endotoxin content, the endotoxin difference is likely attributable to differences in endotoxin extraction. The prototype's disposable thin-film polycarbonate capsule was included with the filter in the 1-hr extraction procedure while the internal plastic cassette of the IOM required a rinse procedure that is susceptible to dust losses. Endotoxin concentrations measured with standard plastic IOM inserts that follow this rinsing procedure may underestimate the true endotoxin exposure concentrations. The maximum concentrations in the study (1.55 mg/m 3 gravimetric, 2328 EU/m 3 endotoxin) were lower than other agricultural or industrial environments. Future work should explore the performance of the prototype sampler in dustier environments, where concentrations approach particulates not otherwise specified (PNOS) limits of 10 mg/m 3 , including using the prototype as a personal sampler.

Biomass Deconstruction and Pretreatment | Bioenergy | NREL

Science.gov Websites

lignocellulose into intermediate streams with low toxicity, high sugar concentrations, and utilizable lignin for illustration of a car driving down a country road into the sunset that leads to Renewable Energy Storage. High refined. The feedstock then goes into a High Solids Enzymatic Digester and then into High Solids

Comparison of stem morphology and anatomy of two alfalfa clonal lines exhibiting divergent cell wall composition

USDA-ARS?s Scientific Manuscript database

In previous research, two alfalfa clonal lines (252, 1283) were identified that exhibited environmentally stable differences in stem cell walls. Compared to stems of 1283, stems of 252 have a higher cell wall concentration and greater amounts of lignin and cellulose but reduced levels of pectic suga...

Effects of hot water extraction pretreatment on pyrolysis of shrub willow

USDA-ARS?s Scientific Manuscript database

Treatment of biomass via hot water extraction (HWE) reduces the amount of hemicellulose and ash in the biomass resulting in a concentration of cellulose and lignin content. In this study, we tested the effect of HWE as a biomass pretreatment on the pyrolysis of shrub willow via both conventional he...

Exploring surface characterization and electrostatic property of Hybrid Pennisetum during alkaline sulfite pretreatment for enhanced enzymatic hydrolysability.

PubMed

Yang, Ming; Wang, Jingfeng; Hou, Xincun; Wu, Juying; Fan, Xifeng; Jiang, Fan; Tao, Pan; Wang, Fan; Peng, Pai; Yang, Fangxia; Zhang, Junhua

2017-11-01

The surface characterization and electrostatic property of Hybrid Pennisetum (HP) after alkaline sulfite pretreatment were explored for enhanced enzymatic hydrolysability. The O/C ratio in HP increased from 0.34 to 0.60, and C1 concentration decreased from 62.5% to 31.6%, indicating that alkaline sulfite pretreatment caused poorer lignin but richer carbohydrate on HP surface. Zeta potential and sulfur element analysis indicated that more enzymes would preferably adsorb on the carbohydrate surface of alkaline sulfite pretreated HP because the lignin was sulfonated, which facilitated the decrease of non-productive adsorption. Glucose yield of alkaline sulfite pretreated HP reached to 100% by synergistic action of cellulase and xylanase in the hydrolysis, which was significantly higher than that of NaOH pretreated, and the concentration of glucose released was 1.52times higher. The results suggested that alkaline sulfite pretreatment had potential for improving the HP hydrolysability, and the surface characterization and electrostatic property facilitated the enzymatic digestibility. Copyright © 2017 Elsevier Ltd. All rights reserved.

Alkaline hydrogen peroxide pretreatment of cashew apple bagasse for ethanol production: study of parameters.

PubMed

Correia, Jessyca Aline da Costa; Júnior, José Edvan Marques; Gonçalves, Luciana Rocha B; Rocha, Maria Valderez Ponte

2013-07-01

The alkaline hydrogen peroxide (AHP) pretreatment of cashew apple bagasse (CAB) was evaluated based on the conversion of the resultant cellulose into glucose. The effects of the concentration of hydrogen peroxide at pH 11.5, the biomass loading and the pretreatment duration performed at 35°C and 250 rpm were evaluated after the subsequent enzymatic saccharification of the pretreated biomass using a commercial cellulase enzyme. The CAB used in this study contained 20.56 ± 2.19% cellulose, 10.17 ± 0.89% hemicellulose and 35.26 ± 0.90% lignin. The pretreatment resulted in a reduced lignin content in the residual solids. Increasing the H2O2 concentration (0-4.3% v/v) resulted in a higher rate of enzymatic hydrolysis. Lower biomass loadings gave higher glucose yields. In addition, no measurable furfural and hydroxymethyl furfural were produced in the liquid fraction during the pretreatment. The results show that alkaline hydrogen peroxide is effective for the pretreatment of CAB. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Paleoreconstruction of organic carbon inputs to an oxbow lake in the Mississippi River watershed: Effects of dam construction and land use change on regional inputs

NASA Astrophysics Data System (ADS)

Bianchi, Thomas S.; Galy, Valier; Rosenheim, Brad E.; Shields, Michael; Cui, Xingqian; Van Metre, Peter

2015-10-01

We use a dated sediment core from Lake Whittington (USA) in the lower Mississippi River to reconstruct linkages in the carbon cycling and fluvial sediment dynamics over the past 80 years. Organic carbon (OC) sources were characterized using bulk (δ13C, ramped pyrolysis-oxidation (PyrOx) 14C, δ15N, and TN:OC ratios) and compound-specific (lignin phenols and fatty acids, including δ13C and 14C of the fatty acids) analyses. Damming of the Missouri River in the 1950s, other hydrological modifications to the river, and soil conservation measures resulted in reduced net OC export, in spite of increasing OC concentrations. Decreasing δ13C values coincided with increases in δ15N, TN:OC ratios, long-chain fatty acids, and lignin-phenol concentrations, suggesting increased inputs of soil-derived OC dominated by C3 vegetation, mainly resulting from changes in farming practices and crop distribution. However, ramped PyrOx 14C showed no discernible differences downcore in thermochemical stability, indicating a limited impact on soil OC turnover.

The emerging role for bacteria in lignin degradation and bio-product formation.

PubMed

Bugg, Timothy D H; Ahmad, Mark; Hardiman, Elizabeth M; Singh, Rahul

2011-06-01

The microbial degradation of lignin has been well studied in white-rot and brown-rot fungi, but is much less well studied in bacteria. Recent published work suggests that a range of soil bacteria, often aromatic-degrading bacteria, are able to break down lignin. The enzymology of bacterial lignin breakdown is currently not well understood, but extracellular peroxidase and laccase enzymes appear to be involved. There are also reports of aromatic-degrading bacteria isolated from termite guts, though there are conflicting reports on the ability of termite gut micro-organisms to break down lignin. If biocatalytic routes for lignin breakdown could be developed, then lignin represents a potentially rich source of renewable aromatic chemicals. Copyright © 2010 Elsevier Ltd. All rights reserved.

Chemical synthesis of beta-O-4 type artificial lignin.

PubMed

Kishimoto, Takao; Uraki, Yasumitsu; Ubukata, Makoto

2006-04-07

An artificial lignin polymer containing only the beta-O-4 substructure was synthesized. The procedure consists of two key steps: 1) polycondensation of a brominated monomer by aromatic Williamson reaction; and 2) subsequent reduction of the carbonyl polymer. 13C-NMR and HMQC spectra of the polymer were consistent with beta-O-4 substructures in milled wood lignin isolated from Japanese fir wood. The weight average degree of polymerization (DP(w)) ranged from 19.5 to 30.6, which is comparable to enzymatically synthesized artificial lignin from p-hydroxycinnamyl alcohols (dehydrogenation polymer, DHP) and some isolated lignins. Using this new lignin model polymer, it will now be possible to reinvestigate the properties and reactivity of the main lignin structure in terms of its polymeric character.

Six-man, self-contained carbon dioxide concentrator subsystem for Space Station Prototype (SSP) application

NASA Technical Reports Server (NTRS)

Kostell, G. D.; Schubert, F. H.; Shumar, J. W.; Hallick, T. M.; Jensen, F. C.

1974-01-01

A six man, self contained, electrochemical carbon dioxide concentrating subsystem for space station prototype use was successfully designed, fabricated, and tested. A test program was successfully completed which covered shakedown testing, design verification testing, and acceptance testing.

Lignin biosynthesis in wheat (Triticum aestivum L.): its response to waterlogging and association with hormonal levels.

PubMed

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 biotic and abiotic stresses and feedstock quality of wheat biomass are closely associated with its lignin content. Therefore, the findings of this study provide important insights into the molecular mechanisms underlying lignin formation in wheat, an important step towards the development of molecular tools that can facilitate the breeding of wheat cultivars for optimized lignin content and enhanced feedstock quality without affecting other lignin-related agronomic benefits.

Roles of lignin biosynthesis and regulatory genes in plant development

PubMed Central

Yoon, Jinmi; Choi, Heebak

2015-01-01

Abstract Lignin is an important factor affecting agricultural traits, biofuel production, and the pulping industry. Most lignin biosynthesis genes and their regulatory genes are expressed mainly in the vascular bundles of stems and leaves, preferentially in tissues undergoing lignification. Other genes are poorly expressed during normal stages of development, but are strongly induced by abiotic or biotic stresses. Some are expressed in non‐lignifying tissues such as the shoot apical meristem. Alterations in lignin levels affect plant development. Suppression of lignin biosynthesis genes causes abnormal phenotypes such as collapsed xylem, bending stems, and growth retardation. The loss of expression by genes that function early in the lignin biosynthesis pathway results in more severe developmental phenotypes when compared with plants that have mutations in later genes. Defective lignin deposition is also associated with phenotypes of seed shattering or brittle culm. MYB and NAC transcriptional factors function as switches, and some homeobox proteins negatively control lignin biosynthesis genes. Ectopic deposition caused by overexpression of lignin biosynthesis genes or master switch genes induces curly leaf formation and dwarfism. PMID:26297385

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

PubMed Central

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

2016-01-01

Due to the enormous abundance of lignin and its unique aromatic nature, lignin has great potential for the production of industrially useful fuels, chemicals, and materials. However, the rigid and compact structure of the plant cell walls significantly blocks the separation of lignin. In this study, wheat straw was hydrothermally pretreated at different temperatures (120–200 °C) followed by post-treatment with 70% ethanol containing 1% NaOH to improve the isolation of lignin. Results demonstrated that the content of associated carbohydrates of the lignin fractions was gradually reduced with the increment of the hydrothermal severity. The structure of the lignins changed regularly with the increase of the pretreatment temperature from 120 to 200 °C. In particular, the contents of β-O-4′, β-β′, β-5′ linkages and aliphatic OH in the lignins showed a tendency of decrease, while the content of phenolic OH and thermal stability of the lignin fractions increased steadily as the increment of the pretreatment temperature. PMID:27982101

Lignin preparation from oil palm empty fruit bunches by sequential acid/alkaline treatment--A biorefinery approach.

PubMed

Medina, Jesus David Coral; Woiciechowski, Adenise; Zandona Filho, Arion; Noseda, Miguel D; Kaur, Brar Satinder; Soccol, Carlos Ricardo

2015-10-01

Lignin is an important raw material for the sustainable biorefineries and also the forerunner of high-value added products, such as biocomposite for chemical, pharmaceutical and cement industries. Oil palm empty fruit bunches (OPEFB) were used for lignin preparation by successive treatment with 1% (w/w) H2SO4 at 121°C for 60 min and 2.5% NaOH at 121°C for 80 min resulting in the high lignin yield of 28.89%, corresponding to 68.82% of the original lignin. The lignin obtained was characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The results indicated a lignin with molecular masses ramping from 4500 kDa to 12,580 kDa. FTIR and NMR of these lignins showed more syringyl and p-hydroxyphenyl than guaiacyl units. Moderate acid/alkaline treatment provided lignin with high industrial potential and acid hydrolyzates rich in fermentable sugars and highly porous cellulosic fibers. Copyright © 2015. Published by Elsevier Ltd.

Fungal biodegradation of lignopolystyrene graft copolymers. [Pleurotus ostreatus; Phanerochaete chrysosporium; Trametes versicolor; Gloeophyllum trabeum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milstein, O.; Gersonde, R.; Huttermann, A.

1992-10-01

White rot basidiomycetes were able to biodegrade styrene (1-phenylethene) graft copolymers of lignin containing different proportions of lignin and polystyrene (poly(1-phenylethylene)). The biodegradation tests were run on lignin-styrene copolymerization products which contained 10.3, 32.2, and 50.4{percent} (wt/wt) lignin. The polymer samples were incubated with the white rot fungi Pleurotus ostreatus, Phanerochaete chrysosporium, and Trametes versicolor and the brown rot fungus Gloeophyllum trabeum. White rot fungi degraded the plastic samples at a rate which increased with increasing lignin content in the copolymer sample. Both polystyrene and lignin components of the copolymer were readily degraded. Polystyrene pellets were not degradable in thesemore » tests. Degradation was verified for both incubated and control samples by weight loss, quantitative UV spectrophotometric analysis of both lignin and styrene residues, scanning electron microscopy of the plastic surface, and the presence of enzymes active in degradation during incubation. Brown rot fungus did not affect any of the plastics. White rot fungi produced and secreted oxidative enzymes associated with lignin degradation in liquid media during incubation with lignin-polystyrene copolymer.« less

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

PubMed Central

2011-01-01

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. PMID:22018114

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

NASA Astrophysics Data System (ADS)

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 environments can be explained by white-rot fungal degradation.