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Sample records for lignin concentration sensor

  1. Development of a prototype lignin concentration sensor. Final report. Draft

    SciTech Connect

    Jeffers, L.A.

    1994-11-01

    The ultimate objective of the DOE-sponsored program discussed in this report is to commercialize an instrument for real-time, in-situ measurement of lignin in wood pulp at a variety of locations in the pulp process stream. The instrument will be used as a primary sensor for process control in the pulp and paper industry. Work done by B&W prior to the initiation of this program had shown: there is a functional relationship between the fluorescence intensity and the Kappa number as measured at the pulp mill laboratory. Kappa number is a standard wet chemical method for determination of the lignin concentration; the relationship is one of decreasing intensity with Kappa number, indicating operation in the quenched fluorescence regime; a great deal of scatter in the data. Because of the preliminary nature of the study, the origin of the scatter was not identified. This report documents the results of laboratory measurements made on a variety of well defined pulp samples to generate the data necessary to: determine the feasibility of an instrument for on-line lignin concentration measurement using laser fluorescence; identify the preferred measurement strategy; define the range of applicability of the instrument; and to provide background information to guide the design of a field-worthy prototype.

  2. Lignin Sensor Based On Flash-Pyrolysis Mass Spectrometry

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  4. Fiber and lignin analysis in concentrate, forage, and feces: detergent versus enzymatic-chemical method.

    PubMed

    Hindrichsen, I K; Kreuzer, M; Madsen, J; Bach Knudsen, K E

    2006-06-01

    Hemicelluloses, cellulose, and lignin contents of contrasting feeds, with emphasis on concentrate ingredients and complete concentrates, were analyzed using the Van Soest detergent procedure (analyzing neutral detergent fiber, acid detergent fiber, and acid detergent lignin) and the enzymatic-chemical procedure (analyzing cellulose, soluble and insoluble noncellulosic polysaccharides, and Klason lignin). Also, feces from cows fed concentrates differing in carbohydrate composition were analyzed by the 2 procedures. The correlation between acid detergent lignin and Klason lignin was significant, but not as close as the one between individual structural polysaccharides measured with the 2 procedures. The correlation between the results of the 2 procedures was highly significant for apparent cellulose digestibility, as were the correlations between digestibilities of hemicelluloses with total as well as with insoluble noncellulosic polysaccharides. The relationship between dietary lignin content and fiber digestibility was weak. The exclusion of a group of cows fed a concentrate with apple pulp, however, improved the respective correlations. Klason lignin correlated more closely with the measured fiber digestibility than acid detergent lignin. The study showed that results of the detergent method were comparable to those of the enzymatic-chemical method with cellulose, hemicelluloses, and their digestibilities. However, acid detergent lignin was much lower than Klason lignin. When the carbohydrate composition of concentrate varied widely, lignin was not suitable for the prediction of fiber digestibility.

  5. 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.

  6. 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 Carrera, Ana; Rencoret, Jorge; Del Rio, Jose Carlos; Kruus, Kristiina; Rahikainen, Jenni; Kellock, Miriam; Gutierrez, Ana; Rojas, Orlando J

    2017-03-13

    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 31P 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 S/G ratio was found for the lignins, which presented a similar hydroxyl group content (31P 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 pre-treatment and highlights the widely contrasting effects of the nature of lignin, which gives guidance to improve lignocellulosic saccharification and related processes.

  7. Optimization of simultaneous saccharification and fermentation conditions with amphipathic lignin derivatives for concentrated bioethanol production.

    PubMed

    Cheng, Ningning; Koda, Keiichi; Tamai, Yutaka; Yamamoto, Yoko; Takasuka, Taichi E; Uraki, Yasumitsu

    2017-05-01

    Amphipathic lignin derivatives (A-LDs) prepared from the black liquor of soda pulping of Japanese cedar are strong accelerators for bioethanol production under a fed-batch simultaneous enzymatic saccharification and fermentation (SSF) process. To improve the bioethanol production concentration, conditions such as reaction temperature, stirring program, and A-LDs loadings were optimized in both small scale and large scale fed-batch SSF. The fed-batch SSF in the presence of 3.0g/L A-LDs at 38°C gave the maximum ethanol production and a high enzyme recovery rate. Furthermore, a jar-fermenter equipped with a powerful mechanical stirrer was designed for 1.5L-scale fed-batch SSF to achieve rigorous mixing during high substrate loading. Finally, the 1.5L fed-batch SSF with a substrate loading of 30% (w/v) produced a high ethanol concentration of 87.9g/L in the presence of A-LDs under optimized conditions.

  8. Lignin extraction--reassessment of the severity factor with respect to hydroxide concentration.

    PubMed

    Lee, Roland A; Berberi, Veronique; Labranche, Joey; Lavoie, Jean-Michel

    2014-10-01

    Steam processes have often been associated with a severity factor, correlating the cooking temperature, time and catalyst used in the process. Although equations for treatments with and without acid catalyst have been suggested, there is so far no simple equation allowing a precise estimation of the amount of lignin extracted from lignocellulosic biomass. In this work, a new version of the severity factor equation is proposed. This has been shown to correlate effectively to the amount of lignin extracted from various types of lignocellulosic materials and different extraction methods. The resulting severity factor is robust with potential to be utilized both for acid and base-catalyzed extraction of lignin. Finally, the proposed correlation between the severity factor and extracted lignin under base conditions has been correlated with empirical data to validate the entire model and especially under mild condition where lesser information was available from open literature.

  9. Through Lignin Biodegradation to Lignin-based Plastics

    NASA Astrophysics Data System (ADS)

    Wang, Yun-Yan

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

  10. 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.

  11. Nano-fiber diameters as liquid concentration sensors

    NASA Astrophysics Data System (ADS)

    Chyad, Radhi M.; Mat Jafri, Mohd Zubir; Ibrahim, Kamarulazizi

    2013-05-01

    Manufacturing technologies of nano-fiber sensors offer a number of approved properties of optical fiber sensors utilized in various sensory applications. The nano-fiber sensor is utilized to sense the difference in the concentration of D-glucose in double-distilled deionized water and to measure the refractive index (RI) of a sugar solution. Our proposed method exhibited satisfactory capability based on bimolecular interactions in the biological system. The response of the nano-fiber sensors indicates a different kind of interaction among various groups of AAs. These results can be interpreted in terms of solute-solute and solute-solvent interactions and the structure making or breaking ability of solutes in the given solution. This study utilized spectra photonics to measure the transmission of light through different concentrations of sugar solution, employing cell cumber and nano-optical fibers as sensors.

  12. Lignin degradation during plant litter photodegradation

    NASA Astrophysics Data System (ADS)

    Lin, Y.; King, J. Y.

    2014-12-01

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

  13. 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.

  14. Enzymatic Glucose Sensor Compensation for Variations in Ambient Oxygen Concentration

    PubMed Central

    Collier, Bradley B.; McShane, Michael J.

    2014-01-01

    Due to the increasing prevalence of diabetes, research toward painless glucose sensing continues. Oxygen sensitive phosphors with glucose oxidase (GOx) can be used to determine glucose levels indirectly by monitoring oxygen consumption. This is an attractive combination because of its speed and specificity. Packaging these molecules together in “smart materials” for implantation will enable non-invasive glucose monitoring. As glucose levels increase, oxygen levels decrease; consequently, the luminescence intensity and lifetime of the phosphor increase. Although the response of the sensor is dependent on glucose concentration, the ambient oxygen concentration also plays a key role. This could lead to inaccurate glucose readings and increase the risk of hyper- or hypoglycemia. To mitigate this risk, the dependence of hydrogel glucose sensor response on oxygen levels was investigated and compensation methods explored. Sensors were calibrated at different oxygen concentrations using a single generic logistic equation, such that trends in oxygen-dependence were determined as varying parameters in the equation. Each parameter was found to be a function of oxygen concentration, such that the correct glucose calibration equation can be calculated if the oxygen level is known. Accuracy of compensation will be determined by developing an overall calibration, using both glucose and oxygen sensors in parallel, correcting for oxygen fluctuations in real time by intentionally varying oxygen, and calculating the error in actual and predicted glucose levels. While this method was developed for compensation of enzymatic glucose sensors, in principle it can also be implemented with other kinds of sensors utilizing oxidases. PMID:26257458

  15. Preparation and Analysis of Biomass Lignins

    NASA Astrophysics Data System (ADS)

    Compere, Alicia L.; Griffith, William L.

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

  16. Does elevated N make lignin more recalcitrant?

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  17. Tracking heat flux sensors for concentrating solar applications

    DOEpatents

    Andraka, Charles E; Diver, Jr., Richard B

    2013-06-11

    Innovative tracking heat flux sensors located at or near the solar collector's focus for centering the concentrated image on a receiver assembly. With flux sensors mounted near a receiver's aperture, the flux gradient near the focus of a dish or trough collector can be used to precisely position the focused solar flux on the receiver. The heat flux sensors comprise two closely-coupled thermocouple junctions with opposing electrical polarity that are separated by a thermal resistor. This arrangement creates an electrical signal proportional to heat flux intensity, and largely independent of temperature. The sensors are thermally grounded to allow a temperature difference to develop across the thermal resistor, and are cooled by a heat sink to maintain an acceptable operating temperature.

  18. 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.

  19. Hydrogen peroxide sensing and cytotoxicity activity of Acacia lignin stabilized silver nanoparticles.

    PubMed

    Aadil, Keshaw Ram; Barapatre, Anand; Meena, Avtar Singh; Jha, Harit

    2016-01-01

    The study is aimed at detection of hydrogen peroxide (H2O2) using Acacia lignin mediated silver nanoparticles (AGNPs). The synthesis of AGNPs was achieved at conditions optimized as, 3 ml of 0.02% lignin and 1mM silver nitrate incubated for 30 min at 80°C and pH 9. Initial screening of AGNPs was performed by measuring the surface plasmon resonance peak at 410-430 nm using UV-vis spectrophotometer. Transmission electron microscopy, atomic force microscopy, X-ray diffraction and particle size analysis confirmed the spherical shaped face centered cubic structure and 10-50 nm size of AGNPs. The infrared spectroscopy study further revealed that the active functional groups present in lignin were responsible for the reduction of silver ions (Ag(+)) to metallic silver (Ag(0)). Lignin stabilized silver nanoparticles showed good sensitivity and a linear response over wide concentrations of H2O2 (10(-1) to 10(-6)M). Further, the in vitrocytotoxicity activity of the lignin mediated AGNPs (5-500 μg/ml) demonstrated toxicity effects in MCF-7 and A375 cell lines. Thus, lignin stabilized silver nanoparticles based optical sensor for H2O2 could be potentially applied in the determination of reactive oxygen species and toxic chemicals which further expands the importance of lignin stabilized silver nanoparticles.

  20. Fabricated nano-fiber diameter as liquid concentration sensors

    NASA Astrophysics Data System (ADS)

    Chyad, Radhi M.; Mat Jafri, Mohd Zubir; Ibrahim, Kamarulazizi

    Nanofiber is characterized by thin, long, and very soft silica. Taper fibers are made using an easy and low cost chemical method. Etching is conducted with a HF solution to remove cladding and then a low molarity HF solution to reduce the fiber core diameter. One approach to on-line monitoring of the etching process uses spectrophotometer with a white light source. In the aforementioned technique, this method aims to determine the diameter of the reduced core and show the evolution of the two different processes from the nanofiber regime to the fixed regime in which the mode was remote from the surrounding evanescent field, intensity can propagate outside the segment fiber when the core diameter is less than 500 nm. Manufacturing technologies of nano-fiber sensors offer a number of approved properties of optical fiber sensors utilized in various sensory applications. The nano-fiber sensor is utilized to sense the difference in the concentration of D-glucose in double-distilled deionized water and to measure the refractive index (RI) of a sugar solution. Our proposed method exhibited satisfactory capability based on bimolecular interactions in the biological system. The response of the nano-fiber sensors indicates a different kind of interaction among various groups of AAs. These results can be interpreted in terms of solute-solute and solute-solvent interactions and the structure making or breaking ability of solutes in the given solution. This study utilized spectra photonics to measure the transmission of light through different concentrations of sugar solution, employing cell cumber and nano-optical fibers as sensors.

  1. Gas sensor characterization at low concentrations of natural oils

    NASA Astrophysics Data System (ADS)

    Sambemana, H.; Siadat, M.; Lumbreras, M.

    2009-05-01

    Inhalation of essential oils can be used in aromatherapy due to their activating or relaxing effects. The study of these effects requires behavioral measurements on living subjects, by varying the nature and also the quantity of the volatile substances to be present in the atmosphere. So, to permit the evaluation of therapeutic effects of a variety of natural oils, we propose to develop an automatic diffusion/detection system capable to create an ambient air with low stabilized concentration of chosen oil. In this work, we discuss the performance of an array of eight gas sensors to discriminate low and constant concentrations of a chosen natural oil.

  2. 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.

  3. Concentric Coplanar Capacitive Sensor System with Quantitative Model

    NASA Technical Reports Server (NTRS)

    Bowler, Nicola (Inventor); Chen, Tianming (Inventor)

    2014-01-01

    A concentric coplanar capacitive sensor includes a charged central disc forming a first electrode, an outer annular ring coplanar with and outer to the charged central disc, the outer annular ring forming a second electrode, and a gap between the charged central disc and the outer annular ring. The first electrode and the second electrode may be attached to an insulative film. A method provides for determining transcapacitance between the first electrode and the second electrode and using the transcapacitance in a model that accounts for a dielectric test piece to determine inversely the properties of the dielectric test piece.

  4. Solvent Fractionation of Lignin

    SciTech Connect

    Chatterjee, Sabornie; Saito, Tomonori

    2014-01-01

    Lignin is a highly abundant source of renewable carbon that can be considered as a valuable sustainable source of biobased materials. The major issues for the commercial production of value added high performance lignin products are lignin s physical and chemical heterogenities. To overcome these problems, a variety of procedures have been developed to produce pure lignin suitable for high performace applications such as lignin-derived carbon materials. However, most of the isolation procedures affect lignin s properties and structure. In this chapter, a short review of the effect of solvent fractionation on lignin s properties and structure is presented.

  5. Micro-LiDAR velocity, temperature, density, concentration sensor

    NASA Technical Reports Server (NTRS)

    Danehy, Paul M. (Inventor); Dorrington, Adrian A. (Inventor)

    2010-01-01

    A light scatter sensor includes a sensor body in which are positioned a plurality of optical fibers. The sensor body includes a surface, in one end of each of the optical fibers terminates at the surface of the sensor body. One of the optical fibers is an illumination fiber for emitting light. A plurality of second optical fibers are collection fibers for collecting scattered light signals. A light sensor processor is connected to the collection fibers to detect the scattered light signals.

  6. Efficiency of Lignin Biosynthesis: a Quantitative Analysis

    PubMed Central

    AMTHOR, JEFFREY S.

    2003-01-01

    Lignin is derived mainly from three alcohol monomers: p‐coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. Biochemical reactions probably responsible for synthesizing these three monomers from sucrose, and then polymerizing the monomers into lignin, were analysed to estimate the amount of sucrose required to produce a unit of lignin. Included in the calculations were amounts of respiration required to provide NADPH (from NADP+) and ATP (from ADP) for lignin biosynthesis. Two pathways in the middle stage of monomer biosynthesis were considered: one via tyrosine (found in monocots) and the other via phenylalanine (found in all plants). If lignin biosynthesis proceeds with high efficiency via tyrosine, 76·9, 70·4 and 64·3 % of the carbon in sucrose can be retained in the fraction of lignin derived from p‐coumaryl alcohol, coniferyl alcohol and sinapyl alcohol, respectively. The corresponding carbon retention values for lignin biosynthesis via phenylalanine are less, at 73·2, 65·7 and 60·7 %, respectively. Energy (i.e. heat of combustion) retention during lignin biosynthesis via tyrosine could be as high as 81·6, 74·5 and 67·8 % for lignin derived from p‐coumaryl alcohol, coniferyl alcohol and sinapyl alcohol, respectively, with the corresponding potential energy retention values for lignin biosynthesis via phenylalanine being less, at 77·7, 69·5 and 63·9 %, respectively. Whether maximum efficiency occurs in situ is unclear, but these values are targets that can be considered in: (1) plant breeding programmes aimed at maximizing carbon or energy retention from photosynthate; (2) analyses of (minimum) metabolic costs of responding to environmental change or pest attack involving increased lignin biosynthesis; (3) understanding costs of lignification in older tissues; and (4) interpreting carbon balance measurements of organs and plants with large lignin concentrations. PMID:12714366

  7. Separation of Alcohols from Solution by Lignin Gels

    SciTech Connect

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

    2008-01-01

    Partition relationships of radioisotope labeled ethanol and 1-butanol between aqueous solutions and a hydrated commercial Kraft softwood lignin gel are presented. These initial evaluations indicate that lignin hydrogels preferentially concentrate 1-butanol and, to a lesser extent, ethanol. The process implications and potential use of lignin as an inexpensive extractant are discussed.

  8. Ultrasonic sensor for predicting sugar concentration using multivariate calibration.

    PubMed

    Krause, D; Hussein, W B; Hussein, M A; Becker, T

    2014-08-01

    This paper presents a multivariate regression method for the prediction of maltose concentration in aqueous solutions. For this purpose, time and frequency domain of ultrasonic signals are analyzed. It is shown, that the prediction of concentration at different temperatures is possible by using several multivariate regression models for individual temperature points. Combining these models by a linear approximation of each coefficient over temperature results in a unified solution, which takes temperature effects into account. The benefit of the proposed method is the low processing time required for analyzing online signals as well as the non-invasive sensor setup which can be used in pipelines. Also the ultrasonic signal sections used in the presented investigation were extracted out of buffer reflections which remain primarily unaffected by bubble and particle interferences. Model calibration was performed in order to investigate the feasibility of online monitoring in fermentation processes. The temperature range investigated was from 10 °C to 21 °C. This range fits to fermentation processes used in the brewing industry. This paper describes the processing of ultrasonic signals for regression, the model evaluation as well as the input variable selection. The statistical approach used for creating the final prediction solution was partial least squares (PLS) regression validated by cross validation. The overall minimum root mean squared error achieved was 0.64 g/100 g.

  9. Modulating lignin in plants

    SciTech Connect

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

    2013-01-29

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

  10. Evaluation of Electrical and Optical Plethysmography Sensors for Noninvasive Monitoring of Hemoglobin Concentration

    PubMed Central

    Phillips, Justin P.; Hickey, Michelle; Kyriacou, Panayiotis A.

    2012-01-01

    Completely noninvasive monitoring of hemoglobin concentration has not yet been fully realized in the clinical setting. This study investigates the viability of measuring hemoglobin concentration noninvasively by evaluating the performance of two types of sensor using a tissue phantom perfused with a blood substitute. An electrical sensor designed to measure blood volume changes during the cardiac cycle was used together with an infrared optical sensor for detection of erythrocyte-bound hemoglobin. Both sensors demonstrated sensitivity to changes in pulse volume (plethysmography). The electrical sensor produced a signal referred to as capacitance plethysmograph (CPG) a quantity which was invariant to the concentration of an infrared absorbing dye present in the blood substitute. The optical sensor signal (photoplethysmograph) increased in amplitude with increasing absorber concentration. The ratio PPG:CPG is invariant to pulse pressure. This quantity is discussed as a possible index of in vivo hemoglobin concentration. PMID:22438739

  11. Lignin reduces ofloxacin-induced mutagenicity in Euglena assay.

    PubMed

    Krizková, L; Polónyi, J; Kosíkova, B; Dobias, J; Belicová, A; Krajcovic, J; Ebringer, L

    2000-01-01

    The possible protective effect of sulphur-free beech lignin polymer on the mutagenicity of ofloxacin in Euglena gracilis was studied. The generation of oxygen species by ofloxacin and their possible interaction with lignin was verified by physico-chemical measurements. The UV absorbance spectra of ofloxacin with and without lignin showed no interaction between these two compounds. The production of superoxide anion radical (O2-) by ofloxacin was significantly reduced in the presence of lignin (AIR = 0.57 +/- 0.03, p < 0.01). Lignin, at concentrations of 125 and 250 micrograms/ml decreased the E. gracilis bleaching activity of ofloxacin to 39.9% and 2.8%, respectively. A lignin concentration of 500 micrograms/ml eliminated the bleaching activity of ofloxacin very efficiently. Our results are consistent with the concept that lignin biopolymer has the capability of reducing genotoxic activity by scavenging reactive oxygen species.

  12. MISPS: Module integrated solar position sensor for concentration photovoltaics

    NASA Astrophysics Data System (ADS)

    Pardell, Ricard

    2012-10-01

    This paper describes a new device, the MISPS (Module Integrated. Solar Position Sensor) for CPV systems. Its main innovation lies in it being module integrated, so that the sensor is a constituent part of the module and uses its optics. The MISPS has been designed within the scope of the CPVRS project, but it can be used in any refractive optics CPV system.

  13. Optoelectronic sensor device for monitoring ethanol concentration in winemaking applications

    NASA Astrophysics Data System (ADS)

    Jiménez-Márquez, F.; Vázquez, J.; Úbeda, J.; Rodríguez-Rey, J.; Sánchez-Rojas, J. L.

    2015-05-01

    The supervision of key variables such as sugar, alcohol, released CO2 and microbiological evolution in fermenting grape must is of great importance in the winemaking industry. However, the fermentation kinetics is assessed by monitoring the evolution of the density as it varies during a fermentation, since density is an indicator of the total amount of sugars, ethanol and glycerol. Even so, supervising the fermentation process is an awkward and non-comprehensive task, especially in wine cellars where production rates are massive, and enologists usually measure the density of the extracted samples from each fermentation tank manually twice a day. This work aims at the design of a fast, low-cost, portable and reliable optoelectronic sensor for measuring ethanol concentration in fermenting grape must samples. Different sets of model solutions, which contain ethanol, fructose, glucose, glycerol dissolved in water and emulate the grape must composition at different stages of the fermentation, were prepared both for calibration and validation. The absorption characteristics of these model solutions were analyzed by a commercial spectrophotometer in the NIR region, in order to identify key wavelengths from which valuable information regarding the sample composition can be extracted. Finally, a customized optoelectronic prototype based on absorbance measurements at two wavelengths belonging to the NIR region was designed, fabricated and successfully tested. The system, whose optoelectronics is reduced after a thorough analysis to only two LED lamps and their corresponding paired photodiodes operating at 1.2 and 1.3 μm respectively, calculates the ethanol content by a multiple linear regression.

  14. Application of a two-stream radiative transfer model for leaf lignin and cellulose concentrations from spectral reflectance measurements, part 1

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

    Lignin and nitrogen contents of leaves constitute the primary rate-limiting parameters for the decomposition of forest litter, and are determinants of nutrient- and carbon-cyclic rates in forest ecosystems (Melillo et al., 1982). Wessman et al. (1988a) developed empirical multivariate relationships between forest canopy lignin amount and the (first-difference) AIS spectral response in three bands spread over the wavelength interval 1256-1555 nm. Wessman et al. (1988b) and McLellan et al. (1991) developed similar regression relationships from laboratory reflectance measurements on dried samples prepared in a standard fashion. They used four to six infrared bands for analysis of nitrogen, lignin and cellulose content of foliage in forest and prairie species. In the present article (Parts 1 and 2) the feasibility of compositional determinations is explored using positions of composite absorption bands that originate from mixtures of lignin, cellulose, and possibly other chemical constituents in the spectral reflectance of green leaves. To carry out this program, we employ full-spectral-resolution single-leaf diffuse reflectance measurements made with a laboratory spectrometer and integrating sphere. The leaf and other chemical reflectance data compiled by Elvidge (1990) have also been utilized extensively.

  15. Sensor development for in situ detection of concentration polarization and fouling of reverse osmosis membranes

    NASA Astrophysics Data System (ADS)

    Detrich, Kahlil T.; Goulbourne, Nakhiah C.

    2009-03-01

    The purpose of this research is to evaluate three polymer electroding techniques in developing a novel in situ sensor for an RO system using the electrical response of a thin film composite sensor. Electrical impedance spectroscopy (EIS) was used to measure the sensor response when exposed to sodium chloride solutions with concentrations from 0.1 M to 0.8 M in both single and double bath configurations. An insulated carbon grease sensor was mechanically stable while a composite Direct Assembly Process (DAP) sensor was fragile upon hydration. Scanning electron microscopy results from an impregnation-reduction technique showed gold nanoparticles were deposited most effectively when presoaked in a potassium hydroxide solution and on an uncoated membrane; surface resistances remained too high for sensor implementation. Through thickness carbon grease sensors showed a transient response to changes in concentration, and no meaningful concentration sensitivity was noted for the time scales over which EIS measurements were taken. Surface carbon grease electrodes attached to the polyamide thin film were not sensitive to concentration. The impedance spectra indicated the carbon grease sensor was unable to detect changes in concentration in double bath experiments when implemented with the polyamide surface exposed to salt solutions. DAP sensors lacked a consistent response to changes in concentration too. A reverse double bath experiment with the polysulfone layer exposed to a constant concentration exhibited a transient impedance response similar to through thickness carbon grease sensors in a single bath at constant concentration. These results suggest that the microporous polysulfone layer is responsible for sensor response to concentration.

  16. The effect of grain size and surface area on organic matter, lignin and carbohydrate concentration, and molecular compositions in Peru Margin sediments

    USGS Publications Warehouse

    Bergamaschi, B.A.; Tsamakis, E.; Keil, R.G.; Eglinton, T.I.; Montlucon, D.B.; Hedges, J.I.

    1997-01-01

    A C-rich sediment sample from the Peru Margin was sorted into nine hydrodynamically-determined grain size fractions to explore the effect of grain size distribution and sediment surface area on organic matter content and composition. The neutral monomeric carbohydrate composition, lignin oxidation product yields, total organic carbon, and total nitrogen contents were determined independently for each size fraction, in addition to sediment surface area and abundance of biogenic opal. The percent organic carbon and percent total nitrogen were strongly related to surface area in these sediments. In turn, the distribution of surface area closely followed mass distribution among the textural size classes, suggesting hydrodynamic controls on grain size also control organic carbon content. Nevertheless, organic compositional distinctions were observed between textural size classes. Total neutral carbohydrate yields in the Peru Margin sediments were found to closely parallel trends in total organic carbon, increasing in abundance among grain size fractions in proportion to sediment surface area. Coincident with the increases in absolute abundance, rhamnose and mannose increased as a fraction of the total carbohydrate yield in concert with surface area, indicating these monomers were preferentially represented in carbohydrates associated with surfaces. Lignin oxidation product yields varied with surface area when normalized to organic carbon, suggesting that the terrestrially-derived component may be diluted by sorption of marine derived material. Lignin-based parameters suggest a separate source for terrestrially derived material associated with sand-size material as opposed to that associated with silts and clays. Copyright ?? 1997 Elsevier Science Ltd.

  17. A Wireless, Passive, Magnetically-soft Harmonic Sensor for Monitoring Sodium Hypochlorite Concentrations in Water

    PubMed Central

    Ong, Keat G.; Paulose, Maggie; Grimes, Craig A.

    2003-01-01

    A wireless, passive, remote-query sensor for monitoring sodium hypochlorite (bleach) solutions is reported. The sensor is comprised of a magnetically-soft ferromagnetic ribbon, coated with a layer of polyurethane and alumina, having a large and nonlinear permeability that supports higher-order harmonics in response to a time varying magnetic field. The hypochlorite ions induce swelling in the coating, with the resultant stress altering the harmonic signature of the sensor from which the sodium hypochlorite concentration can be determined. The wireless, passive nature of the sensor platform enables long-term monitoring of bleach concentrations in the environment. The sensor platform can be extended to other chemical analytes of interest as desired.

  18. 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.

  19. NDIR Gas Sensor for Spatial Monitoring of Carbon Dioxide Concentrations in Naturally Ventilated Livestock Buildings

    PubMed Central

    Mendes, Luciano B.; Ogink, Nico W. M.; Edouard, Nadège; van Dooren, Hendrik Jan C.; Tinôco, Ilda de Fátima F.; Mosquera, Julio

    2015-01-01

    The tracer gas ratio method, using CO2 as natural tracer, has been suggested as a pragmatic option to measure emissions from naturally ventilated (NV) barns without the need to directly estimate the ventilation rate. The aim of this research was to assess the performance of a low-cost Non-Dispersive Infra-Red (NDIR) sensor for intensive spatial field monitoring of CO2 concentrations in a NV dairy cow house. This was achieved by comparing NDIR sensors with two commonly applied methods, a Photo-Acoustic Spectroscope (PAS) Gas Monitor and an Open-Path laser (OP-laser). First, calibrations for the NDIR sensors were obtained in the laboratory. Then, the NDIR sensors were placed in a dairy cow barn for comparison with the PAS and OP-laser methods. The main conclusions were: (a) in order to represent the overall barn CO2 concentration of the dairy cow barn, the number of NDIR sensors to be accounted for average concentration calculation was dependent on barn length and on barn area occupation; and (b) the NDIR CO2 sensors are suitable for multi-point monitoring of CO2 concentrations in NV livestock barns, being a feasible alternative for the PAS and the OP-laser methods to monitor single-point or averaged spatial CO2 concentrations in livestock barns. PMID:25985166

  20. NDIR Gas Sensor for Spatial Monitoring of Carbon Dioxide Concentrations in Naturally Ventilated Livestock Buildings.

    PubMed

    Mendes, Luciano B; Ogink, Nico W M; Edouard, Nadège; van Dooren, Hendrik Jan C; Tinôco, Ilda de Fátima F; Mosquera, Julio

    2015-05-13

    The tracer gas ratio method, using CO2 as natural tracer, has been suggested as a pragmatic option to measure emissions from naturally ventilated (NV) barns without the need to directly estimate the ventilation rate. The aim of this research was to assess the performance of a low-cost Non-Dispersive Infra-Red (NDIR) sensor for intensive spatial field monitoring of CO2 concentrations in a NV dairy cow house. This was achieved by comparing NDIR sensors with two commonly applied methods, a Photo-Acoustic Spectroscope (PAS) Gas Monitor and an Open-Path laser (OP-laser). First, calibrations for the NDIR sensors were obtained in the laboratory. Then, the NDIR sensors were placed in a dairy cow barn for comparison with the PAS and OP-laser methods. The main conclusions were: (a) in order to represent the overall barn CO2 concentration of the dairy cow barn, the number of NDIR sensors to be accounted for average concentration calculation was dependent on barn length and on barn area occupation; and (b) the NDIR CO2 sensors are suitable for multi-point monitoring of CO2 concentrations in NV livestock barns, being a feasible alternative for the PAS and the OP-laser methods to monitor single-point or averaged spatial CO2 concentrations in livestock barns.

  1. Pulsed corona discharge oxidation of aqueous lignin: decomposition and aldehydes formation.

    PubMed

    Panorel, Iris; Kaijanen, Laura; Kornev, Iakov; Preis, Sergei; Louhi-Kultanen, Marjatta; Sirén, Heli

    2014-01-01

    Lignin is the mass waste product of pulp and paper industry mostly incinerated for energy recovery. Lignin is, however, a substantial source of raw material for derivatives currently produced in costly wet oxidation processes. The pulsed corona discharge (PCD) for the first time was applied to lignin oxidation aiming a cost-effective environmentally friendly lignin removal and transformation to aldehydes. The experimental research into treatment of coniferous kraft lignin aqueous solutions was undertaken to establish the dependence of lignin oxidation and aldehyde formation on the discharge parameters, initial concentration of lignin and gas phase composition. The rate and the energy efficiency of lignin oxidation increased with increasing oxygen concentration reaching up to 82 g kW-1 h-1 in 89% vol. oxygen. Oxidation energy efficiency in PCD treatment exceeds the one for conventional ozonation by the factor of two under the experimental conditions. Oxidation at low oxygen concentrations showed a tendency of the increasing aldehydes and glyoxylic acid formation yield.

  2. Lignin as immobilization matrix for HIV p17 peptide used in immunosensing.

    PubMed

    Cerrutti, Bianca M; Moraes, Marli L; Pulcinelli, Sandra H; Santilli, Celso V

    2015-09-15

    Immunosensors based on electrical impedance spectroscopy (EIS) are increasingly being used as a fast and potentially low cost method for clinical diagnostics. In this work we fabricated immunosensors by depositing layer-by-layer (LbL) films made with an antigenic peptide (p17-1) sequence (H2N-LSGGELDRWEKIRLRPGG-OH) and lignin on interdigitated gold electrodes, which could detect anti-p17 (HIV, human immune deficiency virus) antibodies (Ab) in phosphate buffered solutions (PBS). The molecular recognition interaction between the peptide (p17-1) and the specific Ab (anti-p17) yielded substantial changes in morphology of the with LbL films, with increased roughness according to atomic force microscopy data. This interaction is behind the high sensitivity of the immunosensor. Indeed, from the EIS results, we noted that the capacitance increased significantly with the specific Ab concentration, before getting close to saturation of available peptide sites at high concentrations. Concentrations of specific antibodies as low as 0.1 ng/mL could be detected and the immunosensors had their activity preserved for two months at least. The selectivity of the immunosensor was confirmed with two types of control experiments. First, no changes in impedance were observed when the lignin/peptide LbL immunosensor was immersed into a PBS solution containing the non-specific Ab (anti-HCV for Hepatitis C) antibodies. Furthermore, for sensing units made LbL films of lignin only, the electrical response was not affected by adding specific antibodies into the PBS buffer. The successful immunosensing for HIV with antigenic peptides in a lignin matrix is also relevant for valorization of lignin, which is an important biomass component in the sugar and ethanol industry, and brings the prospect for all-organic, biocompatible sensors if implantation is ever required.

  3. Parallels in lignin biosynthesis

    PubMed Central

    Weng, Jing-Ke; Banks, Jo Ann

    2008-01-01

    A hallmark of vascular plants is the development of a complex water-conducting system, which is physically reinforced by the heterogeneous aromatic polymer lignin. Syringyl lignin, a major building block of lignin, is often thought to be uniquely characteristic of angiosperms; however, it was demonstrated over fifty years ago that that syringyl lignin is found in another group of plants, known as the lycophytes, the ancestors of which diverged from all the other vascular plant lineages 400 million years ago.1 To determine the biochemical basis for this common biosynthetic ability, we isolated and characterized cytochrome P450-dependent monooxygenases (P450s) from the lycophyte Selaginella moellendorffii and compared them to the enzyme that is required for syringyl lignin synthesis in angiosperms. Our results showed that one of these P450s encodes an enzyme that is functionally analogous to but phylogenetically independent from its angiosperm counterpart. Here, we discuss the evolution of lignin biosynthesis in vascular plants and the role of Selaginella moellendorffii in plant comparative biology and genomics. PMID:19704782

  4. Nanostructure sensor of presence and concentration of a target molecule

    NASA Technical Reports Server (NTRS)

    Schipper, John F. (Inventor)

    2009-01-01

    Method and system (i) to determine when a selected target molecule is present or absent in a fluid, (2) to estimate concentration of the target molecule in the fluid and (3) estimate possible presence of a second (different) target molecule in the fluid, by analyzing differences in resonant frequencies of vibration of a thin beam suspended in the fluid, after the fluid has moved across the beam.

  5. Fungal demethylation of Kraft lignin.

    PubMed

    Zou, Linyou; Ross, Brian M; Hutchison, Leonard J; Christopher, Lew P; Dekker, Robert F H; Malek, Lada

    2015-06-01

    Demethylation of industrial lignin has been for long coveted as a pathway to the production of an abundant natural substitute for fossil-oil derived phenol. In an attempt to possibly identify a novel Kraft lignin-demethylating enzyme, we surveyed a collection of fungi by using selected ion flow tube-mass spectrometry (SIFT-MS). This method readily identifies methanol resulting from lignin demethylation activity. Absidia cylindrospora, and unidentified Cylindrocladium sp. and Aspergillus sp. were shown to metabolize lignin via different pathways, based on the HPLC analysis of lignin fragments. Of these three, Cylindrocladium and Aspergillus were shown to retain most of the lignin intact after 3 weeks in culture, while removing about 40% of the available methoxy groups. Our results demonstrate that after optimization of culture and lignin recovery methods, biological modification of Kraft lignin may be a feasible pathway to obtaining demethylated lignin for further industrial use.

  6. Determination of chlorine concentration using single temperature modulated semiconductor gas sensor

    NASA Astrophysics Data System (ADS)

    Woźniak, Ł.; Kalinowski, P.; Jasiński, G.; Jasiński, P.

    2016-11-01

    A periodic temperature modulation using sinusoidal heater voltage was applied to a commercial SnO2 semiconductor gas sensor. Resulting resistance response of the sensor was analyzed using a feature extraction method based on Fast Fourier Transformation (FFT). The amplitudes of the higher harmonics of the FFT from the dynamic nonlinear responses of measured gas were further utilized as an input for Artificial Neuron Network (ANN). Determination of the concentration of chlorine was performed. Moreover, this work evaluates the sensor performance upon sinusoidal temperature modulation.

  7. Study of a computer-controlled integrated optical gas-concentration sensor

    SciTech Connect

    Egorov, A A; Egorov, M A; Chekhlova, T K; Timakin, A G

    2008-08-31

    A computer-controlled integrated optical waveguide sensor based on an optical waveguide of the diffusion type with the low attenuation coefficient is developed and studied. It is shown that the response time of the sensor is {approx}0.15 s. According to tests and computer simulations, the sensor can detect gaseous ammonia in air with the limiting theoretical concentration of {approx}0.1 ppm for the signal-to-noise ratio no less than 20. (laser applications and other topics in quantum electronics)

  8. The impact of lignin source on its self-assembly in solution

    DOE PAGES

    Ratnaweera, Dilru R.; Saha, Dipendu; Pingali, Sai Venkatesh; ...

    2015-07-30

    Recently, there has been a growing interest in developing value added uses for lignin, including the utilization of lignins as a precursor for carbon materials. Proper understanding of the association behavior of lignins during solution processing provides important structural information that is needed to rationally optimize the use of lignins in industry in a range of value added applications. In this paper, we follow the assembly of lignin molecules from a variety of sources in dimethyl sulfoxide, a good solvent for lignins, using small angle neutron scattering. In order to mimic industrial processing conditions, concentrations of lignins were kept abovemore » the overlap concentration. At small length scales, short lignin segments with ~4–10 monolignol units associate to form rigid rod-like/cylindrical building blocks, where the number of repeat units in a cylindrical segment decreases with increasing lignin concentration. These cylindrical building blocks associate to form aggregates with low cross-linking densities and a random coil or network like structures from highly branched lignin structures. The degree of branching of the base lignin molecule, which varies with source, plays a crucial role in determining their association behavior. Finally, the overall sizes of the aggregates decrease with increasing concentration at low cross-linking densities, whereas the opposite trend is observed for highly branched lignins.« less

  9. The impact of lignin source on its self-assembly in solution

    SciTech Connect

    Ratnaweera, Dilru R.; Saha, Dipendu; Pingali, Sai Venkatesh; Labbé, Nicole; Naskar, Amit K.; Dadmun, Mark

    2015-07-30

    Recently, there has been a growing interest in developing value added uses for lignin, including the utilization of lignins as a precursor for carbon materials. Proper understanding of the association behavior of lignins during solution processing provides important structural information that is needed to rationally optimize the use of lignins in industry in a range of value added applications. In this paper, we follow the assembly of lignin molecules from a variety of sources in dimethyl sulfoxide, a good solvent for lignins, using small angle neutron scattering. In order to mimic industrial processing conditions, concentrations of lignins were kept above the overlap concentration. At small length scales, short lignin segments with ~4–10 monolignol units associate to form rigid rod-like/cylindrical building blocks, where the number of repeat units in a cylindrical segment decreases with increasing lignin concentration. These cylindrical building blocks associate to form aggregates with low cross-linking densities and a random coil or network like structures from highly branched lignin structures. The degree of branching of the base lignin molecule, which varies with source, plays a crucial role in determining their association behavior. Finally, the overall sizes of the aggregates decrease with increasing concentration at low cross-linking densities, whereas the opposite trend is observed for highly branched lignins.

  10. Lignin isolation process from rice husk by alkaline hydrogen peroxide: Lignin and silica extracted

    NASA Astrophysics Data System (ADS)

    Ma'ruf, Anwar; Pramudono, Bambang; Aryanti, Nita

    2017-03-01

    Biomass is one of abundance resources in the world. Biomass consists of three main materials such as cellulose, hemicelluloses and lignin. Therefore, biomass can be referred to lignocellulosic material. Both the cellulose and hemicelluloses fractions are polymers of sugars, and thereby a potential source of fermentable sugars, or other processes that convert sugars into products. Lignin is a polymer compound which contains of phenolic compounds. Rice husk is one of biomass, which has high contain of lignin. Rice husk has special characteristics because of silica content. The aim of this paper is to analyze lignin and silica extracted during lignin isolation process of rice husk using alkaline hydrogen peroxide. Three main variables such as solvent/solid ratio, concentration of hydrogen peroxide and pH of the mixture are studied. The optimum conditions for lignin isolation are at solvent/solid ratio 9:1 ml/gr, hydrogen peroxide concentration of 1.5%v and pH of the mixture of 11.

  11. Lignin-degrading enzymes.

    PubMed

    Pollegioni, Loredano; Tonin, Fabio; Rosini, Elena

    2015-04-01

    A main goal of green biotechnology is to reduce our dependence on fossil reserves and to increase the use of renewable materials. For this, lignocellulose, which is composed of cellulose, hemicellulose and lignin, represents the most promising feedstock. The latter is a complex aromatic heteropolymer formed by radical polymerization of guaiacyl, syringyl, and p-hydroxyphenyl units linked by β-aryl ether linkages, biphenyl bonds and heterocyclic linkages. Accordingly, lignin appears to be a potentially valuable renewable aromatic chemical, thus representing a main pillar in future biorefinery. The resistance of lignin to breakdown is the main bottleneck in this process, although a variety of white-rot fungi, as well as bacteria, have been reported to degrade lignin by employing different enzymes and catabolic pathways. Here, recent investigations have expanded the range of natural biocatalysts involved in lignin degradation/modification and significant progress related to enzyme engineering and recombinant expression has been made. The present review is focused primarily on recent trends in ligninolytic green biotechnology to suggest the potential (industrial) application of ligninolytic enzymes. Future perspectives could include synergy between natural enzymes from different sources (as well as those obtained by protein engineering) and other pretreatment methods that may be required for optimal results in enzyme-based, environmentally friendly, technologies.

  12. Intelligent Fiber Optic Sensor for Estimating the Concentration of a Mixture-Design and Working Principle

    PubMed Central

    Borecki, Michal

    2007-01-01

    This paper presents the construction and working principles of an intelligent fiber-optic intensity sensor used for examining the concentration of a mixture in conjunction with water. It can find applications e.g. in waste-water treatment plant for selection of a treatment process. The sensor head is the end of a large core polymer optical fiber, which constitutes one arm of an asymmetrical coupler. The head works on the reflection intensity basis. The reflected signal level depends on the Fresnel reflection from the air and from the mixture examined when the head is immersed in it. The sensor head is mounted on a lift. For detection purposes the signal can be measured on head submerging, submersion, emerging and emergence. Therefore, the measured signal depends on the surface tension, viscosity, turbidity and refraction coefficient of the solution. The signal coming from the head is processed electrically in an opto-electronic interface. Then it is fed to a neural network. The novelty of the proposed sensor lies in that it contains an asymmetrical coupler and a neural network that works in the generalization mode. The sensor resolution depends on the efficiency of the asymmetrical coupler, the precision of the opto-electronic signal conversion and the learning accuracy of the neural network. Therefore, the number and quality of the points used for the learning process is very important. By way of example, the paper describes a sensor intended for examining the concentration of liquid soap in water.

  13. Chromium adsorption by lignin

    SciTech Connect

    Lalvani, S.B.; Huebner, A.; Wiltowski, T.S.

    2000-01-01

    Hexavalent chromium is a known carcinogen, and its maximum contamination level in drinking water is determined by the US Environmental Protection Agency (EPA). Chromium in the wastewaters from plating and metal finishing, tanning, and photographic industries poses environmental problems. A commercially available lignin was used for the removal of hexavalent as well as trivalent chromium from aqueous solution. It is known that hexavalent chromium is present as an anionic species in the solution. It was found that lignin can remove up to 63% hexavalent and 100% trivalent chromium from aqueous solutions. The removal of chromium ions was also investigated using a commercially available activated carbon. This absorbent facilitated very little hexavalent and almost complete trivalent chromium removal. Adsorption isotherms and kinetics data on the metal removal by lignin and activated carbon are presented and discussed.

  14. Lignin analysis using microwave digestion.

    PubMed

    Gassara, Fatma; Ajila, C M; Brar, Satinder K; Tyagi, R D; Verma, M; Valero, J R

    2012-10-01

    Lignin quantification in apple pomace residues was carried out using a microwave oven to replace traditional refluxing during the mild acidolysis step to augment the selectivity of this step towards cleavage of lignin-carbohydrate bonds and to reduce the time needed to quantify lignin. The pressure, temperature and time were optimized by response surface methodology and the results were compared to the Klason lignin methodology. Temperature and pressure had a significant positive effect (p < 0.05) on the determination of lignin. However, the time was also significant (p < 0.05) on lignin quantification. The optimal conditions of digestion were: 30 bar, 170 °C for 15 min. The digestion using microwave (lignin content = 33 % w/w) was more accurate (p < 0.05) than the the traditional refluxing (lignin content = 27 % w/w).

  15. An integrated temperature-compensated flexible shear-stress sensor microarray with concentrated leading-wire.

    PubMed

    Tang, Jian; Liu, Wu; Zhang, Weiping; Sun, Yongming; Chen, Honghai

    2016-02-01

    Flexible shear stress sensor is quite important for characterizing curved surface flows. In this work, a novel integrated shear stress sensor microarray is designed with twenty parallel channels, which share the concentrated leading-wire to transmit the ground signal. Electrical pads in rows are easily connected to the circuits with two separate Wheatstone bridges and constant-temperature-difference mode operation is provided for the hot-wires. Temperature crosstalk between adjacent hot-wires is prevented well and the effectiveness of the temperature compensated circuits is verified. Relatively large output response is obtained as the shear stress varies and the sensitivity of the sensors is measured about 0.086 V(2)/Pa(1/3) with nonlinearity lower than 1%, revealing high performance characteristic of the sensors.

  16. Polymer optical fiber compound parabolic concentrator tip for enhanced coupling efficiency for fluorescence based glucose sensors.

    PubMed

    Hassan, Hafeez Ul; Nielsen, Kristian; Aasmul, Soren; Bang, Ole

    2015-12-01

    We demonstrate that the light excitation and capturing efficiency of fluorescence based fiber-optical sensors can be significantly increased by using a CPC (Compound Parabolic Concentrator) tip instead of the standard plane-cut tip. We use Zemax modelling to find the optimum CPC tip profile and fiber length of a polymer optical fiber diabetes sensor for continuous monitoring of glucose levels. We experimentally verify the improved performance of the CPC tipped sensor and the predicted production tolerances. Due to physical size requirements when the sensor has to be inserted into the body a non-optimal fiber length of 35 mm is chosen. For this length an average improvement in efficiency of a factor of 1.7 is experimentally demonstrated and critically compared to the predicted ideal factor of 3 in terms of parameters that should be improved through production optimization.

  17. Extracting lignins from mill wastes

    NASA Technical Reports Server (NTRS)

    Humphrey, M. F.

    1977-01-01

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

  18. Single ZnO Nanowire-Based Gas Sensors to Detect Low Concentrations of Hydrogen

    PubMed Central

    Cardoza-Contreras, Marlene N.; Romo-Herrera, José M.; Ríos, Luis A.; García-Gutiérrez, R.; Zepeda, T. A.; Contreras, Oscar E.

    2015-01-01

    Low concentrations of hazardous gases are difficult to detect with common gas sensors. Using semiconductor nanostructures as a sensor element is an alternative. Single ZnO nanowire gas sensor devices were fabricated by manipulation and connection of a single nanowire into a four-electrode aluminum probe in situ in a dual-beam scanning electron microscope-focused ion beam with a manipulator and a gas injection system in/column. The electrical response of the manufactured devices shows response times up to 29 s for a 121 ppm of H2 pulse, with a variation in the nanowire resistance appreciable at room temperature and at 373.15 K of approximately 8% and 14% respectively, showing that ZnO nanowires are good candidates to detect low concentrations of H2. PMID:26690158

  19. Single ZnO Nanowire-Based Gas Sensors to Detect Low Concentrations of Hydrogen.

    PubMed

    Cardoza-Contreras, Marlene N; Romo-Herrera, José M; Ríos, Luis A; García-Gutiérrez, R; Zepeda, T A; Contreras, Oscar E

    2015-12-04

    Low concentrations of hazardous gases are difficult to detect with common gas sensors. Using semiconductor nanostructures as a sensor element is an alternative. Single ZnO nanowire gas sensor devices were fabricated by manipulation and connection of a single nanowire into a four-electrode aluminum probe in situ in a dual-beam scanning electron microscope-focused ion beam with a manipulator and a gas injection system in/column. The electrical response of the manufactured devices shows response times up to 29 s for a 121 ppm of H₂ pulse, with a variation in the nanowire resistance appreciable at room temperature and at 373.15 K of approximately 8% and 14% respectively, showing that ZnO nanowires are good candidates to detect low concentrations of H₂.

  20. Utilizing existing sensor technology to predict spring wheat grain nitrogen concentration

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Obtaining optimum grain N concentration and yield in spring wheat (Triticum aestivum L.) can be problematic without proper nitrogen (N) fertilizer management. Sensor-based technologies have been used for an accurate and precise application of fertilizers. This technology has also been used to predic...

  1. Temperature Compensation in Determining of Remazol Black B Concentrations Using Plastic Optical Fiber Based Sensor

    PubMed Central

    Chong, Su Sin; Aziz, A.R. Abdul; Harun, Sulaiman W.; Arof, Hamzah

    2014-01-01

    In this study, the construction and test of tapered plastic optical fiber (POF) sensors, based on an intensity modulation approach are described. Tapered fiber sensors with different diameters of 0.65 mm, 0.45 mm, and 0.35 mm, were used to measure various concentrations of Remazol black B (RBB) dye aqueous solutions at room temperature. The concentrations of the RBB solutions were varied from 0 ppm to 70 ppm. In addition, the effect of varying the temperature of the RBB solution was also investigated. In this case, the output of the sensor was measured at four different temperatures of 27 °C, 30 °C, 35 °C, and 40 °C, while its concentration was fixed at 50 ppm and 100 ppm. The experimental results show that the tapered POF with d = 0.45 mm achieves the best performance with a reasonably good sensitivity of 61 × 10−4 and a linearity of more than 99%. It also maintains a sufficient and stable signal when heat was applied to the solution with a linearity of more than 97%. Since the transmitted intensity is dependent on both the concentration and temperature of the analyte, multiple linear regression analysis was performed to combine the two independent variables into a single equation. The resulting equation was then validated experimentally and the best agreement between the calculated and experimental results was achieved by the sensor with d = 0.45 mm, where the minimum discrepancy is less than 5%. The authors conclude that POF-based sensors are suitable for RBB dye concentration sensing and, with refinement in fabrication, better results could be achieved. Their low fabrication cost, simple configuration, accuracy, and high sensitivity would attract many potential applications in chemical and biological sensing. PMID:25166498

  2. Lignin blockers and uses thereof

    SciTech Connect

    Yang, Bin; Wyman, Charles E

    2011-01-25

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

  3. 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.

  4. Lignin-Based Thermoplastic Materials.

    PubMed

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

    2016-04-21

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

  5. Performance of a low-cost methane sensor for ambient concentration measurements in preliminary studies

    NASA Astrophysics Data System (ADS)

    Eugster, W.; Kling, G. W.

    2012-03-01

    Methane is the second most important greenhouse gas after CO2 and contributes to global warming. Its sources are not uniformly distributed across terrestrial and aquatic ecosystems, and most of the methane flux is expected to stem from hotspots which often occupy a very small fraction of the total landscape area. Continuous time-series measurements of CH4 concentrations can help identify and locate these methane hot-spots. Newer, low-cost trace gas sensors such as the Figaro TGS 2600 can detect CH4 even at ambient concentrations. Hence, in this paper we tested this sensor under real-world conditions over Toolik Lake, Alaska, to determine its suitability for preliminary studies before placing more expensive and service-intensive equipment at a given locality. A reasonably good agreement with parallel measurements made using a Los Gatos Research FMA 100 methane analyzer was found after removal of the strong cross-sensitivities for temperature and relative humidity. Correcting for this cross-sensitivity increased the absolute accuracy required for in-depth studies, and the reproducibility between two TGS 2600 sensors run in parallel is very good. We conclude that the relative CH4 concentrations derived from such sensors are sufficient for preliminary investigations in the search of potential methane hot-spots.

  6. Performance of a low-cost methane sensor for ambient concentration measurements in preliminary studies

    NASA Astrophysics Data System (ADS)

    Eugster, W.; Kling, G. W.

    2012-08-01

    Methane is the second most important greenhouse gas after CO2 and contributes to global warming. Its sources are not uniformly distributed across terrestrial and aquatic ecosystems, and most of the methane flux is expected to stem from hotspots which often occupy a very small fraction of the total landscape area. Continuous time-series measurements of CH4 concentrations can help identify and locate these methane hotspots. Newer, low-cost trace gas sensors such as the Figaro TGS 2600 can detect CH4 even at ambient concentrations. Hence, in this paper we tested this sensor under real-world conditions over Toolik Lake, Alaska, to determine its suitability for preliminary studies before placing more expensive and service-intensive equipment at a given locality. A reasonably good agreement with parallel measurements made using a Los Gatos Research FMA 100 methane analyzer was found after removal of the strong sensitivities for temperature and relative humidity. Correcting for this sensitivity increased the absolute accuracy required for in-depth studies, and the reproducibility between two TGS 2600 sensors run in parallel is very good. We conclude that the relative CH4 concentrations derived from such sensors are sufficient for preliminary investigations in the search of potential methane hotspots.

  7. A Spectrometric Method for Hydrogen Peroxide Concentration Measurement with a Reusable and Cost-Efficient Sensor

    PubMed Central

    Hsu, Cheng-Chih; Lo, Yuan-Rong; Lin, Yu-Chian; Shi, Yi-Cen; Li, Pang-Lung

    2015-01-01

    In this study we developed a low cost sensor for measuring the concentration of hydrogen peroxide (H2O2) in liquids utilizing a spectrometric method. The sensor was tested using various concentrations of a peroxidase enzyme immobilized on a glass substrate. H2O2 can be catalyzed by peroxidase and converted into water and oxygen. The reagent 4-amino-phenazone takes up oxygen together with phenol to form a colored product that has absorption peaks at 510 nm and 450 nm. The transmission intensity is strongly related to the hydrogen peroxide concentration, so can be used for quantitative analysis. The measurement range for hydrogen peroxide is from 5 × 10−5% to 1 × 10−3% (0.5 ppm to 10 ppm) and the results show high linearity. This device can achieve a sensitivity and resolution of 41,400 (photon count/%) and 3.49 × 10−5% (0.35 ppm), respectively. The response time of the sensor is less than 3 min and the sensor can be reused for 10 applications with similar performance. PMID:26473862

  8. Cell suspension concentration monitoring by using a miniaturized serial high frequency SAWR sensor

    PubMed Central

    Li, Jian; Feng, Hailin; Fang, Yiming

    2015-01-01

    In this paper, a miniaturized cell suspension concentration monitoring method was investigated. The sensing unit was a carbon screen-printed electrode (CSPE) in serial with a 433MHz vacuum-packaged surface acoustic wave resonator (SAWR). SAWR provided a stable and high operating frequency, which helps to keep the stability and sensitivity of the monitoring system. Living cells suspensions in different concentrations were prepared and dropcast on CSPE. Frequency responses of the sensor were recorded. Cell quantity variation within the same culture media volume changed the dielectric properties of CSPE and finally affected the SAWR frequency. SAWR frequency declined with the decrease of cell concentration. The proposed sensor provided high sensitivity and remarkable stability for the cell suspensions. PMID:26588250

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

    PubMed

    Wang, Guanhua; Chen, Hongzhang

    2014-06-01

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

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

    SciTech Connect

    Sadeghifar, Hasan; Wells, Tyrone; Le, Rosemary Khuu; Sadeghifar, Fatemeh; Yuan, Joshua S.; Jonas Ragauskas, Arthur

    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 fractions showed strong antioxidant activity.

  11. 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

  12. Conversion of lignin into a precursor for the production of graphitic carbon materials

    SciTech Connect

    Nelson, C.M.; Serio, M.A.; Kroo, E.

    1995-11-01

    Lignin is the most abundant renewable aromatic material. There are roughly 25 x 10{sup 6} tons of lignin produced each year as a byproduct of pulp and papermaking which has a fuel value of between $0.00 and $0.04 per pound. Carbon materials are among the highest value products can be produced from lignin. Consequently, the development of processes which can utilize lignins for carbon fibers or the production of other high value carbon materials has the potential for a high payoff. It would also result in the utilization of lignin as a raw material for high technology, internationally competitive industries. The ability to form graphitic carbon materials from pitch depends on the development of a liquid crystal system called mesophase. A major problem with using lignin as a precursor for the production of mesophase pitch is the high oxygen functional group concentration of lignin which makes it reactive toward crosslinking. Hydrothermal treatment of lignin allows for selective removal of the reactive oxygen functional groups from lignin which normally prevent extensive mesophase formation. Hydrothermal pretreatment of lignin substantially increases the mesophase content of lignin-derived pitch. This development will make lignin a suitable precursor for a range of carbon materials applications.

  13. Utilizing an open-microcavity optoacoustic sensor for spectroscopic determination of methemoglobin concentration

    NASA Astrophysics Data System (ADS)

    Peterson, Ralph W.; Kadugodinandareddy, Kavya; Karunakaran, Vinitha; Whitney, Casey; Ling, Jian; Ye, Jing Yong

    2015-03-01

    We present a simple, non-destructive photoacoustic spectroscopy method utilizing a unique open-microcavity optoacoustic sensor to measure the concentration ratio of Methemoglobin (MetHb) in an optically scattering medium. Elevated levels of MetHb, present for example in the blood disorder Methemeglobinemia, cannot be detected by conventional pulse oximetry, and may result in inaccurate arterial oxygen saturation measurements. Samples with different ratios of Oxygenated Hemoglobin (HbO2), Deoxygenated Hemoglobin (HHb), and MetHb were obtained and mixed with nanoscale latex beads to present an optical scattering effect. Polymer encapsulated hemoglobin (PEH) samples were also studied. A sample chamber containing 20 μL of each sample was positioned directly underneath our patented optoacoustic sensor. Unlike a piezoelectric transducer, our optoacoustic sensor allows an excitation laser beam from an OPO laser to pass through and be absorbed by the sample to produce a photoacoustic signal. The cavity layer of the optoacoustic sensor is exposed directly to the resulting ultrasound signal, which causes an intensity modulation of a HeNe laser that is used to monitor the resonance condition of the sensor. A probe laser beam is total internally reflected off of the sensor and detected with a fiber-coupled APD detector. Three wavelengths are chosen for our excitation laser based on the absorption peaks and isobestic points of HHb, HbO2, and MetHb. Using established values of the molar extinction coefficients of HbO2, HHb, and MetHb a set of three simultaneous equations can be solved to accurately determine the concentration ratio of MetHb.

  14. High-sensitivity in situ QCLAS-based ammonia concentration sensor for high-temperature applications

    NASA Astrophysics Data System (ADS)

    Peng, W. Y.; Sur, R.; Strand, C. L.; Spearrin, R. M.; Jeffries, J. B.; Hanson, R. K.

    2016-07-01

    A novel quantum cascade laser (QCL) absorption sensor is presented for high-sensitivity in situ measurements of ammonia (hbox {NH}_3) in high-temperature environments, using scanned wavelength modulation spectroscopy (WMS) with first-harmonic-normalized second-harmonic detection (scanned WMS-2 f/1 f) to neutralize the effect of non-absorption losses in the harsh environment. The sensor utilized the sQ(9,9) transition of the fundamental symmetric stretch band of hbox {NH}_3 at 10.39 {\\upmu }hbox {m} and was sinusoidally modulated at 10 kHz and scanned across the peak of the absorption feature at 50 Hz, leading to a detection bandwidth of 100 Hz. A novel technique was used to select an optimal WMS modulation depth parameter that reduced the sensor's sensitivity to spectral interference from hbox {H}_2hbox {O} and hbox {CO}_2 without significantly sacrificing signal-to-noise ratio. The sensor performance was validated by measuring known concentrations of hbox {NH}_3 in a flowing gas cell. The sensor was then demonstrated in a laboratory-scale methane-air burner seeded with hbox {NH}_3, achieving a demonstrated detection limit of 2.8 ± 0.26 ppm hbox {NH}_3 by mole at a path length of 179 cm, equivalence ratio of 0.6, pressure of 1 atm, and temperatures of up to 600 K.

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

    PubMed

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

    2016-03-15

    Lignin is an abundant biopolymer that has native interfacial functions but aggregates strongly in aqueous media. Polyacrylamide was grafted onto kraft lignin nanoparticles using reversible addition-fragmentation chain transfer (RAFT) chemistry to form polymer-grafted lignin nanoparticles (PGLNs) that tune aggregation strength while retaining interfacial activities in forming Pickering emulsions. Polymer graft density on the particle surface, ionic strength, and initial water and cyclohexane volume fractions were varied and found to have profound effects on emulsion characteristics, including emulsion volume fraction, droplet size, and particle interfacial concentration that were attributed to changes in lignin aggregation and hydrophobic interactions. In particular, salt concentration was found to have a significant effect on aggregation, zeta potential, and interfacial tension, which was attributed to changes in solubility of both the kraft lignin and the polyacrylamide grafts. Dynamic light scattering, UV-vis spectroscopy, optical microscopy, and tensiometry were used to quantify emulsion properties and nanoparticle behavior. Under all conditions, the emulsions exhibited relatively fast creaming but were stable against coalescence and Ostwald ripening for a period of months. All emulsions were also oil-in-water (o/w) emulsions, as predicted by the Bancroft rule, and no catastrophic phase inversions were observed for any nanoparticle compositions. We conclude that lower grafting density of polyacrylamide on a lignin core resulted in high levels of interfacial activity, as characterized by higher concentration at the water-cyclohexane interface with a corresponding decrease in interfacial tension. These results indicate that the interfacial properties of polymer-grafted lignin nanoparticles are primarily due to the native hydrophobic interactions of the lignin core. These results suggest that the forces that drive aggregation are also correlated with interfacial

  16. Dual Mode NOx Sensor: Measuring Both the Accumulated Amount and Instantaneous Level at Low Concentrations

    PubMed Central

    Groß, Andrea; Beulertz, Gregor; Marr, Isabella; Kubinski, David J.; Visser, Jaco H.; Moos, Ralf

    2012-01-01

    The accumulating-type (or integrating-type) NOx sensor principle offers two operation modes to measure low levels of NOx: The direct signal gives the total amount dosed over a time interval and its derivative the instantaneous concentration. With a linear sensor response, no baseline drift, and both response times and recovery times in the range of the gas exchange time of the test bench (5 to 7 s), the integrating sensor is well suited to reliably detect low levels of NOx. Experimental results are presented demonstrating the sensor’s integrating properties for the total amount detection and its sensitivity to both NO and to NO2. We also show the correlation between the derivative of the sensor signal and the known gas concentration. The long-term detection of NOx in the sub-ppm range (e.g., for air quality measurements) is discussed. Additionally, a self-adaption of the measurement range taking advantage of the temperature dependency of the sensitivity is addressed. PMID:22736980

  17. Lignin as renewable raw material.

    PubMed

    Calvo-Flores, Francisco García; Dobado, José A

    2010-11-22

    Lignin is by far the most abundant substance based on aromatic moieties in nature, and the largest contributor to soil organic matter. Millions of tonnes of several lignin preparations are produced by the paper industry every year, and a minimal amount of lignin is isolated by direct extraction of lignin from plants. Lignin is used either directly or chemically modified, as a binder, dispersant agent for pesticides, emulsifier, heavy metal sequestrant, or component for composites and copolymers. For value-added applications of lignin to be improved, medium- and long-term conversion technologies must be developed, especially for the preparation of low-molecular-weight compounds as an alternative to the petrochemical industry.

  18. Development of New Optical Sensors for Measurements of Mercury Concentrations, Speciation, and Chemistry

    SciTech Connect

    Robert Lucht

    2008-09-28

    A diode-laser-based ultraviolet absorption sensor for elemental mercury was developed and applied for measurements in a high-temperature flow reactor and in the exhaust stream of a coal-fired combustor. The final version of the sensor incorporates a 375-nm single-mode laser and a 784-nm distributed feedback (DFB) laser. The output of these lasers is sum-frequency mixed in a non-linear beta-barium borate crystal to generate a 254-nm beam. By tuning the frequency of the DFB laser, the ultraviolet beam frequency is tuned across the transition frequency of mercury at 253.7-nm. The tuning range is large enough that an off-resonant baseline was clearly visible on both sides of the Hg transition. Because of this large tuning range, the effects of broadband absorption can be effectively eliminated during data analysis. Broadband absorption is a major concern for lamp-based mercury sensor, and the sample to be monitored must be chemically treated prior to analysis to remove species such as SO{sub 2} that absorb near 253.7 nm. No pretreatment is required when our diode-laser-based sensor is used for elemental mercury measurements. Our laser sensor measurements were compared to measurements from a commercial mercury analyzer (CMA), and were generally in good agreement except that the insitu diode-laser-based sensor measurements tended to give somewhat higher concentrations than the CMA measurements, presumably due to absorption of elemental mercury in the sampling lines needed for the CMA measurements. At Texas A&M University, the homogeneous oxidation of elemental mercury was studied using a high-temperature flow reactor.

  19. On-line measurement of lignin in wood pulp by color shift of fluorescence

    DOEpatents

    Jeffers, Larry A.; Malito, Michael L.

    1996-01-01

    Lignin concentrations from wood pulp samples are measured by applying an excitation light at a selected wavelength to the samples in order to cause the lignin to emit fluorescence. A spectral distribution of the fluorescence emission is then determined. The lignin concentration is then calculated based on the spectral distribution signal. The spectral distribution is quantified by either a wavelength centroid method or a band ratio method.

  20. On-line measurement of lignin in wood pulp by color shift of fluorescence

    DOEpatents

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

    1996-01-23

    Lignin concentrations from wood pulp samples are measured by applying an excitation light at a selected wavelength to the samples in order to cause the lignin to emit fluorescence. A spectral distribution of the fluorescence emission is then determined. The lignin concentration is then calculated based on the spectral distribution signal. The spectral distribution is quantified by either a wavelength centroid method or a band ratio method. 6 figs.

  1. Design and Operation of an Electrochemical Methanol Concentration Sensor for Direct Methanol Fuel Cell Systems

    NASA Technical Reports Server (NTRS)

    Narayanan, S. R.; Valdez, T. I.; Chun, W.

    2000-01-01

    The development of a 150-Watt packaged power source based on liquid feed direct methanol fuel cells is being pursued currently at the Jet propulsion Laboratory for defense applications. In our studies we find that the concentration of methanol in the fuel circulation loop affects the electrical performance and efficiency the direct methanol fuel cell systems significantly. The practical operation of direct methanol fuel cell systems, therefore, requires accurate monitoring and control of methanol concentration. The present paper reports on the principle and demonstration of an in-house developed electrochemical sensor suitable for direct methanol fuel cell systems.

  2. Lignin blockers and uses thereof

    SciTech Connect

    Yang, Bin; Wyman, Charles E

    2013-11-12

    Disclosed is a method for converting cellulose in a lignocellulosic biomass. The method provides for a lignin-blocking polypeptide and/or protein treatment of high lignin solids. The treatment enhances cellulase availability in cellulose conversion and allows for the determination of optimized pretreatment conditions. Additionally, ethanol yields from a Simultaneous Saccharification and Fermentation process are improved 5-25% by treatment with a lignin-blocking polypeptide and/or protein.

  3. Using Bayesian Inference Framework towards Identifying Gas Species and Concentration from High Temperature Resistive Sensor Array Data

    DOE PAGES

    Liu, Yixin; Zhou, Kai; Lei, Yu

    2015-01-01

    High temperature gas sensors have been highly demanded for combustion process optimization and toxic emissions control, which usually suffer from poor selectivity. In order to solve this selectivity issue and identify unknown reducing gas species (CO, CH 4 , and CH 8 ) and concentrations, a high temperature resistive sensor array data set was built in this study based on 5 reported sensors. As each sensor showed specific responses towards different types of reducing gas with certain concentrations, based on which calibration curves were fitted, providing benchmark sensor array response database, then Bayesian inference framework was utilized to processmore » the sensor array data and build a sample selection program to simultaneously identify gas species and concentration, by formulating proper likelihood between input measured sensor array response pattern of an unknown gas and each sampled sensor array response pattern in benchmark database. This algorithm shows good robustness which can accurately identify gas species and predict gas concentration with a small error of less than 10% based on limited amount of experiment data. These features indicate that Bayesian probabilistic approach is a simple and efficient way to process sensor array data, which can significantly reduce the required computational overhead and training data.« less

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

    SciTech Connect

    Simo Sarkanen

    2002-02-04

    This project constituted an intensive effort devoted to producing, from the white-rot fungus Tramets Cingulata, a lignin degrading enzyme (lignin depolymerase) that is directly able to biobleach or delignify softwood kraft pulp brownstock. To this end, the solutions in which T. cingulata was grown contained dissolved kraft lignin which fulfilled two functions; it behaved as a lignin deploymerase substrate and it also appeared to act as an inducer of enzyme expression. However, the lignin depolymerase isoenzymes (and other extracellular T. cingulata enzymes) interacted very strongly with both the kraft lignin components and the fungal hypae, so the isolating these proteins from the culture solutions proved to be unexpectedly difficult. Even after extensive experimentation with a variety of protein purification techniques, only one approach appeared to be capable of purifying lignin depolymerases to homogeneity. Unfortunately the procedure was extremely laborious; it involved the iso electric focusing of concentrated buffer-exchanged culture solutions followed by electro-elution of the desired protein bands from the appropriate polyacrylamide gel segments

  5. 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

  6. Potentiometric Sensor for Real-Time Monitoring of Multivalent Ion Concentrations in Molten Salt

    SciTech Connect

    Peter A. Zink; Jan-Fong Jue; Brenda E. Serrano; Guy L. Fredrickson; Ben F. Cowan; Steven D. Herrmann; Shelly X. Li

    2010-07-01

    Electrorefining of spent metallic nuclear fuel in high temperature molten salt systems is a core technology in pyroprocessing, which in turn plays a critical role in the development of advanced fuel cycle technologies. In electrorefining, spent nuclear fuel is treated electrochemically in order to effect separations between uranium, noble metals, and active metals, which include the transuranics. The accumulation of active metals in a lithium chloride-potassium chloride (LiCl-KCl) eutectic molten salt electrolyte occurs at the expense of the UCl3-oxidant concentration in the electrolyte, which must be periodically replenished. Our interests lie with the accumulation of active metals in the molten salt electrolyte. The real-time monitoring of actinide concentrations in the molten salt electrolyte is highly desirable for controlling electrochemical operations and assuring materials control and accountancy. However, real-time monitoring is not possible with current methods for sampling and chemical analysis. A new solid-state electrochemical sensor is being developed for real-time monitoring of actinide ion concentrations in a molten salt electrorefiner. The ultimate function of the sensor is to monitor plutonium concentrations during electrorefining operations, but in this work gadolinium was employed as a surrogate material for plutonium. In a parametric study, polycrystalline sodium beta double-prime alumina (Na-ß?-alumina) discs and tubes were subject to vapor-phase exchange with gadolinium ions (Gd3+) using a gadolinium chloride salt (GdCl3) as a precursor to produce gadolinium beta double-prime alumina (Gd-ß?-alumina) samples. Electrochemical impedance spectroscopy and microstructural analysis were performed on the ion-exchanged discs to determine the relationship between ion exchange and Gd3+ ion conductivity. The ion-exchanged tubes were configured as potentiometric sensors in order to monitor real-time Gd3+ ion concentrations in mixtures of gadolinium

  7. Highly Sensitive Multi-Channel IDC Sensor Array for Low Concentration Taste Detection

    PubMed Central

    Khan, Md. Rajibur Rahaman; Kang, Shin-Won

    2015-01-01

    In this study, we designed and developed an interdigitated capacitor (IDC)-based taste sensor array to detect different taste substances. The designed taste sensing array has four IDC sensing elements. The four IDC taste sensing elements of the array are fabricated by incorporating four different types of lipids into the polymer, dioctyl phenylphosphonate (DOPP) and tetrahydrofuran (THF) to make the respective dielectric materials that are individually placed onto an interdigitated electrode (IDE) via spin coating. When the dielectric material of an IDC sensing element comes into contact with a taste substance, its dielectric properties change with the capacitance of the IDC sensing element; this, in turn, changes the voltage across the IDC, as well as the output voltage of each channel of the system. In order to assess the effectiveness of the sensing system, four taste substances, namely sourness (HCl), saltiness (NaCl), sweetness (glucose) and bitterness (quinine-HCl), were tested. The IDC taste sensor array had rapid response and recovery times of about 12.9 s and 13.39 s, respectively, with highly stable response properties. The response property of the proposed IDC taste sensor array was linear, and its correlation coefficient R2 was about 0.9958 over the dynamic range of the taste sensor array as the taste substance concentration was varied from 1 μM to 1 M. The proposed IDC taste sensor array has several other advantages, such as real-time monitoring capabilities, high sensitivity 45.78 mV/decade, good reproducibility with a standard deviation of about 0.029 and compactness, and the circuitry is based on readily available and inexpensive electronic components. The proposed IDC taste sensor array was compared with the potentiometric taste sensor with respect to sensitivity, dynamic range width, linearity and response time. We found that the proposed IDC sensor array has better performance. Finally, principal component analysis (PCA) was applied to

  8. Bioaerosol standoff detection and correlation assessment with concentration and viability point sensors

    NASA Astrophysics Data System (ADS)

    Buteau, Sylvie; Simard, Jean-Robert; Rowsell, Susan; Roy, Gilles

    2010-10-01

    A standoff bioaerosol sensor based on intensified range-gated spectrometric detection of Laser Induced Fluorescence was used to spectrally characterize bioaerosol simulants during in-chamber and open-air releases at Suffield, Canada, in August 2008 from a standoff position. In total, 42 in-chamber Bacillus atrophaeus (formerly Bacillus subtilis var globigii; BG) cloud and 27 open-air releases of either BG, Pantoea agglomerans (formerly Erwinia herbicola; EH), MS2 and ovalbumin (OV) were generated. The clouds were refereed by different point sensors including Aerodynamic Particle Sizer (APS) and slit or impingers samplers. The APS monitored the particle size distribution and concentration and the samplers characterized the viable portion of the cloud. The extracted spectral signatures show robustness to different degree. The correlation assessment showed good results in most cases where the LIF signal to noise ratio was significant. The sensor 4σ sensitivity was evaluated to 1 300, 600, 100 and 30 ppl for BG, OV, MS2 and EH respectively. Correlation results are presented by plotting the SINBAHD metric versus the corresponding particle concentration, in which case, the obtained slope is proportional to the material fluorescence cross-section. The different acquired signal is hence compared in terms of their fluorescence cross-section additionally to their spectral characteristics.

  9. Ethanol vapor above skin: determination by a gas sensor instrument and relationship with plasma concentration.

    PubMed

    Giles, H G; Meggiorini, S; Renaud, G E; Thiessen, J J; Vidins, E I; Compton, K V; Saldivia, V; Orrego, H; Israel, Y

    1987-06-01

    Studies with a new instrument show that blood ethanol concentrations in rats and humans can be estimated by measurement of ethanol vapor above the skin. After intravenous bolus administration of ethanol (1 g/kg) to rats a novel device based on the Figaro sensor was placed above the animal's abdomen. Plasma and skin vapor ethanol concentrations, analyzed by gas chromatography and sensor, respectively, declined in parallel (r = 0.96). In healthy human subjects, plasma and skin vapor concentrations, measured on the palm, also declined in parallel after intravenous ethanol infusion (1 hr, 0.5 g/kg), r = 0.99. In 10 alcoholic liver disease outpatients attending clinic in whom plasma ethanol concentrations ranged from 32-304 mg/dl, the correlation of plasma ethanol determined directly by gas chromatography and indirectly by skin vapor analysis was slope = 0.93, intercept = 1.8, r = 0.94. In controlled studies, skin vapor measurements are comparable with breathalyzer determinations; they may be performed in situations where breathalyzer measurements are inconvenient or where continuous monitoring is desirable.

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

    PubMed

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

    2014-05-16

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

  11. Lignin Valorization: Improving Lignin Processing in the Biorefinery

    SciTech Connect

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

    2014-01-01

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

  12. Development of a diagnostic sensor for measuring blood cell concentrations during haemoconcentration

    PubMed Central

    Robertson, Craig A.; Gourlay, Terence

    2016-01-01

    Background: HemoSep® is a commercial ultrafiltration and haemoconcentration device for the concentration of residual bypass blood following surgery. This technology is capable of reducing blood loss in cardiac and other types of “clean site” procedures, including paediatric surgery. Clinical feedback suggested that the device would be enhanced by including a sensor technology capable of discerning the concentration level of the processed blood product. We sought to develop a novel sensor that can, using light absorption, give an accurate estimate of packed cell volume (PCV). Materials and methods: A sensor-housing unit was 3D printed and the factors influencing the sensor’s effectiveness – supply voltage, sensitivity and emitter intensity - were optimised. We developed a smart system, using comparator circuitry capable of visually informing the user when adequate PCV levels (⩾35%) are attained by HemoSep® blood processing, which ultimately indicates that the blood is ready for autotransfusion. Results: Our data demonstrated that the device was capable of identifying blood concentration at and beyond the 35% PCV level. The device was found to be 100% accurate at identifying concentration levels of 35% from a starting level of 20%. Discussion: The sensory capability was integrated into HemoSep’s® current device and is designed to enhance the user’s clinical experience and to optimise the benefits of HemoSep® therapy. The present study focused on laboratory studies using bovine blood. Further studies are now planned in the clinical setting to confirm the efficacy of the device. PMID:27591743

  13. Lignin Bioproducts to Enable Biofuels

    SciTech Connect

    Wyman, Charles E.; Ragauskas, Arthur J

    2015-09-15

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

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

    PubMed Central

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

    2016-01-01

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

  15. 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.

  16. Determination of D- and L-alanine concentrations using a pyruvic acid sensor.

    PubMed

    Inaba, Yohei; Hamada-Sato, Naoko; Kobayashi, Takeshi; Imada, Chiaki; Watanabe, Etsuo

    2003-08-01

    The concentrations of D- and L-alanine in bivalves are useful as indicators of environmental pollution. Amino acid oxidase with a low substrate specificity catalyzes the oxidation of various amino acids. Among the various amino acids, pyruvic acid can be generated from alanine only by the catalytic oxidative reaction of this oxidase. Therefore, in this study, the concentrations of D- and L-alanine were determined from the concentration of pyruvic acid, which was determined from the consumption of oxygen based on the oxidative reaction of pyruvate oxidase. From this point of view, there is a very strong possibility that biosensors utilizing enzymes with a low substrate specificity can be developed. The results obtained were as follows. (1) The optimum conditions for the use of pyruvic acid sensor were as follows: temperature of 25 degrees C, pH of 6.8, flow rate of 0.1 ml/min, thiamin diphosphate concentration of 1.5 mM, and injection volume of 50 microl. (2) D-Alanine and L-alanine optimally reacted with D- and L-amino acid oxidase at 30 degrees C, pH 8.2, for 30 min and at 37 degrees C, pH 7.8, for 90 min, respectively. (3) The linear relationships between the concentrations of D- and L-alanine and the output of the sensor were obtained at 3.56-106.8 microg of D-alanine and 5.34-71.3 microg of L-alanine. (4) The concentrations of D- and L-alanine in Meretrix iusoria, Patinopecten yessonsi, and Corbicula leana obtained by the proposed assay were in good agreement with those determined by a conventional method.

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

    PubMed Central

    Humpert, Daniel; Ebrahimi, Mehrdad; Czermak, Peter

    2016-01-01

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

  18. Self-Powered Active Sensor with Concentric Topography of Piezoelectric Fibers

    NASA Astrophysics Data System (ADS)

    Fuh, Yiin Kuen; Huang, Zih Ming; Wang, Bo Sheng; Li, Shan Chien

    2017-01-01

    In this study, we demonstrated a flexible and self-powered sensor based on piezoelectric fibers in the diameter range of nano- and micro-scales. Our work is distinctively different from previous electrospinning research; we fabricated this apparatus precisely via near-field electrospinning which has a spectacular performance to harvest mechanical deformation in arbitrary direction and a novel concentrically circular topography. There are many piezoelectric devices based on electrospinning polymeric fibers. However, the fibers were mostly patterned in parallel lines and they could be actuated in limited direction only. To overcome this predicament, we re-arranged the parallel alignment into concentric circle pattern which made it possible to collect the mechanical energy whenever the deformation is along same axis or not. Despite the change of topography, the output voltage and current could still reach to 5 V and 400 nA, respectively, despite the mechanical deformation was from different direction. This new arbitrarily directional piezoelectric generator with concentrically circular topography (PGCT) allowed the piezoelectric device to harvest more mechanical energy than the one-directional alignment fiber-based devices, and this PGCT could perform even better output which promised more versatile and efficient using as a wearable electronics or sensor.

  19. Self-Powered Active Sensor with Concentric Topography of Piezoelectric Fibers.

    PubMed

    Fuh, Yiin Kuen; Huang, Zih Ming; Wang, Bo Sheng; Li, Shan Chien

    2017-12-01

    In this study, we demonstrated a flexible and self-powered sensor based on piezoelectric fibers in the diameter range of nano- and micro-scales. Our work is distinctively different from previous electrospinning research; we fabricated this apparatus precisely via near-field electrospinning which has a spectacular performance to harvest mechanical deformation in arbitrary direction and a novel concentrically circular topography. There are many piezoelectric devices based on electrospinning polymeric fibers. However, the fibers were mostly patterned in parallel lines and they could be actuated in limited direction only. To overcome this predicament, we re-arranged the parallel alignment into concentric circle pattern which made it possible to collect the mechanical energy whenever the deformation is along same axis or not. Despite the change of topography, the output voltage and current could still reach to 5 V and 400 nA, respectively, despite the mechanical deformation was from different direction. This new arbitrarily directional piezoelectric generator with concentrically circular topography (PGCT) allowed the piezoelectric device to harvest more mechanical energy than the one-directional alignment fiber-based devices, and this PGCT could perform even better output which promised more versatile and efficient using as a wearable electronics or sensor.

  20. Comparison of XAD with other dissolved lignin isolation techniques and a compilation of analytical improvements for the analysis of lignin in aquatic settings

    USGS Publications Warehouse

    Spencer, Robert G. M.; Aiken, George R.; Dyda, Rachael Y.; Butler, Kenna; Bergamaschi, Brian; Hernes, Peter J.

    2010-01-01

    This manuscript highlights numerous incremental improvements in dissolved lignin measurements over the nearly three decades since CuO oxidation of lignin phenols was first adapted for environmental samples. Intercomparison of the recovery efficiency of three common lignin phenol concentration and isolation techniques, namely XAD, C18with both CH3OH (C18M) and CH3CN (C18A) used independently for priming and elution steps, and tangential flow filtration (TFF) for a range of aquatic samples including fresh, estuarine and marine waters, was undertaken. With freshwater samples XAD8-1, C18M and TFF were all observed to recover ca. 80–90% of the lignin phenols and showed no fractionation effects with respect to diagnostic lignin parameters. With estuarine and marine samples more lignin phenols were recovered with C18M and XAD8-1 than TFF because of the increased prevalence of low molecular weight lignin phenols in marine influenced samples. For marine systems, differences were also observed between diagnostic lignin parameters isolated via TFF vs. C18M and XAD8-1 as a result of the high molecular weight lignin phenols being less degraded than the bulk. Therefore, it is recommended for future studies of marine systems that only one technique is utilized for ease of intercomparison within studies. It is suggested that for studies solely aimed at recovering bulk dissolved lignin in marine environments that C18M and XAD8-1 appear to be more suitable than TFF as they recover more lignin. Our results highlight that, for freshwater samples, all three common lignin phenol concentration and isolation techniques are comparable to whole water concentrated by rotary evaporation (i.e. not isolated) but, that for marine systems, the choice of concentration and isolation techniques needs to be taken into consideration with respect to both lignin concentration and diagnostic parameters. Finally, as the study highlights XAD8-1 to be a suitable method for the isolation of dissolved

  1. Comparison of XAD with other dissolved lignin isolation techniques and a compilation of analytical improvements for the analysis of lignin in aquatic settings

    USGS Publications Warehouse

    Spencer, R.G.M.; Aiken, G.R.; Dyda, R.Y.; Butler, K.D.; Bergamaschi, B.A.; Hernes, P.J.

    2010-01-01

    This manuscript highlights numerous incremental improvements in dissolved lignin measurements over the nearly three decades since CuO oxidation of lignin phenols was first adapted for environmental samples. Intercomparison of the recovery efficiency of three common lignin phenol concentration and isolation techniques, namely XAD, C18 with both CH3OH (C18M) and CH3CN (C18A) used independently for priming and elution steps, and tangential flow filtration (TFF) for a range of aquatic samples including fresh, estuarine and marine waters, was undertaken. With freshwater samples XAD8-1, C18M and TFF were all observed to recover ca. 80-90% of the lignin phenols and showed no fractionation effects with respect to diagnostic lignin parameters. With estuarine and marine samples more lignin phenols were recovered with C18M and XAD8-1 than TFF because of the increased prevalence of low molecular weight lignin phenols in marine influenced samples. For marine systems, differences were also observed between diagnostic lignin parameters isolated via TFF vs. C18M and XAD8-1 as a result of the high molecular weight lignin phenols being less degraded than the bulk. Therefore, it is recommended for future studies of marine systems that only one technique is utilized for ease of intercomparison within studies. It is suggested that for studies solely aimed at recovering bulk dissolved lignin in marine environments that C18M and XAD8-1 appear to be more suitable than TFF as they recover more lignin. Our results highlight that, for freshwater samples, all three common lignin phenol concentration and isolation techniques are comparable to whole water concentrated by rotary evaporation (i.e. not isolated) but, that for marine systems, the choice of concentration and isolation techniques needs to be taken into consideration with respect to both lignin concentration and diagnostic parameters. Finally, as the study highlights XAD8-1 to be a suitable method for the isolation of dissolved lignin

  2. Novel multi wavelength sensor concept to measure carboxy- and methemoglobin concentration non-invasively

    NASA Astrophysics Data System (ADS)

    Timm, Ulrich; Kraitl, Jens; Gewiss, Helge; Kamysek, Svend; Brock, Beate; Ewald, Hartmut

    2016-03-01

    This paper will describe a novel multi-wavelength photometric method to measure carboxyhemoglobin (COHb) and methemoglobin (MetHb) concentration non-invasively. COHb and MetHb are so called dysfunctional hemoglobin derivatives and they are not able to carry oxygen. Standard pulse oximeters are only able to measure two derivatives, namely oxyhemoglobin (O2Hb) and deoxyhemoglobin (HHb) but the presence of other derivatives in the blood may distort the readings. The paper presents a new approach of a noninvasive sensor system to measure COHb and MetHb and the validation in vivo and in vitro.

  3. On-chip pressure sensor using single-layer concentric chambers

    PubMed Central

    Tsai, Chia-Hung Dylan; Kaneko, Makoto

    2016-01-01

    A vision-based on-chip sensor for sensing local pressure inside a microfluidic device is proposed and evaluated in this paper. The local pressure is determined from the change of color intensity in the sensing chamber which is pre-filled with colored fluid. The working principle of the sensor is based on polydimethylsiloxane deformation. The pressure at the point of interest is guided into a deformation chamber, where the structural stiffness is softened by chamber geometry, and thus, the chamber deforms as a result of pressure changes. Such deformation is transmitted to the sensing chamber, a same-layer concentric inside the deformation chamber. The deformation in the sensing chamber causes the colored fluid flowing in or out the chamber and leads to different color intensity from the top view through a microscope. Experimental evaluations on static and dynamic responses by regulated input pressures were conducted. The correlation in static response is 0.97 while the dynamic responses are successfully observed up to 16 Hz. The greatest advantage is that the local pressure can be directly seen without any additional hardware or electricity. The whole sensor is on a single-layer microfluidic design, so that the fabrication is simple, consistent, and low-cost. The single-layer design also provides the convenience of easy integration for existing microfluidic systems. PMID:27076864

  4. Development of novel potentiometric sensors for determination of tartrazine dye concentration in foodstuff products.

    PubMed

    Abu Shawish, Hazem M; Ghalwa, Nasser Abu; Saadeh, Salman M; El Harazeen, Heba

    2013-05-01

    Tartrazine dye Na(3)TZ in foodstuff products was determined by a new modified carbon paste electrode, encoded sensor A, and a coated silver wire electrode, encoded sensor B, based on tartrazine TZ- cetryltrimethyl ammoniumbromide CTAB as a chemical modifier TZ-CTA. The electrodes exhibit the following characteristics listed respectively: a Nernstian slope of 17.9±0.5 and 19.4±0.2 mV/decade for tartrazine ion over a wide concentration range from 4.3×10(-7) to 1.0×10(-2) and 1.1×10(-7) to 1.0×10(-2) M. The lower detection limits: 3.2×10(-7) and 5.5×10(-8) M. Short response time (5-8 s) over the pH range 3.8-7.7 and 4.2-8.1. The proposed sensors display significantly high selectivity for TZ ion over a wide variety of sugars, some anions, common organic, inorganic compounds and additives. The developed electrodes were applied to the potentiometric determination of tartrazine ion in different kinds of foodstuffs: solid jelly (strawberry and custard) powder samples and soft drink (orange) samples with satisfactory results.

  5. The Impact of Sepiolite on Sensor Parameters during the Detection of Low Concentrations of Alcohols

    PubMed Central

    Suchorska-Woźniak, Patrycja; Rac, Olga; Fiedot, Marta; Teterycz, Helena

    2016-01-01

    The article presents the results of the detection of low-concentration C1–C4 alcohols using a planar sensor, in which a sepiolite filter was applied next to the gas-sensitive layer based on tin dioxide. The sepiolite layer is composed of tubes that have a length of several microns, and the diameter of the single tube ranges from several to tens of nanometers. The sepiolite layer itself demonstrated no chemical activity in the presence of volatile organic compounds (VOC), and the passive filter made of this material did not modify the chemical composition of the gaseous atmosphere diffusing to the gas-sensitive layer. The test results revealed that the structural remodelling of the sepiolite that occurs under the influence of temperature, as well as the effect of the filter (a compound with ionic bonds) with molecules of water, has a significant impact on the improvement of the sensitivity of the sensor in relation to volatile organic compounds when compared to the sensor without a filter. PMID:27834879

  6. A spherical-structure based fiber sensor for simultaneous measurement of ammonia gas concentration and temperature

    NASA Astrophysics Data System (ADS)

    Han, Wei; Liu, Dejun; Lian, Xiaokang; Mallik, Arun Kumar; Wei, Fangfang; Sun, Lei; Farrell, Gerald; Semenova, Yuliya; Wu, Qiang

    2016-11-01

    A novel fiber sensor for simultaneous measurement of ammonia gas concentration and temperature is proposed. The sensor is fabricated from two sections of single-mode fiber which are cleaved and then a fusion splicer and which is then used to fabricate spherically shaped structures at the end facets. The fusion arc is used to soften the glass which naturally assumes a spherical shape due to surface tension. A short section of multimode fiber is then fusion spliced with the two spherical-shaped ends of the single mode fibers so both the core modes and the cladding modes of the multimode fiber are excited to create two kinds of interference dips: One is created by core modes only which is not sensitive to ammonia gas since the core is isolated by the cladding so the effective refractive index of the core does not change when the refractive index of the environment changes, The other dip is created by the coupling of the core mode and cladding mod, which with a suitable coating is sensitive to ammonia gas. Silica sol-gel was prepared and coated on the fiber surface as a sensing layer for detecting ammonia gas concentration. The experimental results show that the two dips have linear wavelength shift responses but with different sensitivities to ammonia gas concentration (5.03×10-4nm/ppm for dip1 and -2.5×10- 5nm/ppm for dip2) and temperature (0.0067 nm/ºC for dip1 and 0.0149 nm/ºC for dip2. By constructing a wavelength shifts matrix for the two dips vs. ammonia gas concentration and temperature, both the ammonia gas concentration and temperature can be measured simultaneously.

  7. Effects of suspended sediment concentration and grain size on three optical turbidity sensors

    USGS Publications Warehouse

    Merten, Gustavo Henrique; Capel, Paul D.; Minella, Jean P.G.

    2014-01-01

    Purpose: Optical turbidity sensors have been successfully used to determine suspended sediment flux in rivers, assuming the relation between the turbidity signal and suspended sediment concentration (SSC) has been appropriately calibrated. Sediment size, shape and colour affect turbidity and are important to incorporate into the calibration process. Materials and methods: This study evaluates the effect of SSC and particle size (i.e. medium sand, fine sand, very fine sand, and fines (silt + clay)) on the sensitivity of the turbidity signal. Three different turbidity sensors were used, with photo detectors positioned at 90 and 180 degrees relative to the axis of incident light. Five different sediment ratios of sand:fines (0:100, 25:75, 50:50, 75:25 and 100:0) were also evaluated for a single SSC (1000 mg l-1). Results and discussion: The photo detectors positioned at 90 degrees were more sensitive than sensor positioned at 180 degrees in reading a wide variety of grain size particles. On average for the three turbidity sensors, the sensitivity for fines were 170, 40, and 4 times greater than sensitivities for medium sand, fine sand, and very fine sand, respectively. For an SSC of 1000 mg l-1 with the treatments composed of different proportions of sand and fines, the presence of sand in the mixture linearly reduced the turbidity signal. Conclusions: The results indicate that calibration of the turbidity signal should be carried out in situ and that the attenuation of the turbidity signal due to sand can be corrected, as long as the proportion of sand in the SSC can be estimated.

  8. Design of reflective optical fiber sensor for determining refractive index and sugar concentration of aqueous solutions

    NASA Astrophysics Data System (ADS)

    Marzuki, Ahmad; Wulan Sari, Nila; Riatun

    2016-02-01

    A reflective optical fiber sensor designed for measuring refractive index and sugar concentration of aqueous solutions is described. Two strains of parallel polymer optical fibers (POF) were wrapped in a bundle such that one of their fiber's end cross-sections had the same distance to the mirror surface. The light coming out from one strain of the fiber was reflected by the mirror to the second fiber. Sugar concentration of the aqueous solution filling the space between the fiber ends and the mirror was varied (1.0 M, 1.5 M, 2.0 M, 2.5 M, 3.0 M, 4.0 M, and 5.0 M). It was shown from the experiment that light intensity detected by photo-detector is linearly related to the percentage of the dissolved sugar in the solution as well as the variation of the sugar solution refractive index (R2 = 0.987).

  9. A Multifunctional Sensor for Concentrations of Ternary Solution with NaCl and Sucrose Employed in Osmotic Dehydration Process

    NASA Astrophysics Data System (ADS)

    Wei, Guo; Shida, Katsunori

    2003-08-01

    Ternary solution with NaCl and sucrose is widely employed in the osmotic dehydration process of food. In this paper we present a multifunctional sensor capable of directly sensing temperature and two physical parameters of solutions, namely ultrasonic velocity and electrical conductivity. By combination measurement of these three measurable parameters, the concentrations of various components in ternary solution with NaCl and sucrose can be simultaneously determined. A regression algorithm based on natural cubic spline interpolation and the least squares method is developed to estimate the concentrations of NaCl and sucrose, which considers the temperature influence on the multifunctional sensor and then enables decoupling of the reconstruction of concentrations in 4D space into 3D space. This sensor could prove valuable as a process control sensor in food industry.

  10. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

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

  11. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

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

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

    PubMed

    Pamidipati, Sirisha; Ahmed, Asma

    2016-11-03

    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.

  13. 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

  14. Enhanced Uranium Ore Concentrate Analysis by Handheld Raman Sensor: FY15 Status Report

    SciTech Connect

    Bryan, Samuel A.; Johnson, Timothy J.; Orton, Christopher R.

    2015-11-11

    High-purity uranium ore concentrates (UOC) represent a potential proliferation concern. A cost-effective, “point and shoot” in-field analysis capability to identify ore types, phases of materials present, and impurities, as well as estimate the overall purity would be prudent. Handheld, Raman-based sensor systems are capable of identifying chemical properties of liquid and solid materials. While handheld Raman systems have been extensively applied to many other applications, they have not been broadly studied for application to UOC, nor have they been optimized for this class of chemical compounds. PNNL was tasked in Fiscal Year 2015 by the Office of International Safeguards (NA-241) to explore the use of Raman for UOC analysis and characterization. This report summarizes the activities in FY15 related to this project.

  15. Effects of lignin-metal complexation on enzymatic hydrolysis of cellulose.

    PubMed

    Liu, H; Zhu, J Y; Fu, S Y

    2010-06-23

    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 15% when SL was added to a concentration of 0.1 g/L due to nonproductive adsorption of enzymes onto lignin. Cu(II) and Fe(III) were found to inhibit enzymatic cellulose hydrolysis in the presence of lignin. Ca(II) and Mg(II) were found to reduce or eliminate nonproductive enzyme adsorption by the formation of lignin-metal complex. The addition of Ca(II) or Mg(II) to a concentration of 10 mM can almost completely eliminate the reduction in SED caused by the nonproductive enzyme adsorption onto the lignins studied (SL, OL, or KL at concentration of 0.1 g/L). Ca(II) was also found to reduce the inhibitive effect of bound lignin in pretreated wood substrate, suggesting that Ca(II) can also form complex with bound lignin on pretreated solid lignocelluloses. Significant improvement in SED of about over 27% of a eucalyptus substrate produced by sulfite pretreatment to overcome recalcitrance of lignocellulose (SPORL) was achieved with the application of Ca(II).

  16. Microfabricated Collector-Generator Electrode Sensor for Measuring Absolute pH and Oxygen Concentrations.

    PubMed

    Dengler, Adam K; Wightman, R Mark; McCarty, Gregory S

    2015-10-20

    Fast-scan cyclic voltammetry (FSCV) has attracted attention for studying in vivo neurotransmission due to its subsecond temporal resolution, selectivity, and sensitivity. Traditional FSCV measurements use background subtraction to isolate changes in the local electrochemical environment, providing detailed information on fluctuations in the concentration of electroactive species. This background subtraction removes information about constant or slowly changing concentrations. However, determination of background concentrations is still important for understanding functioning brain tissue. For example, neural activity is known to consume oxygen and produce carbon dioxide which affects local levels of oxygen and pH. Here, we present a microfabricated microelectrode array which uses FSCV to detect the absolute levels of oxygen and pH in vitro. The sensor is a collector-generator electrode array with carbon microelectrodes spaced 5 μm apart. In this work, a periodic potential step is applied at the generator producing transient local changes in the electrochemical environment. The collector electrode continuously performs FSCV enabling these induced changes in concentration to be recorded with the sensitivity and selectivity of FSCV. A negative potential step applied at the generator produces a transient local pH shift at the collector. The generator-induced pH signal is detected using FSCV at the collector and correlated to absolute solution pH by postcalibration of the anodic peak position. In addition, in oxygenated solutions a negative potential step at the generator produces hydrogen peroxide by reducing oxygen. Hydrogen peroxide is detected with FSCV at the collector electrode, and the magnitude of the oxidative peak is proportional to absolute oxygen concentrations. Oxygen interference on the pH signal is minimal and can be accounted for with a postcalibration.

  17. RECENT ADVANCES IN UNDERSTANDING LIGNIN BIOSYNTHESIS.

    PubMed

    Whetten, Ross W.; MacKay, John J.; Sederoff, Ronald R.

    1998-06-01

    After a long period of little change, the basic concepts of lignin biosynthesis have been challenged by new results from genetic modification of lignin content and composition. New techniques for making directed genetic changes in plants, as well as improvements in the analytical techniques used to determine lignin content and composition in plant cell walls, have been used in experimental tests of the accepted lignin biosynthetic pathway. The lignins obtained from genetically modified plants have shown unexpected properties, and these findings have extended the known range of variation in lignin content and composition. These results argue that the accepted lignin biosynthetic pathway is either incomplete or incorrect, or both; and also suggest that plants may have a high level of metabolic plasticity in the formation of lignins. If this is so, the properties of novel lignins could be of significant scientific and practical interest.

  18. Increasing the lignin yield of the Alkaline Polyol Pulping process by treating black liquor with laccases of Myceliophthora thermophila.

    PubMed

    Engel, Norman; Hundt, Martin; Schapals, Tino

    2016-03-01

    The Alkaline Polyol Pulping process separates cellulose from lignocellulosic biomass by dissolving lignin to a great extent. Due to the pulping conditions the dissolved lignin depolymerises and only 75% can be precipitated. To increase this amount, a 24 h reaction of laccases of Myceliophthora thermophila with lignin dissolved in black liquor of the AlkaPolP process was investigated. The influence of pH, temperature, enzyme concentration and partial oxygen pressure was examined in a batch stirred tank reactor using a Box-Behnken factorial design. Due to the enzymatic reaction the lignin polymerises which results in an enhanced lignin precipitation. The addition of a mediator improves the polymerisation but decreases the amount of precipitable lignin. The influence of the parameters on precipitation yield and molecular mass can sufficiently be described with a second-order model and optimum conditions can be assessed. FT-IR spectra of the obtained lignins revealed that its typical phenolic structure is preserved.

  19. Diagnostics of two-phase flows with high concentration of a solid dispersed phase using fiber-optic sensors

    NASA Astrophysics Data System (ADS)

    Evseev, A. R.

    2016-10-01

    This paper is focused on the physical modeling of two-phase flows with high concentration of the dispersed phase. The fiber-optical sensors and their calibration procedure were developed for bubble concentration measurements in the fluidized bed apparatus (FB). Distributions of bubble concentration in the 2D and 3D FB apparatuses, which determine the quality of fluidization and local density of filling material, were obtained. The techniques of particle velocity and concentration measurements in the circulating fluidized bed (CFB) was developed using three-fiber sensor (the differential scheme of LDA) operated in backscattering regime. Sensor operation was analyzed and the main systematic measurement errors were determined; the original construction of the sensor was designed. The data on the velocity and concentration profiles of dispersed phase in a large-scale CFB apparatus were obtained for fluidization of particles by air. It was found that with increasing circulation velocity in the CFB apparatus, the particle concentration increases in the near-wall region much higher than in the flow core. The method of particle velocity measurements in a liquid was developed using the laser Doppler fiber anemometer (LDFA-1), operating in the backscattering regime. The signal to noise ratio was obtained for particles of different size and material in test measurements. The rates of consolidated precipitation of cryolite particles in a sedimentation apparatus with the inclined walls were measured.

  20. Fluorescence-based proxies for lignin in freshwater dissolved organic matter

    USGS Publications Warehouse

    Hernes, Peter J.; Bergamaschi, Brian A.; Eckard, Robert S.; Spencer, Robert G.M.

    2009-01-01

    Lignin phenols have proven to be powerful biomarkers in environmental studies; however, the complexity of lignin analysis limits the number of samples and thus spatial and temporal resolution in any given study. In contrast, spectrophotometric characterization of dissolved organic matter (DOM) is rapid, noninvasive, relatively inexpensive, requires small sample volumes, and can even be measured in situ to capture fine-scale temporal and spatial detail of DOM cycling. Here we present a series of cross-validated Partial Least Squares models that use fluorescence properties of DOM to explain up to 91% of lignin compositional and concentration variability in samples collected seasonally over 2 years in the Sacramento River/San Joaquin River Delta in California, United States. These models were subsequently used to predict lignin composition and concentration from fluorescence measurements collected during a diurnal study in the San Joaquin River. While modeled lignin composition remained largely unchanged over the diurnal cycle, changes in modeled lignin concentrations were much greater than expected and indicate that the sensitivity of fluorescence-based proxies for lignin may prove invaluable as a tool for selecting the most informative samples for detailed lignin characterization. With adequate calibration, similar models could be used to significantly expand our ability to study sources and processing of DOM in complex surface water systems.

  1. Lignin-Derived Advanced Carbon Materials

    SciTech Connect

    Chatterjee, Sabornie; Saito, Tomonori

    2015-11-16

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

  2. Lignin-Derived Advanced Carbon Materials.

    PubMed

    Chatterjee, Sabornie; Saito, Tomonori

    2015-12-07

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

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

    SciTech Connect

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

    2016-09-26

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

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

    NASA Astrophysics Data System (ADS)

    Guo, Xiaojie; Zhang, Jinwen; Xin, Junna

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

  5. 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

  6. A coal mine multi-point fiber ethylene gas concentration sensor

    NASA Astrophysics Data System (ADS)

    Wei, Yubin; Chang, Jun; Lian, Jie; Liu, Tongyu

    2015-03-01

    Spontaneous combustion of the coal mine goaf is one of the main disasters in the coal mine. The detection technology based on symbolic gas is the main means to realize the spontaneous combustion prediction of the coal mine goaf, and ethylene gas is an important symbol gas of spontaneous combustion in the coal accelerated oxidation stage. In order to overcome the problem of current coal ethylene detection, the paper presents a mine optical fiber multi-point ethylene concentration sensor based on the tunable diode laser absorption spectroscopy. Based on the experiments and analysis of the near-infrared spectrum of ethylene, the system employed the 1.62 μm (DFB) wavelength fiber coupled distributed feedback laser as the light source. By using the wavelength scanning technique and developing a stable fiber coupled Herriot type long path gas absorption cell, a ppm-level high sensitivity detecting system for the concentration of ethylene gas was realized, which could meet the needs of coal mine fire prevention goaf prediction.

  7. Fractionation and physicochemical characterization of lignin from waste jute bags: Effect of process parameters on yield and thermal degradation.

    PubMed

    Ahuja, Dheeraj; Kaushik, Anupama; Chauhan, Ghanshyam S

    2017-04-01

    In this work lignin was extracted from waste jute bags using soda cooking method and effect of varying alkali concentration and pH on yield, purity, structure and thermal degradation of lignin were studied. The Lignin yield, chemical composition and purity were assessed using TAPPI method and UV-vis spectroscopy. Yield and purity of lignin ranged from 27 to 58% and 50-94%, respectively for all the samples and was maximum for 8% alkali concentration and at pH 2 giving higher thermal stability. Chemical structure, thermal stability and elementary analysis of lignin were studied using FTIR, (H)NMR, thermo gravimetric analysis (TGA) and Elemental analyzer. FTIR and (H)NMR results showed that core structure of lignin starts breaking beyond 10% alkali concentration. S/G ratio shows the dominance of Syringyl unit over guaiacyl unit.

  8. ''The control of lignin synthesis''

    SciTech Connect

    Carlson, John E.

    2005-04-07

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

  9. Unravelling lignin formation and structure

    SciTech Connect

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

    1991-01-01

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

  10. The fate of lignin during hydrothermal pretreatment

    PubMed Central

    2013-01-01

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

  11. In situ measurement of Cl- concentrations and pH at the reinforcing steel/concrete interface by combination sensors.

    PubMed

    Du, Rong-Gui; Hu, Rong-Gang; Huang, Ruo-Shuang; Lin, Chang-Jian

    2006-05-01

    This paper presents an in situ, nondestructive method of monitoring Cl- concentrations and pH values at the steel/concrete interface. The Ag/AgCl electrodes prepared by the electrochemical anodization and the Ir/IrO2 electrodes prepared by thermal oxidation in carbonate served as Cl- concentration and pH sensors, respectively. The potentiometric response of the Ag/AgCl electrode to the logarithm of Cl- concentrations ranging from 1 x 10(-4) to 2 M in saturated Ca(OH)2 solution simulating the inner electrolytic medium of concrete shows good linearity. The Ir/IrO2 electrode also exhibits an ideal Nernstian response in the range of pH 1-14. The Ag/AgCl and Ir/IrO2 electrodes were combined into a multiplex Cl-/pH sensor, and the sensor was embedded in concrete close to the steel/concrete interface to realize an in situ and long-term measurement of Cl- concentrations and pH values. The results indicate that the combined sensor is robust and sensitive enough to in situ measure Cl- concentrations and pH quantitatively at the steel/concrete interface, which is of indispensable importance to the study of corrosion and protection of the steel in concrete.

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

    PubMed

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

    2009-09-01

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

  13. Measurement of sucrose and ethanol concentrations in process streams and effluents of sugarcane bioethanol industry by optical fiber sensor

    NASA Astrophysics Data System (ADS)

    Fujiwara, Eric; Ono, Eduardo; Manfrim, Tarcio P.; Santos, Juliana S.; Suzuki, Carlos K.

    2011-05-01

    The measurement of process streams and effluents from sugar-ethanol industry by using optical fiber sensor based on Fresnel reflection principle is reported. Firstly, binary sucrose-water and ethanol-water solutions were measured in order to determine the calibration curves. Secondly, the co-products from various processing stages were analyzed in order to identify the sucrose or ethanol concentration. The absolute error was calculated by comparison between the nominal concentration values obtained by plant laboratory analysis and the sensor response, yielding errors <= 5 wt% and <= 5 vol% for sucrose and ethanol content, respectively. The fiber sensor provided reliable results even for samples with more complex compositions than pure sucrose or ethanol solutions, with perspectives of application on the several stages of the plant facility.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  15. Lignin poly(lactic acid) copolymers

    DOEpatents

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

    2017-02-14

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

  16. 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.

  17. 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.

  18. Enzymatic monitoring of lignin and lignin derivatives biooxidation.

    PubMed

    Ibrahim, Victor; Mamo, Gashaw

    2016-01-01

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

  19. Cationic electrodepositable coating composition comprising lignin

    DOEpatents

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

    2013-07-30

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

  20. Liquid Fuels from Lignins: Annual Report

    SciTech Connect

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

    1986-01-01

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

  1. 40 CFR 721.5460 - Organosolv lignin.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Organosolv lignin. 721.5460 Section... Substances § 721.5460 Organosolv lignin. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an organosolv lignin (PMN P-95-1584; CAS No. 8068-03-9)...

  2. 40 CFR 721.5460 - Organosolv lignin.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Organosolv lignin. 721.5460 Section... Substances § 721.5460 Organosolv lignin. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an organosolv lignin (PMN P-95-1584; CAS No. 8068-03-9)...

  3. 40 CFR 721.5460 - Organosolv lignin.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Organosolv lignin. 721.5460 Section... Substances § 721.5460 Organosolv lignin. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an organosolv lignin (PMN P-95-1584; CAS No. 8068-03-9)...

  4. 40 CFR 721.5460 - Organosolv lignin.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Organosolv lignin. 721.5460 Section... Substances § 721.5460 Organosolv lignin. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an organosolv lignin (PMN P-95-1584; CAS No. 8068-03-9)...

  5. 40 CFR 721.5460 - Organosolv lignin.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  6. Analyzer for measurement of nitrogen oxide concentration by ozone content reduction in gas using solid state chemiluminescent sensor

    NASA Astrophysics Data System (ADS)

    Chelibanov, V. P.; Ishanin, G. G.; Isaev, L. N.

    2014-05-01

    Role of nitrogen oxide in ambient air is described and analyzed. New method of nitrogen oxide concentration measurement in gas phase is suggested based on ozone concentration measurement with titration by nitrogen oxide. Research of chemiluminescent sensor composition is carried out on experimental stand. The sensor produced on the base of solid state non-activated chemiluminescent composition is applied as ozone sensor. Composition is put on the surface of polymer matrix with developed surface. Sensor compositions includes gallic acid with addition of rodamine-6G. Model of interaction process between sensor composition and ozone has been developed, main products appeared during reaction are identified. The product determining the speed of luminescense appearance is found. This product belongs to quinone class. Then new structure of chemiluminescent composition was suggested, with absence of activation period and with high stability of operation. Experimental model of gas analyzer was constructed and operation algorithm was developed. It was demonstrated that developed NO measuring instrument would be applied for monitoring purposes of ambient air. This work was partially financially supported by Government of Russian Federation, Grant 074-U01

  7. Fractionation of organosolv lignin from olive tree clippings and its valorization to simple phenolic compounds.

    PubMed

    Toledano, Ana; Serrano, Luis; Balu, Alina Mariana; Luque, Rafael; Pineda, Antonio; Labidi, Jalel

    2013-03-01

    Lignin valorization practices have attracted a great deal of interest in recent years due to the large excess of lignin produced by the pulp and paper industry, together with second-generation bioethanol plants. In this work, a new lignin valorization approach is proposed. It involves ultrafiltration as a fractionation process to separate different molecular weight lignin fractions followed by a hydrogen-free, mild, hydrogenolytic, heterogeneously catalyzed methodology assisted by microwave irradiation to obtain simple phenolic, monomeric products by depolymerization using a nickel-based catalyst. The main products obtained were desaspidinol, syringaldehyde, and syringol; this proves the efficiency of the depolymerization conditions applied. The concentration of these observed compounds increased when the molecular weights of the lignin fractions increased. The applied depolymerization conditions, which take advantage of the use of formic acid as a hydrogen-donating solvent, did not generate any biochar in the systems.

  8. Optimization of lignin production from empty fruit bunch via liquefaction with ionic liquid.

    PubMed

    Sidik, Dilaeleyana Abu Bakar; Ngadi, Norzita; Amin, Nor Aishah Saidina

    2013-05-01

    The production of lignin from empty fruit bunch (EFB) has been carried out using liquefaction method with 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid (IL), in presence of sulfuric acid (H2SO4) as a catalyst. Response surface methodology (RSM) based on a factorial Central Composite Design (CCD) was employed to identify the optimum condition for lignin yield. The result indicated that the second order model was adequate for all the independent variables on the response with R(2)=0.8609. The optimum temperature, time, ionic liquid to EFB ratio, and catalyst concentration were 150.5 °C, 151 min, 3:1 wt/wt and 4.73 wt%, respectively for lignin yield=26.6%. The presence of lignin liquefied product was confirmed by UV-Vis and FTIR analysis. It was also demonstrated lignin extraction from lignocellulosic using recycled IL gave sufficient performance.

  9. Fiber Optic Raman Sensor to Monitor Concentration Ratio of Nitrogen and Oxygen in a Cryogenic Mixture

    NASA Technical Reports Server (NTRS)

    Tiwari, Vidhu S.; Kalluru, Rajamohan R.; Yueh, Fang-Yu; Singh, Jagdish P.; SaintCyr, William

    2007-01-01

    A spontaneous Raman scattering optical fiber sensor is developed for a specific need of NASA/SSC for long-term detection and monitoring of the quality of liquid oxygen (LOX) in the delivery line during ground testing of rocket engines. The sensor performance was tested in the laboratory and with different excitation light sources. To evaluate the sensor performance with different excitation light sources for the LOX quality application, we have used the various mixtures of liquid oxygen and liquid nitrogen as samples. The study of the sensor performance shows that this sensor offers a great deal of flexibility and provides a cost effective solution for the application. However, an improved system response time is needed for the real-time, quantitative monitoring of the quality of cryogenic fluids in harsh environment.

  10. Augmented Switching Linear Dynamical System Model for Gas Concentration Estimation with MOX Sensors in an Open Sampling System

    PubMed Central

    Di Lello, Enrico; Trincavelli, Marco; Bruyninckx, Herman; De Laet, Tinne

    2014-01-01

    In this paper, we introduce a Bayesian time series model approach for gas concentration estimation using Metal Oxide (MOX) sensors in Open Sampling System (OSS). Our approach focuses on the compensation of the slow response of MOX sensors, while concurrently solving the problem of estimating the gas concentration in OSS. The proposed Augmented Switching Linear System model allows to include all the sources of uncertainty arising at each step of the problem in a single coherent probabilistic formulation. In particular, the problem of detecting on-line the current sensor dynamical regime and estimating the underlying gas concentration under environmental disturbances and noisy measurements is formulated and solved as a statistical inference problem. Our model improves, with respect to the state of the art, where system modeling approaches have been already introduced, but only provided an indirect relative measures proportional to the gas concentration and the problem of modeling uncertainty was ignored. Our approach is validated experimentally and the performances in terms of speed of and quality of the gas concentration estimation are compared with the ones obtained using a photo-ionization detector. PMID:25019637

  11. Augmented switching linear dynamical system model for gas concentration estimation with MOX sensors in an open sampling system.

    PubMed

    Di Lello, Enrico; Trincavelli, Marco; Bruyninckx, Herman; De Laet, Tinne

    2014-07-11

    In this paper, we introduce a Bayesian time series model approach for gas concentration estimation using Metal Oxide (MOX) sensors in Open Sampling System (OSS). Our approach focuses on the compensation of the slow response of MOX sensors, while concurrently solving the problem of estimating the gas concentration in OSS. The proposed Augmented Switching Linear System model allows to include all the sources of uncertainty arising at each step of the problem in a single coherent probabilistic formulation. In particular, the problem of detecting on-line the current sensor dynamical regime and estimating the underlying gas concentration under environmental disturbances and noisy measurements is formulated and solved as a statistical inference problem. Our model improves, with respect to the state of the art, where system modeling approaches have been already introduced, but only provided an indirect relative measures proportional to the gas concentration and the problem of modeling uncertainty was ignored. Our approach is validated experimentally and the performances in terms of speed of and quality of the gas concentration estimation are compared with the ones obtained using a photo-ionization detector.

  12. Enzymatic conversion of lignin into renewable chemicals.

    PubMed

    Bugg, Timothy D H; Rahmanpour, Rahman

    2015-12-01

    The aromatic heteropolymer lignin is a major component of plant cell walls, and is produced industrially from paper/pulp manufacture and cellulosic bioethanol production. Conversion of lignin into renewable chemicals is a major unsolved problem in the development of a biomass-based biorefinery. The review describes recent developments in the understanding of bacterial enzymes for lignin breakdown, such as DyP peroxidases, bacterial laccases, and beta-etherase enzymes. The use of pathway engineering methods to construct genetically modified microbes to convert lignin to renewable chemicals (e.g. vanillin, adipic acid) via fermentation is discussed, and the search for novel applications for lignin (e.g. carbon fibre).

  13. A novel partially biobased PAN-lignin blend as a potential carbon fiber precursor.

    PubMed

    Seydibeyoğlu, M Özgür

    2012-01-01

    Blends of polyacrylonitrile (PAN) and lignin were prepared with three different lignin types by solution blending and solution casting. Among three types of lignin, one type was chosen and different blend concentrations were prepared and casted. The casted blend films were characterized chemically with fourier transform infrared spectroscopy (FTIR), and thermally with thermogravimetric analysis (TGA). The mechanical properties of the blends were measured using dynamic mechanical analysis (DMA). FTIR analysis shows an excellent interaction of PAN and lignin. The interaction of the lignins and PAN was confirmed by TGA analysis. The DMA results reveal that the lignin enhance the mechanical properties of PAN at room temperature and elevated temperatures. The blend structure and morphology were observed using scanning electron microscopy (SEM). SEM images show that excellent polymer blends were prepared. The results show that it is possible to develop a new precursor material with a blend of lignin and PAN. These studies show that the side product of paper and cellulosic bioethanol industries, namely, lignin can be used for new application areas.

  14. Structural modification of lignin and characterization of pretreated wheat straw by ozonation.

    PubMed

    Bule, Mahesh V; Gao, Allan H; Hiscox, Bill; Chen, Shulin

    2013-04-24

    Ozonolysis is potentially an effective method for pretreating lignocellulosic biomass to improve the production of fermentable sugars via enzymatic hydrolysis. Further understanding of the ozonolysis process and identifying specific lignin structural changes are crucial for improving the pretreatment process. Investigation into pretreatment of wheat straw using ozonolysisis is reported in this paper, with special emphasis on selective modification/degradation of lignin subunits. The ozonolysis was performed for 2 h with less than 60 mesh particles in order to achieve maximum lignin oxidation. The results showed that the lignin structure was significantly modified under these conditions, leading to higher sugar recovery of more than 50% which increased from 13.11% to 63.17% corresponding to the control and ozone treated samples, respectively. Moisture content was found to be an important parameter for improving sugar recovery. Ninety percent (w/w) moisture produced the highest sugar recovery. The concentration of acid soluble lignin in the ozone treated sample increased from 4% to 11% after 2 h treatment. NMR analysis revealed that the S2/6 and G2 lignin units in the wheat straw were most prone to oxidation by ozone as the concentration of aromatic units decreased while the carboxylic acids became more abundant. The experimental data suggest the degradation of β-O-4 moieties and aromatic ring opening in lignin subunits. The pyrolysis-gas chromatography/mass spectrometry results revealed that the rate of lignin unit degradation was in the following order: syringyl > guaiacyl > p-hydroxyphenyl. Long ozone exposure resulted in few condensed lignin structure formation. In addition, the formation of condensed units during this process increased the activation energy from ASTM-E, 259.74 kJ/mol; Friedman-E, 270.08 kJ/mol to ASTM-E, 509.29 kJ/mol; Friedman-E, 462.17 kJ/mol. The results provide new information in overcoming lignin barrier for lignocellulose utilization.

  15. 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 106 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

  16. Advanced chemical design for efficient lignin bioconversion

    SciTech Connect

    Xie, Shangxian; Sun, Qining; Pu, Yunqiao; Lin, Furong; Sun, Su; Wang, Xin; Ragauskas, Arthur J.; Yuan, Joshua S.

    2016-12-22

    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 analysis 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 106 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.

  17. Effect of ionic liquid treatment on the structures of lignins in solutions

    SciTech Connect

    Cheng, Gang; Kent, Michael S; He, Lilin; Varanasi, Patanjali; Dibble, Dean; Melnichenko, Yuri B; Simmons, Blake; Singh, Seema

    2012-01-01

    The solution structures of three types of isolated lignin - organosolv (OS), Kraft (K), and low sulfonate (LS) - before and after treatment with 1-ethyl-3-methylimidazolium acetate were studied using small-angle neutron scattering (SANS) and dynamic light scattering (DLS) over a concentration range of 0.3-2.4 wt %. The results indicate that each of these lignins is comprised of aggregates of well-defined basal subunits, the shapes and sizes of which, in D{sub 2}O and DMSO-d{sub 6}, are revealed using these techniques. LS lignin contains a substantial amount of nanometer-scale individual subunits. In aqueous solution these subunits have a well-defined elongated shape described well by ellipsoidal and cylindrical models. At low concentration the subunits are highly expanded in alkaline solution, and the effect is screened with increasing concentration. OS lignin dissolved in DMSO was found to consist of a narrow distribution of aggregates with average radius 200 {+-} 30 nm. K lignin in DMSO consists of aggregates with a very broad size distribution. After ionic liquid (IL) treatment, LS lignin subunits in alkaline solution maintained the elongated shape but were reduced in size. IL treatment of OS and K lignins led to the release of nanometer-scale subunits with well-defined size and shape.

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

    SciTech Connect

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

    1988-01-01

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

  19. A Novel Sensor to Measure the Concentration of Nitrous Oxide in Anesthetic Mixtures

    DTIC Science & Technology

    2007-11-02

    II. METODOLOGY The sensor was built from a poli-metil-metacrilate (PMMA) POF manufactured by Mitsubishi Rayon Co. Those fibers have an optic...support to the sensor, a segment of POF was embedded in a block of polyester resin of 1 x 2 x 12 cm. After a period of 24 h, enough to cure the resin...linear regression and standard deviation were respectively 0,996 and 0,00169. The sensitivity of this sensor was –2.32 x 10-3 dB/V%. The graph in

  20. Proceedings of the DOE/Industry Sensor Working Group meeting, Austin, Texas

    SciTech Connect

    Not Available

    1988-11-01

    This paper report contains topics presented at a sensor workshop group meeting. The topics describe measuring instruments of use in the pulp and paper industry. Topics include: measurement of solids fraction; process instrumentation research for the pulp paper industry; real-time non-contact optical surface motion monitor; on-machine sensors to measure paper mechanical properties; hierarchical intelligent control of industrial processes -- an in-parallel lime kiln application; proposal for research on lignin concentration measurement in pulping liquors; and advanced polymeric sensor materials for industrial drying.

  1. A low frequency electromagnetic sensor for indirect measurement of glucose concentration: in vitro experiments in different conductive solutions.

    PubMed

    Tura, Andrea; Sbrignadello, Stefano; Cianciavicchia, Domenico; Pacini, Giovanni; Ravazzani, Paolo

    2010-01-01

    In recent years there has been considerable interest in the study of glucose-induced dielectric property variations of human tissues as a possible approach for non-invasive glycaemia monitoring. We have developed an electromagnetic sensor, and we tested in vitro its ability to estimate variations in glucose concentration of different solutions with similarities to blood (sodium chloride and Ringer-lactate solutions), differing though in the lack of any cellular components. The sensor was able to detect the effect of glucose variations over a wide range of concentrations (∼78-5,000 mg/dL), with a sensitivity of ∼0.22 mV/(mg/dL). Our proposed system may thus be useful in a new approach for non-invasive and non-contact glucose monitoring.

  2. Fractionation of hemp hurds by organosolv pretreatment and its effect on production of lignin and sugars.

    PubMed

    Gandolfi, Stefano; Ottolina, Gianluca; Consonni, Roberto; Riva, Sergio; Patel, Ilabahen

    2014-07-01

    Fractionation of hemp hurds into its three main components, cellulose, hemicellulose, and lignin, was carried out using organosolv pretreatment. The effect of processing parameters, such as temperature, catalyst concentration, reaction time, and methanol (MeOH) concentration, on the dissolution and recovery of hemicellulose and lignin was determined. More than 75% of total hemicellulose and 75% of total lignin was removed in a single step with low amounts of degradation products under the following conditions: 165 °C, 3% H2 SO4 , 20 min reaction time, and 45% MeOH. Enzymatic hydrolysis of the residual pretreated biomass yielded up to 60% of cellulose-to-glucose conversion. The maximum recovery of the main components was obtained at a combined severity factor value of around one. Characterization of pretreated biomass and isolated lignin was carried out with FTIR and 2D (13) C-(1) H correlation HSQC NMR spectroscopy, the latter technique providing detailed structural information about the obtained methanol organosolv lignin (MOSL). Results suggested that xylopyranoside is the major carbohydrate associated with hemp lignin. The chemical properties of MOSL samples in terms of their phenolic group content and antioxidant capacity were also investigated. The results showed that MOSL samples have a high phenolic group content and antioxidant capacity relative to Klason lignin.

  3. Biodegradable lignin/polyolefin composite films

    SciTech Connect

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

    1993-12-31

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

  4. 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.

  5. Design and application of a class of sensors to monitor Ca2+ dynamics in high Ca2+ concentration cellular compartments

    PubMed Central

    Tang, Shen; Wong, Hing-Cheung; Wang, Zhong-Min; Huang, Yun; Zou, Jin; Zhuo, You; Pennati, Andrea; Gadda, Giovanni; Delbono, Osvaldo; Yang, Jenny J.

    2011-01-01

    Quantitative analysis of Ca2+ fluctuations in the endoplasmic/sarcoplasmic reticulum (ER/SR) is essential to defining the mechanisms of Ca2+-dependent signaling under physiological and pathological conditions. Here, we developed a unique class of genetically encoded indicators by designing a Ca2+ binding site in the EGFP. One of them, calcium sensor for detecting high concentration in the ER, exhibits unprecedented Ca2+ release kinetics with an off-rate estimated at around 700 s−1 and appropriate Ca2+ binding affinity, likely attributable to local Ca2+-induced conformational changes around the designed Ca2+ binding site and reduced chemical exchange between two chromophore states. Calcium sensor for detecting high concentration in the ER reported considerable differences in ER Ca2+ dynamics and concentration among human epithelial carcinoma cells (HeLa), human embryonic kidney 293 cells (HEK-293), and mouse myoblast cells (C2C12), enabling us to monitor SR luminal Ca2+ in flexor digitorum brevis muscle fibers to determine the mechanism of diminished SR Ca2+ release in aging mice. This sensor will be invaluable in examining pathogenesis characterized by alterations in Ca2+ homeostasis. PMID:21914846

  6. Elicitor-Induced Spruce Stress Lignin (Structural Similarity to Early Developmental Lignins).

    PubMed Central

    Lange, B. M.; Lapierre, C.; Sandermann, H.

    1995-01-01

    Suspension cultures of Picea abies (L.) Karst released polymeric material into the culture medium when treated with an elicitor preparation from the spruce needle pathogen Rhizosphaera kalkhoffii. The presence of lignin (about 35%, w/w) was demonstrated by phloroglucinol/HCI reactivity and quantitation with thioglycolic acid. Carbohydrate (about 14%, w/w) and protein (about 32%, w/w) were also detected. Amino acid analysis revealed that hydroxyproline and proline predominated. Thioacidolysis and subsequent Raney nickel desulfurization allowed the analysis of lignin-building units and interunit bonds. Compared with spruce wood lignin, an approximately 20-fold higher relative amount of p-hydroxyphenyl units was determined. A high content of p-hydroxyphenyl units is typical for certain developmental lignins, such as conifer compression wood and middle lamella lignins, as well as all induced cell culture lignins so far analyzed. Cross-linkages of the pinoresinol type ([beta]-[beta]) in the excreted cell culture lignin were markedly increased, whereas [beta]-1 interunit linkages were decreased relative to spruce wood lignin. The amount and nature of cross-linkages were shown to be intermediate between those in wood lignin and in enzymatically prepared lignins. In summary, the elicitor-induced stress lignin was excreted as a lignin-extensin complex that closely resembled early developmental lignins. PMID:12228544

  7. Lignin phenols derivatives in lichens.

    PubMed

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

    2015-01-01

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

  8. 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.

  9. 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

  10. Preparing spherical lignin from rice husk.

    PubMed

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

    2013-08-01

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

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

    PubMed Central

    Austin, Amy T.; Ballaré, Carlos L.

    2010-01-01

    Plant litter decomposition is a critical step in the formation of soil organic matter, the mineralization of organic nutrients, and the carbon balance in terrestrial ecosystems. Biotic decomposition in mesic ecosystems is generally negatively correlated with the concentration of lignin, a group of complex aromatic polymers present in plant cell walls that is recalcitrant to enzymatic degradation and serves as a structural barrier impeding microbial access to labile carbon compounds. Although photochemical mineralization of carbon has recently been shown to be important in semiarid ecosystems, litter chemistry controls on photodegradative losses are not understood. We evaluated the importance of litter chemistry on photodegradation of grass litter and cellulose substrates with varying levels of lignin [cellulose-lignin (CL) substrates] under field conditions. Using wavelength-specific light attenuation filters, we found that light-driven mass loss was promoted by both UV and visible radiation. The spectral dependence of photodegradation correlated with the absorption spectrum of lignin but not of cellulose. Field incubations demonstrated that increasing lignin concentration reduced biotic decomposition, as expected, but linearly increased photodegradation. In addition, lignin content in CL substrates consistently decreased in photodegradative incubations. We conclude that lignin has a dual role affecting litter decomposition, depending on the dominant driver (biotic or abiotic) controlling carbon turnover. Under photodegradative conditions, lignin is preferentially degraded because it acts as an effective light-absorbing compound over a wide range of wavelengths. This mechanistic understanding of the role of lignin in plant litter decomposition will allow for more accurate predictions of carbon dynamics in terrestrial ecosystems. PMID:20176940

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

    PubMed

    Austin, Amy T; Ballaré, Carlos L

    2010-03-09

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

  13. Bisphenol A Sensors on Polyimide Fabricated by Laser Direct Writing for Onsite River Water Monitoring at Attomolar Concentration.

    PubMed

    Cheng, Cheng; Wang, Shutong; Wu, Jayne; Yu, Yongchao; Li, Ruozhou; Eda, Shigetoshi; Chen, Jiangang; Feng, Guoying; Lawrie, Benjamin; Hu, Anming

    2016-07-20

    This work presents an aptamer-based, highly sensitive and specific sensor for atto- to femtomolar level detection of bisphenol A (BPA). Because of its widespread use in numerous products, BPA enters surface water from effluent discharges during its manufacture, use, and from waste landfill sites throughout the world. On-site measurement of BPA concentrations in water is important for evaluating compliance with water quality standards or environmental risk levels of the harmful compound in the environment. The sensor in this work is porous, conducting, interdigitated electrodes that are formed by laser-induced carbonization of flexible polyimide sheets. BPA-specific aptamer is immobilized on the electrodes as the probe, and its binding with BPA at the electrode surface is detected by capacitive sensing. The binding process is aided by ac electroosmotic effect that accelerates the transport of BPA molecules to the nanoporous graphene-like structured electrodes. The sensor achieved a limit of detection of 58.28 aM with a response time of 20 s. The sensor is further applied for recovery analysis of BPA spiked in surface water. This work provides an affordable platform for highly sensitive, real time, and field-deployable BPA surveillance critical to the evaluation of the ecological impact of BPA exposure.

  14. Magnetic Modeling of a Rotating Flux Concentrator System Designed to Mitigate Noise in Large Magnetic Sensors

    DTIC Science & Technology

    2010-09-01

    a piezoelectric material sandwiched between slabs of a magnetostrictive material. Sensitivity is already under 1 nT...piezoelectric material sandwiched between slabs of a magnetostrictive material. In a magnetic field the magnetostrictive material stresses the...Schematic of magnetoelectric sensor. The gray region consists of a piezoelectric material sandwiched between slabs of a magnetostrictive material

  15. 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 (Ea) for its relaxationmore » but caused stiffening of the soft phase and increased its Ea. 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

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

    SciTech Connect

    Akato, Kokouvi M.; Tran, Chau D.; Chen, Jihua; Naskar, Amit K.

    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 (Ea) for its relaxation but caused stiffening of the soft phase and increased its Ea. 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.

  17. Lignin Analysis by HPLC and FTIR.

    PubMed

    Reyes-Rivera, Jorge; Terrazas, Teresa

    2017-01-01

    Fourier transform infrared spectroscopy (FTIR) is a simple non-destructive technique which allows the user to obtain quick and accurate information about the structure of the constituents of wood. High performance liquid chromatography (HPLC) is an analytical technique useful to determine the ratio of the lignin monomers obtained by the alkaline nitrobenzene oxidation method. Furthermore, lignin content has been commonly determined by wet chemical methods; Klason lignin determination is a quick and accessible method. Here, we detail the procedures for chemical analysis of the wood lignin using these techniques.

  18. Isolation and further structural characterization of lignins from the valonea of Quercus variabilis.

    PubMed

    Yang, Lina; Wang, Dongmei; Zhou, Dan; Zhang, Yawei; Yang, Tingting

    2017-04-01

    The isolation process of alkali lignin (AL) from the valonea of Quercus variabilis Blume was optimized (liquid/solid ratio, 12.21; isolation time, 4.21h; isolation temperature, 42.21°C; and alkali concentration, 0.85mol/L) using the response surface method (RSM), with the highest isolation rate obtained being 22.67%. Then, the apparent structures of AL, enzymatic hydrolysis lignin (CEL) and milled wood lignin (MWL) were studied by scanning electron microscopy (SEM), which indicated that the isolation processes of AL and CEL caused some damage to the apparent structure of lignin. The comprehensive structure characteristics of lignin samples was studied using (1)H, (13)C and 2D-HSQC techniques based on former studies. It was found that (1) three lignins were GSH-type; (2) the relative content of β-O-4' linkages in CEL (75.91%) was lower than those in AL (91.57%) and MWL (83.23%), suggesting that the β-O-4' linkages were largely cleaved during the CEL isolation process. In addition, the existence of phenylcoumarane, ferulic acid, p-coumarates and p-hydroxycinnamyl alcohol end groups can be found; (3) The S/G ratios were estimated to be 8.72, 1.30 and 0.98 for AL, MWL and CEL, respectively, suggesting that the lignin fragment rich in S-units was easily released under the alkali conditions.

  19. 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.

  20. Headwater Nutrient Concentration Patterns in Response to Storm Events Across Land Use Types using In Situ Sensors

    NASA Astrophysics Data System (ADS)

    Price, A.; Wollheim, W. M.; Mulukutla, G. K.; Carey, R. O.; McDowell, W. H.

    2012-12-01

    Understanding the aquatic biogeochemical impacts of land use change and climate variability will require improved understanding of nutrient variability over temporal scales ranging from storms to seasons. New in situ sensor technology offers the prospect of efficient nutrient measurements over multiple time scales. We quantified nutrient flux patterns in response to storm events across seasons using in situ nutrient sensors deployed in headwater streams draining three land use types (forest, suburban, and agriculture) within the Lamprey River watershed, New Hampshire, between April-December 2012. We utilized two sensor suites, each consisting of a Satlantic Submersible Ultraviolet Nitrate Analyzer (NO3-N), Turner Designs C6 Multi-Sensor Platform (CDOM, Turbidity, Chl), Hydrolab MS5 (Dissolved Oxygen, pH), WET Labs Cycle P (PO4-P), and Hobo Water Level & Conductivity meters. Preliminary spring/summer comparisons at the suburban site suggest increased baseflow nitrate concentrations and decreased diurnal nitrate variability (~0.05 vs. 0.035 mg/L daily fluctuation) following leaf emergence in spring. Nitrate concentrations were diluted during storms. Hysteresis was evident, suggesting groundwater nitrate sources attributable to septic systems were diluted by surface runoff during spring storms. The agricultural stream showed similar but more extreme patterns of increasing baseflow nitrate during the summer (~2.4 to 4.1 mg/L) and dilution during storms. The compilation of a high-frequency dataset for headwater streams across seasons and land-use types will provide valuable insight into complex land use/water quality relationships in urbanizing watersheds.

  1. ZnCl 2 induced catalytic conversion of softwood lignin to aromatics and hydrocarbons

    SciTech Connect

    Wang, Hongliang; Zhang, Libing; Deng, Tiansheng; Ruan, Hao; Hou, Xianglin; Cort, John R.; Yang, Bin

    2016-01-01

    Selective cleavage of C-O-C bonds in lignin without disrupting C-C linkages can result in releasing aromatic monomers and dimers that can be subsequently converted into chemicals and fuels. Results showed that both biomass-derived lignin and lignin model compounds were depolymerized in a highly concentrated ZnCl2 solution. Zn2+ ions in highly concentrated ZnCl2 solutions appeared to selectively coordinate with C-O-C bonds to cause key linkages of lignin much easier to cleave. In 63 wt.% ZnCl2 solution at 200 °C for 6 h, nearly half of the softwood technical lignin was converted to liquid products, of which the majority was alkylphenols. Results indicated that most β-O-4 and Cmethyl-OAr bonds of model compounds were cleaved undersame conditions, providing a foundation towards understanding lignin depolymerization in a concentrated ZnCl2 solution. The phenolic products were further converted into cyclic hydrocarbons via hydrodeoxygenation and coupling reactions by co-catalyst Ru/C.

  2. 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

  3. Synergistic enzymatic and microbial lignin conversion

    SciTech Connect

    Zhao, Cheng; Xie, Shangxian; Pu, Yunqiao; Zhang, Rui; Huang, Fang; Ragauskas, Arthur J.; Yuan, Joshua S.

    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 iron 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.

  4. 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.

  5. Arctic sea ice concentrations from special sensor microwave imager and advanced very high resolution radiometer satellite data

    NASA Technical Reports Server (NTRS)

    Emery, W. J.; Fowler, C.; Maslanik, J.

    1994-01-01

    Nearly coincident data from the special sensor microwave imager (SSM/I) and the advanced very high resolution radiometer (AVHRR) are used to compute and compare Arctic sea ice concentrations for different regions and times of the year. To help determine overall accuracies and to highlight sources of differences between passive microwave, optical wavelength, and thermal wavelength data, ice concentrations are estimated using two operational SSM/I ice concentration algorithms and with visible- and thermal-infrared wavelength AVHRR data. All algorithms capture the seasonal patterns of ice growth and melt. The ranges of differences fall within the general levels of uncertainty expected for each method and are similar to previous accuracy estimates. The estimated ice concentrations are all highly correlated, with uniform biases, although differences between individual pairs of observations can be large. On average, the NASA Team algorithm yielded 5% higher ice concentrations than the Bootstrap algorithm, while during nonmelt periods the two SSM/I algorithms agree to within 0.5%. These seasonal differences are consistent with the ways that the 19-GHz and 37-GHz microwave channels are used in the algorithms. When compared to the AVHRR-derived ice concentrations, the Team-algorithm results are more similar on average in terms of correlation and mean differences. However, the Team algorithm underestimates concentrations relative to the AVHRR output by 6% during cold months and overestimates by 3% during summer. Little seasonal difference exists between the Bootstrap and AVHRR results, with a mean difference of about 5%. Although the mean differences are less between the SSM/I-derived concentrations and concentrations estimated using AVHRR channel 1, the correlations appear substantially better between the SSM/I data and concentrations derived from AVHRR channel 4, particularly for the Team algorithm output.

  6. 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/Al2O3) 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, HY zeolitemore » was found crucial for lignin depolymerization, while Ru/Al2O3 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

  7. 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.

  8. 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.

  9. Method for regulation of plant lignin composition

    DOEpatents

    Chapple, Clint

    1999-01-01

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

  10. Lignin: Characterization of a Multifaceted Crop Component

    PubMed Central

    2013-01-01

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

  11. Effect of Penicillium chrysogenum on Lignin Transformation

    PubMed Central

    Rodríguez, A.; Carnicero, A.; Perestelo, F.; de la Fuente, G.; Milstein, O.; Falcón, M. A.

    1994-01-01

    A strain of Penicillium chrysogenum has been isolated from pine forest soils in Tenerife (Canary Islands). This strain was capable of utilizing hydroxylated and nonhydroxylated aromatic compounds, in particular cinnamic acid, as its sole carbon source. In an optimum medium with high levels of nitrogen (25.6 mM) and low levels of glucose (5.5 mM), it was able to decolorize Poly B-411 and to transform kraft, organosolv, and synthetic dehydrogenative polymerisate lignins. After 30 days of incubation, the amount of recovered kraft lignin was reduced to 83.5 and 91.3% of that estimated for uninoculated controls by spectrophotometry and klason lignin, respectively. At the same time, the pattern of molecular mass distribution of the lignin remaining in cultures was changed. The amount of organosolv lignin recovered from cultures was reduced to 90.1 and 94.6% of the initial amount as evaluated by spectrophotometry and klason lignin, respectively. About 6% of total applied radioactivity of O14CH3-organosolv lignin was recovered as 14CO2 after 30 days of incubation, and 18.5% of radioactivity from insoluble O14CH3-organosolv lignin was solubilized. After 26 days of incubation, 2.9% of 14C-β-dehydrogenative polymerisate and 4.1% of 14C-ring-dehydrogenative polymerisate evolved as 14CO2. PMID:16349361

  12. Development of Lignin-Based Polyurethane Thermoplastics

    SciTech Connect

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

    2013-01-01

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

  13. 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%.

  14. Structural elucidation of inhomogeneous lignins from bamboo.

    PubMed

    Wen, Jia-Long; Sun, Shao-Long; Xue, Bai-Liang; Sun, Run-Cang

    2015-01-01

    A better understanding of the inhomogeneous molecular structure of lignin from bamboo is a prerequisite for promoting the "biorefinery" technologies of the bamboo feedstock. A mild and successive method for fractionating native lignin from bamboo species was proposed in the present study. The molecular structure and structural inhomogeneity of the isolated lignin polymers were comprehensively investigated by elemental analysis, carbohydrate analysis, state-of-the-art NMR and analytical pyrolysis techniques (quantitative (13)C NMR, (13)C-DEPT 135 NMR, 2D-HSQC NMR, (31)P NMR, and pyrolysis-GC-MS). The results showed that the proposed method is effective for extracting lignin from bamboo. NMR results showed that syringyl (S) was the predominant unit in bamboo lignin over guaiacyl (G) and p-hydroxyphenyl (H) units. In addition, the lignin was associated with p-coumarates and ferulates via ester and ether bonds, respectively. Moreover, various substructures, such as β-O-4, β-β, β-5, β-1, and α,β-diaryl ether linkages, were identified and quantified by NMR techniques. Based on the results obtained, a proposed schematic diagram of structural heterogeneity of the lignin polymers extracted from the bamboo is presented. In short, well-defined inhomogeneous structures of native lignin from bamboo will facilitate further applications of bamboo in current biorefineries.

  15. Elimination of Flammable Gas Effects in Cerium Oxide Semiconductor-Type Resistive Oxygen Sensors for Monitoring Low Oxygen Concentrations

    PubMed Central

    Itoh, Toshio; Izu, Noriya; Akamatsu, Takafumi; Shin, Woosuck; Miki, Yusuke; Hirose, Yasuo

    2015-01-01

    We have investigated the catalytic layer in zirconium-doped cerium oxide, Ce0.9Zr0.1O2 (CeZr10) resistive oxygen sensors for reducing the effects of flammable gases, namely hydrogen and carbon monoxide. When the concentration of flammable gases is comparable to that of oxygen, the resistance of CeZr10 is affected by the presence of these gases. We have developed layered thick films, which consist of an oxygen sensor layer (CeZr10), an insulation layer (Al2O3), and a catalytic layer consisting of CeZr10 with 3 wt% added platinum, which was prepared via the screen printing method. The Pt-CeZr10 catalytic layer was found to prevent the detrimental effects of the flammable gases on the resistance of the sensor layer. This effect is due to the catalytic layer promoting the oxidation of hydrogen and carbon monoxide through the consumption of ambient O2 and/or the lattice oxygen atoms of the Pt-CeZr10 catalytic layer. PMID:25905705

  16. Minimizing 1/f Noise in Magnetic Sensors with a MEMS Flux Concentrator

    DTIC Science & Technology

    2004-12-01

    information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and...observe a field change of I nT at low sent time , we are in the process of completing a fabrica- fields, one would have to detect a voltage change of...4] Moodera, J.S., et al., Phys. Rev. Lett., 1995. device can be fabricated by batch processing at the same Vol. 74, p. 3273. time that the sensor is

  17. 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.

  18. Opportunities and challenges in biological lignin valorization

    SciTech Connect

    Beckham, Gregg T.; Johnson, Christopher W.; Karp, Eric M.; Salvachúa, Davinia; Vardon, Derek R.

    2016-12-01

    Lignin is a primary component of lignocellulosic biomass that is an underutilized feedstock in the growing biofuels industry. Despite the fact that lignin depolymerization has long been studied, the intrinsic heterogeneity of lignin typically leads to heterogeneous streams of aromatic compounds, which in turn present significant technical challenges when attempting to produce lignin-derived chemicals where purity is often a concern. In Nature, microorganisms often encounter this same problem during biomass turnover wherein powerful oxidative enzymes produce heterogeneous slates of aromatics compounds. Some microbes have evolved metabolic pathways to convert these aromatic species via ‘upper pathways’ into central intermediates, which can then be funneled through ‘lower pathways’ into central carbon metabolism in a process we dubbed ‘biological funneling’. This funneling approach offers a direct, biological solution to overcome heterogeneity problems in lignin valorization for the modern biorefinery. Coupled to targeted separations and downstream chemical catalysis, this concept offers the ability to produce a wide range of molecules from lignin. This perspective describes research opportunities and challenges ahead for this new field of research, which holds significant promise towards a biorefinery concept wherein polysaccharides and lignin are treated as equally valuable feedstocks. In particular, we discuss tailoring the lignin substrate for microbial utilization, host selection for biological funneling, ligninolytic enzyme–microbe synergy, metabolic engineering, expanding substrate specificity for biological funneling, and process integration, each of which presents key challenges. Ultimately, for biological solutions to lignin valorization to be viable, multiple questions in each of these areas will need to be addressed, making biological lignin valorization a multidisciplinary, co-design problem.

  19. Opportunities and challenges in biological lignin valorization.

    PubMed

    Beckham, Gregg T; Johnson, Christopher W; Karp, Eric M; Salvachúa, Davinia; Vardon, Derek R

    2016-12-01

    Lignin is a primary component of lignocellulosic biomass that is an underutilized feedstock in the growing biofuels industry. Despite the fact that lignin depolymerization has long been studied, the intrinsic heterogeneity of lignin typically leads to heterogeneous streams of aromatic compounds, which in turn present significant technical challenges when attempting to produce lignin-derived chemicals where purity is often a concern. In Nature, microorganisms often encounter this same problem during biomass turnover wherein powerful oxidative enzymes produce heterogeneous slates of aromatics compounds. Some microbes have evolved metabolic pathways to convert these aromatic species via 'upper pathways' into central intermediates, which can then be funneled through 'lower pathways' into central carbon metabolism in a process we dubbed 'biological funneling'. This funneling approach offers a direct, biological solution to overcome heterogeneity problems in lignin valorization for the modern biorefinery. Coupled to targeted separations and downstream chemical catalysis, this concept offers the ability to produce a wide range of molecules from lignin. This perspective describes research opportunities and challenges ahead for this new field of research, which holds significant promise towards a biorefinery concept wherein polysaccharides and lignin are treated as equally valuable feedstocks. In particular, we discuss tailoring the lignin substrate for microbial utilization, host selection for biological funneling, ligninolytic enzyme-microbe synergy, metabolic engineering, expanding substrate specificity for biological funneling, and process integration, each of which presents key challenges. Ultimately, for biological solutions to lignin valorization to be viable, multiple questions in each of these areas will need to be addressed, making biological lignin valorization a multidisciplinary, co-design problem.

  20. Detection of Volatile Organic Compounds by Self-assembled Monolayer Coated Sensor Array with Concentration-independent Fingerprints

    PubMed Central

    Chang, Ye; Tang, Ning; Qu, Hemi; Liu, Jing; Zhang, Daihua; Zhang, Hao; Pang, Wei; Duan, Xuexin

    2016-01-01

    In this paper, we have modeled and analyzed affinities and kinetics of volatile organic compounds (VOCs) adsorption (and desorption) on various surface chemical groups using multiple self-assembled monolayers (SAMs) functionalized film bulk acoustic resonator (FBAR) array. The high-frequency and micro-scale resonator provides improved sensitivity in the detections of VOCs at trace levels. With the study of affinities and kinetics, three concentration-independent intrinsic parameters (monolayer adsorption capacity, adsorption energy constant and desorption rate) of gas-surface interactions are obtained to contribute to a multi-parameter fingerprint library of VOC analytes. Effects of functional group’s properties on gas-surface interactions are also discussed. The proposed sensor array with concentration-independent fingerprint library shows potential as a portable electronic nose (e-nose) system for VOCs discrimination and gas-sensitive materials selections. PMID:27045012

  1. Detection of Volatile Organic Compounds by Self-assembled Monolayer Coated Sensor Array with Concentration-independent Fingerprints

    NASA Astrophysics Data System (ADS)

    Chang, Ye; Tang, Ning; Qu, Hemi; Liu, Jing; Zhang, Daihua; Zhang, Hao; Pang, Wei; Duan, Xuexin

    2016-04-01

    In this paper, we have modeled and analyzed affinities and kinetics of volatile organic compounds (VOCs) adsorption (and desorption) on various surface chemical groups using multiple self-assembled monolayers (SAMs) functionalized film bulk acoustic resonator (FBAR) array. The high-frequency and micro-scale resonator provides improved sensitivity in the detections of VOCs at trace levels. With the study of affinities and kinetics, three concentration-independent intrinsic parameters (monolayer adsorption capacity, adsorption energy constant and desorption rate) of gas-surface interactions are obtained to contribute to a multi-parameter fingerprint library of VOC analytes. Effects of functional group’s properties on gas-surface interactions are also discussed. The proposed sensor array with concentration-independent fingerprint library shows potential as a portable electronic nose (e-nose) system for VOCs discrimination and gas-sensitive materials selections.

  2. Chlorophyll pigment concentration using spectral curvature algorithms - An evaluation of present and proposed satellite ocean color sensor bands

    NASA Technical Reports Server (NTRS)

    Hoge, Frank E.; Swift, Robert N.

    1986-01-01

    During the past several years symmetric three-band (460-, 490-, 520-nm) spectral curvature algorithm (SCA) has demonstrated rather accurate determination of chlorophyll pigment concentration using low-altitude airborne ocean color data. It is shown herein that the in-water asymmetric SCA, when applied to certain recently proposed OCI (NOAA-K and SPOT-3) and OCM (ERS-1) satellite ocean color bands, can adequately recover chlorophyll-like pigments. These airborne findings suggest that the proposed new ocean color sensor bands are in general satisfactorily, but not necessarily optimally, positioned to allow space evaluation of the SCA using high-precision atmospherically corrected satellite radiances. The pigment concentration recovery is not as good when existing Coastal Zone Color Scanner bands are used in the SCA. The in-water asymmetric SCA chlorophyll pigment recovery evaluations were performed using (1) airborne laser-induced chlorophyll fluorescence and (2) concurrent passive upwelled radiances. Data from a separate ocean color sensor aboard the aircraft were further used to validate the findings.

  3. Isolation of lignin by organosolv process from different varieties of rice husk: Understanding their physical and chemical properties.

    PubMed

    Singh, Sandip K; Dhepe, Paresh L

    2016-12-01

    The aim of this work was to study the difference in properties of lignins, those (organosolv lignins (ORGLs, 12±3% yield and 93±5% mass balance) were isolated from diverse rice husk (RH) substrates using organosolv procedure (water:ethanol, H2SO4) carried out at 180°C for 1h. To identify the possible alterations in lignin structures several bulk and molecular level advanced characterization tools were employed. Even though lignins were extracted using common isolation procedure from three varieties of similar species of RH; from XRD, GPC, and elemental analysis it was found that those have comparable properties on bulk level. But molecular level analysis conducted using UV-vis, ATR, 1D/2D HSQC NMR techniques could help disclose that isolated lignins have varying concentrations of G, H, S and T substructures. Additionally, the double bond equivalence of 4.4-4.7 reveals that few of the aromatic rings are devoid of substituent.

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

    SciTech Connect

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

    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 of 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.

  5. Methanol Fractionation of Softwood Kraft Lignin: Impact on the Lignin Properties

    SciTech Connect

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

    2014-01-01

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

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

    PubMed

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

    2014-01-01

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

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

    SciTech Connect

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

    2004-11-10

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

  8. 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.

  9. Accuracy of different sensors for the estimation of pollutant concentrations (total suspended solids, total and dissolved chemical oxygen demand) in wastewater and stormwater.

    PubMed

    Lepot, Mathieu; Aubin, Jean-Baptiste; Bertrand-Krajewski, Jean-Luc

    2013-01-01

    Many field investigations have used continuous sensors (turbidimeters and/or ultraviolet (UV)-visible spectrophotometers) to estimate with a short time step pollutant concentrations in sewer systems. Few, if any, publications compare the performance of various sensors for the same set of samples. Different surrogate sensors (turbidity sensors, UV-visible spectrophotometer, pH meter, conductivity meter and microwave sensor) were tested to link concentrations of total suspended solids (TSS), total and dissolved chemical oxygen demand (COD), and sensors' outputs. In the combined sewer at the inlet of a wastewater treatment plant, 94 samples were collected during dry weather, 44 samples were collected during wet weather, and 165 samples were collected under both dry and wet weather conditions. From these samples, triplicate standard laboratory analyses were performed and corresponding sensors outputs were recorded. Two outlier detection methods were developed, based, respectively, on the Mahalanobis and Euclidean distances. Several hundred regression models were tested, and the best ones (according to the root mean square error criterion) are presented in order of decreasing performance. No sensor appears as the best one for all three investigated pollutants.

  10. 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.

  11. Characterization of electrospun lignin based carbon fibers

    NASA Astrophysics Data System (ADS)

    Poursorkhabi, Vida; Mohanty, Amar; Misra, Manjusri

    2015-05-01

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

  12. Characterization of asparagus lignin by HPLC.

    PubMed

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

    2008-09-01

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

  13. Aerosol assisted self-assembly as a route to synthesize solid and hollow spherical lignin colloids and its utilization in layer by layer deposition.

    PubMed

    Mishra, P K; Wimmer, R

    2017-03-01

    Lignin, a major constituent of plant cell-wall and by-product of paper based industries is traditionally used for low value applications (heat or electricity generation), but its potential in high value utilization has also been widely reported. In this work, we synthesized lignin colloidal particles using ultrasonic spray-freezing route without any chemical functionalization of material, and stabilized it by electrostatic route. As per our knowledge, this technique is the first reported method which yields hollow/solid lignin colloids having good particle size control without any chemical functionalization of material. Dioxane soluble fraction of Alkali lignin (d-lignin) was used without any further chemical functionalization. d-lignin dissolved in DMSO was sprayed upon liquid nitrogen cooled copper plate using an ultrasonic nebulizer. The resulting frozen droplets were collected and found to possess hollow and solid morphology. Particles thus obtained were characterized for their size distribution and morphology, and compared to theoretically anticipated values. Size tunability of particles in relation to concentration of sprayed lignin solution was also studied. In addition to that, six layers of lignin colloids were deposited on quartz slide with the aid of negligible UV absorbing polyelectrolyte aqueous solution PDADMAC [Poly (diallyldimethylammonium chloride)]. Gradation in UV absorbing ability of lignin with increase in number of layers could be clearly observed. Hollow and solid lignin colloids, apart from their application in sunscreen cosmetics owing to their UV absorbing ability, show potential applications in drug delivery also.

  14. Challenging/interesting lignin times

    DOE PAGES

    Ragauskas, Arthur J.

    2016-08-31

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

  15. Challenging/interesting lignin times

    SciTech Connect

    Ragauskas, Arthur J.

    2016-08-31

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

  16. Computing time-series suspended-sediment concentrations and loads from in-stream turbidity-sensor and streamflow data

    USGS Publications Warehouse

    Rasmussen, Patrick P.; Gray, John R.; Glysson, G. Doug; Ziegler, Andrew C.

    2010-01-01

    Over the last decade, use of a method for computing suspended-sediment concentration and loads using turbidity sensors—primarily nephelometry, but also optical backscatter—has proliferated. Because an in- itu turbidity sensor is capa le of measuring turbidity instantaneously, a turbidity time series can be recorded and related directly to time-varying suspended-sediment concentrations. Depending on the suspended-sediment characteristics of the measurement site, this method can be more reliable and, in many cases, a more accurate means for computing suspended-sediment concentrations and loads than traditional U.S. Geological Survey computational methods. Guidelines and procedures for estimating time s ries of suspended-sediment concentration and loading as a function of turbidity and streamflow data have been published in a U.S. Geological Survey Techniques and Methods Report, Book 3, Chapter C4. This paper is a summary of these guidelines and discusses some of the concepts, s atistical procedures, and techniques used to maintain a multiyear suspended sediment time series.

  17. Solution Concentration and Flow Rate of Fe3+-modified Porphyrin (Red Blood Model) on Giant Magnetoresistance (GMR) Sensor Efficiency

    NASA Astrophysics Data System (ADS)

    Aminudin, A.; Tjahyono, D. H.; Suprijadi; Djamal, M.; Zaen, R.; Nandiyanto, A. B. D.

    2017-03-01

    Red blood has been of great interest for scientists since it relates to human’ and living creature’s life sustainability. One of the important compounds in red blood is porphyrin. Here, the purpose of this study was to develop a method for detecting porphyrin concentration using the assistance of giant magnetoresistance. In short of the method, we added Fe3+ solution to the porphyrin, and the mixed solution was introduced to the magnetic field. Next, the magnetized solution was introduced to the magnetic sensor to indicate the existence of porphyrin in the solution. To confirm the effectiveness of our method in detecting porphyrin, we varied the flow rate and concentration of Fe3+-modified porphyrin solution. The result showed that the more concentration and the slower flow rate affected the higher sensitivity gained. Since this developed method is simple but effective for detecting porphyrin concentration, we believe that further development of this method will be benefit for many applications, specifically relating to the medical uses.

  18. Animal bioavailability of defined xenobiotic lignin metabolites

    SciTech Connect

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

    1990-09-01

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

  19. Novel multienzyme oxidative biocatalyst for lignin bioprocessing.

    PubMed

    Crestini, Claudia; Melone, Federica; Saladino, Raffaele

    2011-08-15

    A novel multienzyme biocatalyst, based on coimmobilization of the laccase and horseradish peroxidase by cross linking and layer-by-layer coating with polyelectrolyte, was designed, synthesized and applied at the development of an oxidative cascade process on lignin. The efficiency and specificity of the new LbL-multienzyme system, the occurrence of a synergy of the co-immobilized enzymes, the lignin oxidation pathway and the nature of the structural modifications occurred in treated lignins have been investigated in the present effort by means of GPC analysis and quantitative (31)P NMR techniques.

  20. Lignin hydrolysis and phosphorylation mechanism during phosphoric acid-acetone pretreatment: a DFT study.

    PubMed

    Qin, Wu; Wu, Lingnan; Zheng, Zongming; Dong, Changqing; Yang, Yongping

    2014-12-18

    The study focused on the structural sensitivity of lignin during the phosphoric acid-acetone pretreatment process and the resulting hydrolysis and phosphorylation reaction mechanisms using density functional theory calculations. The chemical stabilities of the seven most common linkages (β-O-4, β-β, 4-O-5, β-1, 5-5, α-O-4, and β-5) of lignin in H3PO4, CH3COCH3, and H2O solutions were detected, which shows that α-O-4 linkage and β-O-4 linkage tend to break during the phosphoric acid-acetone pretreatment process. Then α-O-4 phosphorylation and β-O-4 phosphorylation follow a two-step reaction mechanism in the acid treatment step, respectively. However, since phosphorylation of α-O-4 is more energetically accessible than phosphorylation of β-O-4 in phosphoric acid, the phosphorylation of α-O-4 could be controllably realized under certain operational conditions, which could tune the electron and hole transfer on the right side of β-O-4 in the H2PO4- functionalized lignin. The results provide a fundamental understanding for process-controlled modification of lignin and the potential novel applications in lignin-based imprinted polymers, sensors, and molecular devices.

  1. In vitro antioxidant and antidiabetic activities of biomodified lignin from Acacia nilotica wood.

    PubMed

    Barapatre, Anand; Aadil, Keshaw Ram; Tiwary, Bhupendra Nath; Jha, Harit

    2015-04-01

    The antioxidant and antidiabetic activity of biomodified alkali lignin extracted from a deciduous plant Acacia nilotica, was evaluated in vitro. The extracted alkali lignin was subjected to microbial biotransformation by ligninolytic fungus Aspergillus flavus and Emericella nidulans. These modifications were done under varying concentration of carbon to nitrogen sources. The structural feature of the lignin samples were compared by FTIR, functional group analysis and (13)C solid state NMR. All lignin samples were tested for antioxidant efficiency, reducing power and H2O2 scavenging power. Modifications in all lignin samples showed correlation with their antioxidant scavenging activity and reducing power. Antidiabetic properties were evaluated in terms of in vitro glucose movement inhibition and α-amylase inhibition assay. Modified samples exhibited increased glucose binding efficiency as demonstrated by the decreased glucose diffusion (55.5-76.3%) and 1.16-1.18-fold enhanced α-amylase inhibition in comparison to their control samples. The results obtained demonstrate that the structure and functional modifications in lignin significantly affects its bioefficacy in term of antioxidant and antidiabetic activities.

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

    PubMed

    Hu, Fan; Jung, Seokwon; Ragauskas, Arthur

    2012-08-01

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

  3. Investigation of trace metal binding properties of lignin by diffusive gradients in thin films.

    PubMed

    Hojaji, Elahe

    2012-09-01

    The binding behavior of lignin for Pb, Cu, Co, Mn, Cd and Ni was studied using the diffusive gradients in thin films technique (DGT). Samplers with different structures of diffusive gel were used in the well-stirred systems containing known concentrations of metals along with (a) 10, 20 and 40 μM lignin and; (b) 0.64 and 6.47 μM Suwannee river fulvic acid+40 μM lignin at an ionic strength of 0.01 M (NaNO(3)) and pH=7. Diffusion coefficients of lignin complexes in acrylamide gels were estimated and found to be less than 5% of the equivalent coefficients for the uncomplexed metal ions. These values were used to calculate concentrations of labile metals from DGT measurements in solutions, where lignin could discriminate metals in the order of Pb(+2)>Cu(+2)>Cd(+2)>Ni(+2)>Co(+2)>Mn(+2). Stability constants (LogK) were calculated using Visual MINTEQ II and WHAM V software. The K values were compared with the stability constants from titration of Pb and Cd with 10 μM lignin aqueous samples and with those of humic substances in natural waters. The constants obtained from measurement of complexing capacities might bias the real corresponding values unless two line regression analyses on titration data are considered. The DGT study of fractionation of metal species at varying ratios indicated that the proportion of organic complexes decreased with increasing ratios and gradually more metals were exchanged with inorganic phases. Speciation of Pb and Cd is affected by the concentrations of FA, Cd is dominantly bound with FA while Pb is evenly partitioned between the ligands. The comprehensive knowledge of metal-lignin complexes sheds some light on in situ operational speciation information that can be achieved by DGT.

  4. Improved noncontact optical sensor for detection of glucose concentration and indication of dehydration level

    PubMed Central

    Ozana, Nisan; Arbel, Nadav; Beiderman, Yevgeny; Mico, Vicente; Sanz, Martin; Garcia, Javier; Anand, Arun; Javidi, Baharam; Epstein, Yoram; Zalevsky, Zeev

    2014-01-01

    The ability to extract different bio-medical parameters from one single wristwatch device can be very applicable. The wearable device that is presented in this paper is based on two optical approaches. The first is the extraction and separation of remote vibration sources and the second is the rotation of linearly polarized light by certain materials exposed to magnetic fields. The technique is based on tracking of temporal changes of reflected secondary speckles produced in the wrist when being illuminated by a laser beam. Change in skin’s temporal vibration profile together with change in the magnetic medium that is generated by time varied glucose concentration caused these temporal changes. In this paper we present experimental tests which are the first step towards an in vivo noncontact device for detection of glucose concentration in blood. The paper also shows very preliminary results for qualitative capability for indication of dehydration. PMID:24940550

  5. Novel multi wavelength sensor concept to detect total hemoglobin concentration, methemoglobin and oxygen saturation

    NASA Astrophysics Data System (ADS)

    Timm, Ulrich; Gewiss, Helge; Kraitl, Jens; Stuepmann, Kirstin; Hinz, Michael; Koball, Sebastian; Ewald, Hartmut

    2015-03-01

    The paper will describe the novel multi-wavelength photometric device OxyTrue Hb® which is capable to measure the hemoglobin (Hb) and methemoglobin (MetHb) concentration non-invasively. Clinic trails in blood donation centers and during the dialysis are done to prove and demonstrate the performance of the system. The results are compared to the gold standard, the BGA measurement.

  6. 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

  7. Heterogeneous Ozonolysis of Surface Adsorbed Lignin Pyrolysis Products

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.

    2012-12-01

    Biomass combustion releases semi-volatile organic compounds into the troposphere, including many phenols and methoxyphenols as the result of lignin pyrolysis. Given their relatively low vapor pressures, these compounds readily adsorb on inorganic and organic aerosol substrates where they may alter aerosol properties and undergo heterogeneous chemistry. We use infrared spectroscopy (DRIFTS and ATR-FTIR) to monitor the adsorption and subsequent heterogeneous ozonolysis of model lignin pyrolysis products, including catechol, eugenol, and 4-propylguaiacol. Ozonolysis reaction kinetics were compared on various inorganic substrates - such as Al2O3 and NaCl, which serve as mineral and sea salt aerosol substrates, respectively - and as a function of ozone concentration and relative humidity. Following in situ FTIR analysis, the adsorbed organics were extracted and analyzed using gas chromatography-mass spectroscopy to identify reaction products and quantify product branching ratios. Ozonolysis of catechol and 4-propylguaiacol readily resulted in ring cleavage forming dicarboxylic acids (e.g., muconic acid). Eugenol ozonolysis proceeded rapidly at the alkene side chain producing homovanillic acid and homovanillin in an approximate 2:1 branching ratio at 0% RH; ring cleavage was also observed. For all lignin pyrolysis products, heterogeneous ozonolysis was faster on NaCl versus Al2O3. Implications for the atmospheric chemistry of semi-volatile methoxylphenols adsorbed on aerosol substrates will be discussed.

  8. Aircraft active and passive microwave validation of sea ice concentration from the Defense Meteorological Satellite Program special sensor microwave imager

    NASA Technical Reports Server (NTRS)

    Cavalieri, D. J.; Crawford, J. P.; Drinkwater, M. R.; Eppler, D. T.; Farmer, L. D.; Jentz, R. R.; Wackerman, C. C.

    1991-01-01

    Results are presented of a series of coordinate special sensor microwave imager (SSM/I) underflights that were carried out during March 1988 with NASA and Navy aircraft over portions of the Bering, Beaufort, and Chukchi seas. NASA DC-8 AMMR data from Bering Sea ice edge crossings were used to verify that the ice edge location, defined as the position of the initial ice bands encountered by the aircraft, corresponds to an SSM/I ice concentration of 15 percent. Direct comparison of SSM/I and aircraft ice concentrations for regions having at least 80 percent aircraft coverage reveals that the SSM/I total ice concentration is lower on average by 2.4 +/-2.4 percent. For multiyear ice, NASA and Navy flights across the Beaufort and Chukchi seas show that the SSM/I algorithm correctly maps the large-scale distribution of multiyear ice: the zone of first-year ice off the Alaskan coast, the large areas of mixed first-year and multiyear ice, and the region of predominantly multiyear ice north of the Canadian archipelago.

  9. Comparison of chlorophyll a concentration detected by remote sensors and other chlorophyll indices in inhomogeneous turbid waters.

    PubMed

    Sokoletsky, Leonid G; Yacobi, Yosef Z

    2011-10-20

    A new analytical approach for retrieval of the vertically weighted chlorophyll a concentration (Chl(rs)) detected by remote sensors is presented. Model calculations were carried out for the turbid waters of Lake Kinneret, Israel, and showed that Chl(rs) may be replaced by the average chlorophyll a concentration (Chl(p)) within the upper "penetration layer" 0-Z(p). The study also showed a high correlation between Chl(rs) and Chl concentration averaged in the other depth layers, namely, the 0-1 m layer, the euphotic layer (0-Z(e)), and the production layer (0-Z(pr)). Our findings are closely related to models developed for the world ocean, with the exception of periods when the dinoflagellate Peridinium gatunense blooms in the lake. We showed the effect of the pattern of vertical Chl distributions within the penetration layer on the difference between Chl(rs) and other Chl indices was conspicuous when the Chl maximum was in the uppermost 0- m layer of the water column. We assume that the presented approaches are instrumental for further development of optimal, locally adapted algorithms for remote sensing of Chl in any type of natural waters.

  10. A Portable Low-Power Acquisition System with a Urease Bioelectrochemical Sensor for Potentiometric Detection of Urea Concentrations

    PubMed Central

    Ma, Wei-Jhe; Luo, Ching-Hsing; Lin, Jiun-Ling; Chou, Sin-Houng; Chen, Ping-Hung; Syu, Mei-Jywan; Kuo, Shin-Hung; Lai, Shin-Chi

    2016-01-01

    This paper presents a portable low-power battery-driven bioelectrochemical signal acquisition system for urea detection. The proposed design has several advantages, including high performance, low cost, low-power consumption, and high portability. A LT1789-1 low-supply-voltage instrumentation amplifier (IA) was used to measure and amplify the open-circuit potential (OCP) between the working and reference electrodes. An MSP430 micro-controller was programmed to process and transduce the signals to the custom-developed software by ZigBee RF module in wireless mode and UART in able mode. The immobilized urease sensor was prepared by embedding urease into the polymer (aniline-co-o-phenylenediamine) polymeric matrix and then coating/depositing it onto a MEMS-fabricated Au working electrode. The linear correlation established between the urea concentration and the potentiometric change is in the urea concentrations range of 3.16 × 10−4 to 3.16 × 10−2 M with a sensitivity of 31.12 mV/log [M] and a precision of 0.995 (R2 = 0.995). This portable device not only detects urea concentrations, but can also operate continuously with a 3.7 V rechargeab-le lithium-ion battery (500 mA·h) for at least four days. Accordingly, its use is feasible and even promising for home-care applications. PMID:27049390

  11. A Portable Low-Power Acquisition System with a Urease Bioelectrochemical Sensor for Potentiometric Detection of Urea Concentrations.

    PubMed

    Ma, Wei-Jhe; Luo, Ching-Hsing; Lin, Jiun-Ling; Chou, Sin-Houng; Chen, Ping-Hung; Syu, Mei-Jywan; Kuo, Shin-Hung; Lai, Shin-Chi

    2016-04-02

    This paper presents a portable low-power battery-driven bioelectrochemical signal acquisition system for urea detection. The proposed design has several advantages, including high performance, low cost, low-power consumption, and high portability. A LT1789-1 low-supply-voltage instrumentation amplifier (IA) was used to measure and amplify the open-circuit potential (OCP) between the working and reference electrodes. An MSP430 micro-controller was programmed to process and transduce the signals to the custom-developed software by ZigBee RF module in wireless mode and UART in able mode. The immobilized urease sensor was prepared by embedding urease into the polymer (aniline-co-o-phenylenediamine) polymeric matrix and then coating/depositing it onto a MEMS-fabricated Au working electrode. The linear correlation established between the urea concentration and the potentiometric change is in the urea concentrations range of 3.16 × 10(-4) to 3.16 × 10(-2) M with a sensitivity of 31.12 mV/log [M] and a precision of 0.995 (R² = 0.995). This portable device not only detects urea concentrations, but can also operate continuously with a 3.7 V rechargeab-le lithium-ion battery (500 mA·h) for at least four days. Accordingly, its use is feasible and even promising for home-care applications.

  12. Computational Design of Lignin Depolymerization Catalysts

    SciTech Connect

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

    2012-01-01

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

  13. Lignin degradation in wood-feeding insects.

    PubMed

    Geib, Scott M; Filley, Timothy R; Hatcher, Patrick G; Hoover, Kelli; Carlson, John E; Jimenez-Gasco, Maria del Mar; Nakagawa-Izumi, Akiko; Sleighter, Rachel L; Tien, Ming

    2008-09-02

    The aromatic polymer lignin protects plants from most forms of microbial attack. Despite the fact that a significant fraction of all lignocellulose degraded passes through arthropod guts, the fate of lignin in these systems is not known. Using tetramethylammonium hydroxide thermochemolysis, we show lignin degradation by two insect species, the Asian longhorned beetle (Anoplophora glabripennis) and the Pacific dampwood termite (Zootermopsis angusticollis). In both the beetle and termite, significant levels of propyl side-chain oxidation (depolymerization) and demethylation of ring methoxyl groups is detected; for the termite, ring hydroxylation is also observed. In addition, culture-independent fungal gut community analysis of A. glabripennis identified a single species of fungus in the Fusarium solani/Nectria haematococca species complex. This is a soft-rot fungus that may be contributing to wood degradation. These results transform our understanding of lignin degradation by wood-feeding insects.

  14. Sequestration and Transport of Lignin Monomeric Precursors

    SciTech Connect

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

    2011-01-18

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

  15. Design and test of a low-cost RGB sensor for online measurement of microalgae concentration within a photo-bioreactor.

    PubMed

    Benavides, Micaela; Mailier, Johan; Hantson, Anne-Lise; Muñoz, Gerardo; Vargas, Alejandro; Van Impe, Jan; Vande Wouwer, Alain

    2015-02-26

    In this study, a low-cost RGB sensor is developed to measure online the microalgae concentration within a photo-bioreactor. Two commercially available devices, i.e., a spectrophotometer for offline measurements and an immersed probe for online measurements, are used for calibration and comparison purposes. Furthermore, the potential of such a sensor for estimating other variables is illustrated with the design of an extended Luenberger observer.

  16. 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

  17. 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

  18. Biologically produced acid precipitable polymeric lignin

    DOEpatents

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

    1984-01-01

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

  19. Chemical factors that control lignin polymerization

    SciTech Connect

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

    2014-01-01

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

  20. Non-contact optical sensor for detection of glucose concentration using a magneto-optic effect

    NASA Astrophysics Data System (ADS)

    Ozana, Nisan; Beiderman, Yevgeny; Anand, Arun; Javidi, Baharam; Polani, Sagi; Schwarz, Ariel; Shemer, Amir; García, Javier; Zalevsky, Zeev

    2016-03-01

    In this paper we aim to experimentally verify a speckle based technique for non-contact measurement of glucose concentration in blood stream while the vision for the final device aims to contain a single wristwatch-style device containing an AC (alternating) electro-magnet generated by a solenoid, a laser and a camera. The experiments presented in work are performed in-vitro in order to verify the effects that are responsible for the operation principle. When a glucose substance is inserted into a solenoid generating an alternating magnetic field it exhibits Faraday rotation which affects the temporal changes of the secondary speckle patterns distribution. The temporal frequency resulting from the AC magnetic field was found to have a lock-in amplification role which increased the observability of the relatively small magneto-optic effect. Experimental results to support the proposed concept are presented.

  1. Noncontact speckle-based optical sensor for detection of glucose concentration using magneto-optic effect

    NASA Astrophysics Data System (ADS)

    Ozana, Nisan; Beiderman, Yevgeny; Anand, Arun; Javidi, Baharam; Polani, Sagi; Schwarz, Ariel; Shemer, Amir; Garcia, Javier; Zalevsky, Zeev

    2016-06-01

    We experimentally verify a speckle-based technique for noncontact measurement of glucose concentration in the bloodstream. The final device is intended to be a single wristwatch-style device containing a laser, a camera, and an alternating current (ac) electromagnet generated by a solenoid. The experiments presented are performed in vitro as proof of the concept. When a glucose substance is inserted into a solenoid generating an ac magnetic field, it exhibits Faraday rotation, which affects the temporal changes of the secondary speckle pattern distributions. The temporal frequency resulting from the ac magnetic field was found to have a lock-in amplification role, which increased the observability of the relatively small magneto-optic effect. Experimental results to support the proposed concept are presented.

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

    SciTech Connect

    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 this 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.

  3. 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

  4. Depolymerization of steam-treated lignin for the production of green chemicals.

    PubMed

    Lavoie, Jean-Michel; Baré, Wadou; Bilodeau, Mathieu

    2011-04-01

    In this short communication, lignin produced by steam processing of agricultural (hemp) and forestry (softwood) was depolymerised via a base catalysis to produce a combination of monomers, dimers, trimers and residual char. The lignin broth produced directly after the base-catalysed steam treatment was treated under pressure (from 1300 to 1900 psi) at temperatures varying from 300 to 330 °C in a custom-made batch reactor. The lignin concentration in the aqueous base solution was 10 wt% whilst the NaOH concentration was 5 wt%. Identification of 26 compounds has been done: 17 compounds were common to the two feedstocks while the remaining 9 were specific to each feedstock used.

  5. Recovering ultraclean lignins of controlled molecular weight from Kraft black-liquor lignins.

    PubMed

    Klett, A S; Chappell, P V; Thies, M C

    2015-08-18

    By operating in a region of liquid-liquid equilibrium, hot acetic acid-water mixtures can be used to simultaneously clean, fractionate, and solvate Kraft black-liquor lignins. Lignin-rich liquid phases of controlled molecular weight with key metals contents reduced to <50 ppm are obtained without a washing step.

  6. Characterization of electrospun lignin based carbon fibers

    SciTech Connect

    Poursorkhabi, Vida; Mohanty, Amar; Misra, Manjusri

    2015-05-22

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

  7. 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.

  8. Green Diesel from Kraft Lignin in Three Steps.

    PubMed

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

    2016-06-22

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

  9. Influence of Mn concentration on magnetic topological insulator MnxBi2−xTe3 thin-film Hall-effect sensor

    DOE PAGES

    Ni, Y.; Zhang, Z.; Nlebedim, I. C.; ...

    2015-06-11

    Hall-effect (HE) sensors based on high-quality Mn-doped Bi2Te3 topological insulator (TI) thin films have been systematically studied in this paper. Improvement of Hall sensitivity is found after doping the magnetic element Mn into Bi2Te3. The sensors with low Mn concentrations, MnxBi2-xTe3, x = 0.01 and 0.08 show the linear behavior of Hall resistance with sensitivity about 5 Ω/T. And their Hall sensitivity shows weak dependence on temperature. For sensors with high Mn concentration (x = 0.23), the Hall resistance with respect to magnetic field shows a hysteretic behavior. Moreover, its sensitivity shows almost eight times as high as that ofmore » the HE sensors with low Mn concentration. The highest sensitivity can reach 43 Ω/T at very low magnetic field. This increase of Hall sensitivity is caused by the occurrence of anomalous HE (AHE) after ferromagnetic phase transition. Our work indicates that the magnetic-element-doped TIs with AHE are good candidates for HE sensors.« less

  10. Using in-situ spectrophotometric sensors to monitoring dissolved organic carbon concentration: our S::CAN experience

    NASA Astrophysics Data System (ADS)

    Coleman, Martin; Waldron, Susan; Scott, Marian; Drew, Simon

    2013-04-01

    Dissolved organic carbon, (DOC), is the component of the organic carbon that can pass through a membrane filter, with the accepted maximum pore size of 0.7 μm. There is growing interest in high resolution time series of such data e.g. heterotrophic respiration of DOC in freshwater systems can fuel atmospheric CO2 efflux so observing variation in DOC concentration, [DOC], is meaningful. Field deployable sensors, capable of measuring [DOC] on a continuous basis, have the potential to provide us with a far higher resolution time series data than we can obtain through manual sampling. At a catchment area draining Europe's largest windfarm, Whitelee, we have deployed an S::CAN Spectrolyser. This device scans wavelengths from 200 to 735nm, generating a spectral fingerprint and then, using an inbuilt algorithm, returns a value for the DOC concentration, termed DOC-equivalent, [DOC-eq]. The Spectrolyser also estimates other parameters such as total organic carbon and the true colour of the water. Unfortunately, our field Spectrolyser [DOC] are different from lab based measurement of [DOC] of the same field filtered samples (measured using a Thermalox high temperature catalytic oxidation system). Comparing 28 lab measured [DOC] with Spectrolyser [DOC-eq] shows an average difference of 7.6 mg/l C. Here we discuss our interpretation of why this disparity exists and how to accommodate this offset such that accuracy is improved. We have tried various methods of keeping the lens and path length clean through brushing, acid cleaning and the recent installation of a high pressure air hose (recommended by S::CAN). We will compare output before and after this installation. Further complexity is added because light may be absorbed by other components of the field sample, such as particulate material, and this could compromise the estimated [DOC-eq]. [DOC] may be estimated using absorption measurements made at 254nm and 340nm (Tipping et al, 2009). We have implemented this formula

  11. Reductive Catalytic Fractionation of Corn Stover Lignin

    SciTech Connect

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

    2016-12-05

    Reductive catalytic fractionation (RCF) has emerged as an effective biomass pretreatment strategy to depolymerize lignin into tractable fragments in high yields. We investigate the RCF of corn stover, a highly abundant herbaceous feedstock, using carbon-supported Ru and Ni catalysts at 200 and 250 degrees C in methanol and, in the presence or absence of an acid cocatalyst (H3PO4 or an acidified carbon support). Three key performance variables were studied: (1) the effectiveness of lignin extraction as measured by the yield of lignin oil, (2) the yield of monomers in the lignin oil, and (3) the carbohydrate retention in the residual solids after RCF. The monomers included methyl coumarate/ferulate, propyl guaiacol/syringol, and ethyl guaiacol/syringol. The Ru and Ni catalysts performed similarly in terms of product distribution and monomer yields. The monomer yields increased monotonically as a function of time for both temperatures. At 6 h, monomer yields of 27.2 and 28.3% were obtained at 250 and 200 degrees C, respectively, with Ni/C. The addition of an acid cocatalysts to the Ni/C system increased monomer yields to 32% for acidified carbon and 38% for phosphoric acid at 200 degrees C. The monomer product distribution was dominated by methyl coumarate regardless of the use of the acid cocatalysts. The use of phosphoric acid at 200 degrees C or the high temperature condition without acid resulted in complete lignin extraction and partial sugar solubilization (up to 50%) thereby generating lignin oil yields that exceeded the theoretical limit. In contrast, using either Ni/C or Ni on acidified carbon at 200 degrees C resulted in moderate lignin oil yields of ca. 55%, with sugar retention values >90%. Notably, these sugars were amenable to enzymatic digestion, reaching conversions >90% at 96 h. Characterization studies on the lignin oils using two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance and gel permeation chromatrography revealed

  12. Sorption of 2,4-dinitroanisole (DNAN) on lignin.

    PubMed

    Saad, Rabih; Radovic-Hrapovic, Zorana; Ahvazi, Behzad; Thiboutot, Sonia; Ampleman, Guy; Hawari, Jalal

    2012-01-01

    The present study describes the use of two commercially available lignins, namely, alkali and organosolv lignin, for the removal of 2,4-dinitroanisole (DNAN), a chemical widely used by the military and the dye industry, from water. Sorption of DNAN on both lignins reached equilibrium within 10 hr and followed pseudo second-order kinetics with sorption being faster with alkali than with organosolv lignin, i.e. k2 10.3 and 0.3 g/(mg x hr), respectively. In a separate study we investigated sorption of DNAN between 10 and 40 degrees C and found that the removal of DNAN by organosolv lignin increased from 0.8 to 7.5 mg/g but reduced slightly from 8.5 to 7.6 mg/g in the case of alkali lignin. Sorption isotherms for either alkali or organosolv lignin best fitted Freundlich equation with enthalpy of formation, deltaH0 equaled to 14 or 80 kJ/mol. To help understand DNAN sorption mechanisms we characterized the two lignins by elemental analysis, BET nitrogen adsorption-desorption and 31P NMR. Variations in elemental compositions between the two lignins indicated that alkali lignin should have more sites (O- and S-containing functionalities) for H-bonding. The BET surface area and calculated total pore volume of alkali lignin were almost 10 times greater than that of organosolv lignin suggesting that alkali lignin should provide more sites for sorption. 31P NMR showed that organosolv lignin contains more phenolic -OH groups than alkali lignin, i.e., 70% and 45%, respectively. The variations in the type of OH groups between the two lignins might have affected the strength of H-bonding between DNAN and the type of lignin used.

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

    SciTech Connect

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

    2013-01-01

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

  14. Lignin Peroxidase Oxidation of Aromatic Compounds in Systems Containing Organic Solvents

    PubMed Central

    Vazquez-Duhalt, Rafael; Westlake, Donald W. S.; Fedorak, Phillip M.

    1994-01-01

    Lignin peroxidase from Phanerochaete chrysosporium was used to study the oxidation of aromatic compounds, including polycyclic aromatic hydrocarbons and heterocyclic compounds, that are models of moieties of asphaltene molecules. The oxidations were done in systems containing water-miscible organic solvents, including methanol, isopropanol, N, N-dimethylformamide, acetonitrile, and tetrahydrofuran. Of the 20 aromatic compounds tested, 9 were oxidized by lignin peroxidase in the presence of hydrogen peroxide. These included anthracene, 1-, 2-, and 9-methylanthracenes, acenaphthene, fluoranthene, pyrene, carbazole, and dibenzothiophene. Of the compounds studied, lignin peroxidase was able to oxidize those with ionization potentials of <8 eV (measured by electron impact). The reaction products contain hydroxyl and keto groups. In one case, carbon-carbon bond cleavage, yielding anthraquinone from 9-methylanthracene, was detected. Kinetic constants and stability characteristics of lignin peroxidase were determined by using pyrene as the substrate in systems containing different amounts of organic solvent. Benzyl alkylation of lignin peroxidase improved its activity in a system containing water-miscible organic solvent but did not increase its resistance to inactivation at high solvent concentrations. PMID:16349176

  15. 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.

  16. 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.

  17. Fungal biodegradation and enzymatic modification of lignin

    PubMed Central

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

    2010-01-01

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

  18. Lignin-derivatives based polymers, blends and composites: A review.

    PubMed

    Naseem, Amina; Tabasum, Shazia; Zia, Khalid Mahmood; Zuber, Mohammad; Ali, Muhammad; Noreen, Aqdas

    2016-12-01

    Lignin and lignin derivatives biopolymers have several properties, such as high thermal stability, antioxidant, biodegradability, antimicrobial actions, adhesive properties, etc., and thus they can be extensively used in wide range of areas. Although human history mostly depend on the biopolymers, however derivatives of lignin such as sulfonate, phenolic, organosolv, Kraft and sodium sulfonate lignin have good mechanical and physicochemical properties. Well-designed materials such as coatings and paints, manufacturing of plastics and resins, for rubber packaging, for fuel production etc., can be obtained by the functionalizations of chemically modified lignin. Considering multi purposes properties of the lignin and lignin derivatives and extensive industrial applications of derivatives, this review sheds a light on lignin derivatives based materials with their prospective applications. All the technical scientific issues have been addressed highlighting the recent advancement.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    SciTech Connect

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

    1984-05-01

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

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

    PubMed Central

    Rüttimann-Johnson, C; Lamar, R T

    1996-01-01

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

  2. Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons.

    PubMed

    Bu, Quan; Lei, Hanwu; Wang, Lu; Wei, Yi; Zhu, Lei; Zhang, Xuesong; Liu, Yupeng; Yadavalli, Gayatri; Tang, Juming

    2014-06-01

    The aim of this study is to explore catalytic microwave pyrolysis of lignin for renewable phenols and fuels using activated carbon (AC) as a catalyst. A central composite experimental design (CCD) was used to optimize the reaction condition. The effects of reaction temperature and weight hourly space velocity (WHSV, h(-1)) on product yields were investigated. GC/MS analysis showed that the main chemical compounds of bio-oils were phenols, guaiacols, hydrocarbons and esters, most of which were ranged from 71% to 87% of the bio-oils depending on different reaction conditions. Bio-oils with high concentrations of phenol (45% in the bio-oil) were obtained. The calorific value analysis revealed that the high heating values (HHV) of the lignin-derived biochars were from 20.4 to 24.5 MJ/kg in comparison with raw lignin (19 MJ/kg). The reaction mechanism of this process was analyzed.

  3. 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.

  4. Insight into the solvent, temperature and time effects on the hydrogenolysis of hydrolyzed lignin.

    PubMed

    Shu, Riyang; Zhang, Qi; Ma, Longlong; Xu, Ying; Chen, Pengru; Wang, Chenguang; Wang, Tiejun

    2016-12-01

    The aim of this study is to explore the reaction mediums and conditions for producing high yield of valuable monomers from concentrated sulfuric acid hydrolyzed lignin. The solvent, temperature and time effects on the hydrogenolysis of hydrolyzed lignin were investigated under the catalysis of Pd/C and CrCl3. Supercritical methanol exhibits the best depolymerization performance, because of its unique diffusion, dissolution and acid-base properties. Afterwards, the influence of reaction temperature and time on depolymerization, repolymerization and coking during hydrogenolysis was examined in methanol. The high temperature is found to favor the depolymerization, with the β-O-4 linkages cleaved significantly. However, the repolymerization is promoted simultaneously, and a high amount of β-β groups form. These reactions are in constant competition with each other and the repolymerization is preferred at excessive high temperature, producing bulk char residues, that is coking. This study will provide a beneficial reference for the maximization of lignin waste valorization.

  5. Selective conversion of biorefinery lignin into dicarboxylic acids.

    PubMed

    Ma, Ruoshui; Guo, Mond; Zhang, Xiao

    2014-02-01

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

  6. Selective Conversion of Biorefinery Lignin into Dicarboxylic Acids

    SciTech Connect

    Ma, Ruoshui; Guo, Mond; Zhang, Xiao

    2014-02-01

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

  7. Process for producing phenolic compounds from lignins

    SciTech Connect

    Agblevor, F.A.

    1998-09-15

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

  8. Process for producing phenolic compounds from lignins

    DOEpatents

    Agblevor, Foster A.

    1998-01-01

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

  9. Chemical linkage of pine polysaccharides to lignin

    SciTech Connect

    Minor, J.L.

    1982-01-01

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

  10. Radical Nature of C-Lignin

    SciTech Connect

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

    2016-05-17

    The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxane $\\alpha$- and β-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the $\\alpha$-bond within the benzodioxane linkage is consistently greater than that of the β-bond in all dimers of each stereochemical arrangement, explained by the ability the $\\alpha$-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest-energy stereoisomer

  11. Radical Nature of C-Lignin

    DOE PAGES

    Berstis, Laura; Elder, Thomas; Crowley, Michael; ...

    2016-05-17

    The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxanemore » $$\\alpha$$- and β-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the $$\\alpha$$-bond within the benzodioxane linkage is consistently greater than that of the β-bond in all dimers of each stereochemical arrangement, explained by the ability the $$\\alpha$$-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest

  12. Performance of solid-state sensors for continuous, real-time measurement of soil CO2 concentrations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recent advances in sensor technology provide a robust capability for continuous measurement of soil gases. The performance of solid-state CO2 sensors (Model GMM220 series, Vaisala, Finland) was evaluated in laboratory, greenhouse, and irrigated wheat (Triticum aestivum L.). In ambient CO2 concentrat...

  13. Lignin removal enhancement from prehydrolysis liquor of kraft-based dissolving pulp production by laccase-induced polymerization.

    PubMed

    Wang, Qiang; Jahan, M Sarwar; Liu, Shanshan; Miao, Qingxian; Ni, Yonghao

    2014-07-01

    Lignin removal is essential for value-added utilization of hemicelluloses and acetic acid present in the prehydrolysis liquor (PHL) of a kraft-based hardwood dissolving pulp production. In this paper, a novel process concept, consisting of laccase-induced lignin polymerization, followed by filtration/flocculation, was developed to enhance the lignin removal. The results showed that the lignin removal increased from 11% to 46-61% at laccase concentration of 1-4 U mL(-1). The GPC results showed that the molecular weight of the lignin from the laccase treated PHL was increased by 160% in comparison with the original one. The subsequent flocculation using singular Poly-DADMAC system or dual polymer system of Poly-DADMAC/CPAM can further remove 10-15% lignin. The concentrations of hemicelluloses and acetic acid were negligibly affected during the laccase treatment, while flocculation caused 12-15% of total sugar loss. Additionally, the process incorporates this new concept into the kraft-based dissolving pulp production process was proposed.

  14. Bayesian probabilistic approach for inverse source determination from limited and noisy chemical or biological sensor concentration measurements

    NASA Astrophysics Data System (ADS)

    Yee, Eugene

    2007-04-01

    Although a great deal of research effort has been focused on the forward prediction of the dispersion of contaminants (e.g., chemical and biological warfare agents) released into the turbulent atmosphere, much less work has been directed toward the inverse prediction of agent source location and strength from the measured concentration, even though the importance of this problem for a number of practical applications is obvious. In general, the inverse problem of source reconstruction is ill-posed and unsolvable without additional information. It is demonstrated that a Bayesian probabilistic inferential framework provides a natural and logically consistent method for source reconstruction from a limited number of noisy concentration data. In particular, the Bayesian approach permits one to incorporate prior knowledge about the source as well as additional information regarding both model and data errors. The latter enables a rigorous determination of the uncertainty in the inference of the source parameters (e.g., spatial location, emission rate, release time, etc.), hence extending the potential of the methodology as a tool for quantitative source reconstruction. A model (or, source-receptor relationship) that relates the source distribution to the concentration data measured by a number of sensors is formulated, and Bayesian probability theory is used to derive the posterior probability density function of the source parameters. A computationally efficient methodology for determination of the likelihood function for the problem, based on an adjoint representation of the source-receptor relationship, is described. Furthermore, we describe the application of efficient stochastic algorithms based on Markov chain Monte Carlo (MCMC) for sampling from the posterior distribution of the source parameters, the latter of which is required to undertake the Bayesian computation. The Bayesian inferential methodology for source reconstruction is validated against real

  15. Genetic engineering of syringyl-enriched lignin in plants

    DOEpatents

    Chiang, Vincent Lee; Li, Laigeng

    2004-11-02

    The present invention relates to a novel DNA sequence, which encodes a previously unidentified lignin biosynthetic pathway enzyme, sinapyl alcohol dehydrogenase (SAD) that regulates the biosynthesis of syringyl lignin in plants. Also provided are methods for incorporating this novel SAD gene sequence or substantially similar sequences into a plant genome for genetic engineering of syringyl-enriched lignin in plants.

  16. Structure and radical scavenging activity relationships of pyrolytic lignins

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  17. Flocculation of high purity wheat straw soda lignin

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  18. Genetics and chemistry of lignin degradation by Streptomyces

    SciTech Connect

    Crawford, D.L.

    1992-01-01

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

  19. Plant lignin content altered by soil microbial community.

    PubMed

    Bennett, Alison E; Grussu, Dominic; Kam, Jason; Caul, Sandra; Halpin, Claire

    2015-04-01

    Questions have been raised in various fields of research about the consequences of plants with modified lignin production. As a result of their roles in nutrient cycling and plant diversity, plant-soil interactions should be a major focus of ecological studies on lignin-modified plants. However, most studies have been decomposition studies conducted in a single soil or in sterile soil. Thus, we understand little about plant-soil interactions in living lignin-modified plants. In lignin mutants of three different barley (Hordeum vulgare) cultivars and their corresponding wild-types associated with three different soil microbial communities, we asked: do plant-soil microbiome interactions influence the lignin content of plants?; does a mutation in lignin production alter the outcome of plant-soil microbiome interactions?; does the outcome of plant-soil microbiome interactions depend on host genotype or the presence of a mutation altering lignin production? In roots, the soil community explained 6% of the variation in lignin content, but, in shoots, the soil community explained 21% of the variation in lignin content and was the only factor influencing lignin content. Neither genotype nor mutations in lignin production explained associations with fungi. Lignin content changes in response to a plant's soil microbial community, and may be a defensive response to particular components of the soil community.

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

    NASA Astrophysics Data System (ADS)

    Hamilton, Susan E.; Hedges, John I.

    1988-01-01

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

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

    PubMed

    Gupta, Chetali; Washburn, Newell R

    2014-08-12

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

  2. Optical water quality model of Lake Ontario. 2: Determination of chlorophyll a and suspended mineral concentrations of natural waters from submersible and low altitude optical sensors.

    PubMed

    Bukata, R P; Bruton, J E; Jerome, J H; Jain, S C; Zwick, H H

    1981-05-01

    Spectrooptical and water quality data collected from a 1979 coordinated in situ and airborne study of western Lake Ontario are used to devise a five-component model from which subsurface chlorophyll a and suspended solids concentrations may be determined from submersible optical sensors capable of measuring spectral irradiance reflectance just beneath the free-surface layer. A water-air interface model, which incorporates the effects of surface reflection, is also presented in an attempt to extend such water quality estimations to low altitude remote sensors. Special emphasis is given to the spectral wavelength bands of the Coastal Zone Color Scanner aboard Nimbus-7.

  3. 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.

  4. Extracellular Enzyme Production and Synthetic Lignin Mineralization by Ceriporiopsis subvermispora

    PubMed Central

    Rüttimann-Johnson, Carmen; Salas, Loreto; Vicuña, Rafael; Kirk, T. Kent

    1993-01-01

    The ability of the white rot fungus Ceriporiopsis subvermispora to mineralize 14C-synthetic lignin was studied under different culture conditions, and the levels of two extracellular enzymes were monitored. The highest mineralization rates (28% after 28 days) were obtained in cultures containing a growth-limiting amount of nitrogen source (1.0 mM ammonium tartrate); under this condition, the levels of manganese peroxidase (MnP) and laccase present in the culture supernatant solutions were very low compared with cultures containing 10 mM of the nitrogen source. In contrast, cultures containing a limiting concentration of the carbon source (0.1% glucose) showed low levels of both enzymes and also very low mineralization rates compared with cultures containing 1% glucose. Cultures containing 11 ppm of Mn(II) showed a higher rate of mineralization than those containing 0.3 or 40 ppm of this cation. Levels of MnP and laccase were higher when 40 ppm of Mn(II) was used. Mineralization rates were slightly higher in cultures flushed daily with oxygen, whereas laccase levels were lower and MnP levels were approximately the same as in cultures maintained under an air atmosphere. The presence of 0.4 mM veratryl alcohol reduced both mineralization rates and MnP levels, without affecting laccase levels. Lignin peroxidase activity was not detected under any condition. Addition of purified lignin peroxidase to the cultures in the presence or absence of veratryl alcohol did not enhance mineralization rates significantly. PMID:16348955

  5. 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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    PubMed

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

    2008-12-01

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

  9. Flash vacuum pyrolysis of lignin model compounds

    SciTech Connect

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

    1997-03-01

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

  10. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

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

  11. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

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

  12. 21 CFR 573.600 - Lignin sulfonates.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

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

  13. Kinetic Model Development for Lignin Pyrolysis

    SciTech Connect

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

    2012-01-01

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

  14. 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...

  15. Lignin-blocking treatment of biomass and uses thereof

    DOEpatents

    Yang, Bin; Wyman, Charles E.

    2009-10-20

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

  16. Separation characteristics of lignin from Eucalyptus camaldulensis lignin celluloses for biomedical cellulose.

    PubMed

    Peng, Wanxi; Wang, Lansheng; Zhang, Minglong; Lin, Zhi

    2014-05-01

    The separation characteristics of Eucalyptus camaldulensis biomass cell wall were investigated and analyzed by FTIR, UV and XRD. The result showed that the crystallinity of untreated sample were lower than ones of treated samples at 10° C, 20° C and 30° C. Effect of temperature was very notable so as to use the lower temperature if cellulose would be kept natural structure during lignin separation from lignincellulose. Treatment time and temperature had a notably significant effect on SLR of E. camaldulensis lignin cellulose, and the SLR increased gradually with the temperature increment, and SLR were 73.35% at 10° C, 80.14% at 20° C, 83.73% at 30° C. The maximum of SLR increased with the rising of temperature 10° C, 20° C and 30° C. Consequently, the best separation conditions of lignin were 24h and 30° C. During hemicelluloses separation, the peak of C=O disappeared, and the peak of CO-OR, O-H and C-O abated, resulting that acetyl in hemicelluloses were mainly broken by the dehydration, heat decomposition reaction and mild thermal degradation. During lignin separation, the side chain and benzene ring of lignin of E. urophynis lignin cellulose reached the largest bond breaking characteristics under the temperature of 10° C at 7h, 20° C at 7h and 30° C at 24h.

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

    SciTech Connect

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

    2013-01-01

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

  18. Enhancing Signal Output and Avoiding BOD/Toxicity Combined Shock Interference by Operating a Microbial Fuel Cell Sensor with an Optimized Background Concentration of Organic Matter.

    PubMed

    Jiang, Yong; Liang, Peng; Liu, Panpan; Bian, Yanhong; Miao, Bo; Sun, Xueliang; Zhang, Helan; Huang, Xia

    2016-08-24

    In the monitoring of pollutants in an aquatic environment, it is important to preserve water quality safety. Among the available analysis methods, the microbial fuel cell (MFC) sensor has recently been used as a sustainable and on-line electrochemical microbial biosensor for biochemical oxygen demand (BOD) and toxicity, respectively. However, the effect of the background organic matter concentration on toxicity monitoring when using an MFC sensor is not clear and there is no effective strategy available to avoid the signal interference by the combined shock of BOD and toxicity. Thus, the signal interference by the combined shock of BOD and toxicity was systematically studied in this experiment. The background organic matter concentration was optimized in this study and it should be fixed at a high level of oversaturation for maximizing the signal output when the current change (ΔI) is selected to correlate with the concentration of a toxic agent. When the inhibition ratio (IR) is selected, on the other hand, it should be fixed as low as possible near the detection limit for maximizing the signal output. At least two MFC sensors operated with high and low organic matter concentrations and a response chart generated from pre-experiment data were both required to make qualitative distinctions of the four types of combined shock caused by a sudden change in BOD and toxicity.

  19. Enhancing Signal Output and Avoiding BOD/Toxicity Combined Shock Interference by Operating a Microbial Fuel Cell Sensor with an Optimized Background Concentration of Organic Matter

    PubMed Central

    Jiang, Yong; Liang, Peng; Liu, Panpan; Bian, Yanhong; Miao, Bo; Sun, Xueliang; Zhang, Helan; Huang, Xia

    2016-01-01

    In the monitoring of pollutants in an aquatic environment, it is important to preserve water quality safety. Among the available analysis methods, the microbial fuel cell (MFC) sensor has recently been used as a sustainable and on-line electrochemical microbial biosensor for biochemical oxygen demand (BOD) and toxicity, respectively. However, the effect of the background organic matter concentration on toxicity monitoring when using an MFC sensor is not clear and there is no effective strategy available to avoid the signal interference by the combined shock of BOD and toxicity. Thus, the signal interference by the combined shock of BOD and toxicity was systematically studied in this experiment. The background organic matter concentration was optimized in this study and it should be fixed at a high level of oversaturation for maximizing the signal output when the current change (ΔI) is selected to correlate with the concentration of a toxic agent. When the inhibition ratio (IR) is selected, on the other hand, it should be fixed as low as possible near the detection limit for maximizing the signal output. At least two MFC sensors operated with high and low organic matter concentrations and a response chart generated from pre-experiment data were both required to make qualitative distinctions of the four types of combined shock caused by a sudden change in BOD and toxicity. PMID:27563887

  20. 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.

  1. 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.

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

    PubMed

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

    2016-02-23

    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.

  3. 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

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

    SciTech Connect

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

    1983-11-01

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

  5. 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.

  6. Fractionation of bagasse into cellulose, hemicelluloses, and lignin with ionic liquid treatment followed by alkaline extraction.

    PubMed

    Lan, Wu; Liu, Chuan-Fu; Sun, Run-Cang

    2011-08-24

    Lignocellulose materials are potentially valuable resources for transformation into biofuels and bioproducts. However, their complicated structures make it difficult to fractionate them into cellulose, hemicelluloses, and lignin, which limits their utilization and economical conversion into value-added products. This study proposes a novel and feasible fractionation method based on complete dissolution of bagasse in 1-butyl-3-methylimidazolium chloride ([C(4)mim]Cl) followed by precipitation in acetone/water (9:1, v/v) and extraction with 3% NaOH solution. The ionic liquid [C(4)mim]Cl was easily recycled after concentration and treatment with acetonitrile. (1)H NMR analysis confirmed that there was no obvious difference between the recycled [C(4)mim]Cl and fresh material. Bagasse was fractionated with this method to 36.78% cellulose, 26.04% hemicelluloses, and 10.51% lignin, accounting for 47.17 and 33.85% of the original polysaccharides and 54.62% of the original lignin, respectively. The physicochemical properties of the isolated fractions were characterized by chemical analysis, high-performance anion exchange chromatography (HPAEC), gel permeation chromatography (GPC), Fourier transform infrared (FT-IR), and (1)H and 2D (13)C-(1)H correlation (HSQC) nuclear magnetic resonance spectroscopy. The results showed that the acetone-soluble lignin and alkaline lignin fractions had structures similar to those of milled wood lignin (MWL). The easy extraction of the noncellulose components from homogeneous bagasse solution and amorphous regenerated materials resulted in the relatively high purity of cellulosic fraction (>92%). The hemicellulosic fraction was mainly 4-O-methyl-D-glucuronoxylans with some α-L-arabinofuranosyl units substituted at C-2 and C-3.

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

    SciTech Connect

    Obst, J.R.

    1983-01-01

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

  8. Phyto-availability and speciation change of heavy metals in soils amended with lignin as micro-fertilizer.

    PubMed

    Wang, Songxue; Zhang, Shuzhen; Shan, Xiaoquan; Mu, Huanzhen

    2005-05-01

    Lignin is a primary byproduct from the black liquor treatment in paper making industries, its application as micro-fertilizer in agricultural land might provide a promising alternative to sewage discharge. However, application of such a micro-fertilizer might affect the soil properties and result in soil pollution. In this study, the effects of lignin application on phyto-availability and speciation change of heavy metals in soils were investigated. Greenhouse experiments showed that lignin application improved the growth of winter wheat (Triticum aestivum L.) in all three soils investigated. The increase of the biomass for wheat shoot was 59.7%, 39.8% and 12.3% for Beijing soil, Jiangxi soil and Dongbei soil, respectively. In contrast, lignin amendment decreased the concentrations of heavy metals in wheat shoots from 2.2% to 61.0%. Sequential extraction procedure of a three-step BCR was used to investigate the fraction distribution. The extractable fractions were specified as fraction B1: water soluble, exchangeable and carbonate bound or weakly specifically adsorbed; B2: Fe-Mn oxide bound; B3: organic matter and sulfide bound. The results showed that lignin application led to the redistribution of heavy metals in each fraction. Generally, heavy metals decreased in B1 and B2 fractions and increased in B3 fraction. Upon the results short-term application of lignin in agricultural land not only improves the growth of wheat but also reduces the phyto-abailability of heavy metal in wheat.

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

    PubMed

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

    2011-06-01

    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 l 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.

  10. 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

  11. Lignin depolymerization by fungal secretomes and a microbial sink

    SciTech Connect

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

    2016-08-25

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

  12. 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 (Mw) 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. Altogether, this study demonstrates that ligninolytic enzymes can be used to partially depolymerize

  13. Lignin Formation and the Effects of Gravity: A New Approach

    NASA Technical Reports Server (NTRS)

    Lewis, Norman G.

    1997-01-01

    Two aspects of considerable importance in the enigmatic processes associated with lignification have made excellent progress. The first is that, even in a microgravity environment, compression wood formation, and hence altered lignin deposition, can be induced upon mechanically bending the stems of woody gymnosperms. It now needs to be established if an organism reorientating its woody stem tissue will generate this tissue in microgravity, in the absence of externally applied pressure. If it does not, then gravity has no effect on its formation, and instead it results from alterations in the stress gradient experienced by the organism impacted. The second area of progress involves establishing how the biochemical pathway to lignin is regulated, particularly with respect to selective monolignol biosynthesis. This is an important question since individual monomer deposition occurs in a temporally and spatially specific manner. In this regard, the elusive metabolic switch between E-p-coumaryl alcohol and E-coniferyl alcohol synthesis has been detected, the significance of which now needs to be defined at the enzyme and gene level. Switching between monolignol synthesis is important, since it is viewed to be a consequence of different perceptions by plants in the gravitational load experienced, and thus in the control of the type of lignification response. Additional experiments also revealed the rate-limiting processes involved in monolignol synthesis, and suggest that a biological system (involving metabolite concentrations, as well as enzymatic and gene (in)activation processes) is involved, rather than a single rate-limiting step.

  14. Ethanol and lignin production from Brazilian empty fruit bunch biomass.

    PubMed

    Raman, Jegannathan Kenthorai; Gnansounou, Edgard

    2014-11-01

    Brazil Government is promoting palm plantations to use degraded land for biofuels. Palm production is expected to increase 35 per cent in future and there would be profuse biomass available that needs to be handled efficiently. Therefore, in this study the potential of EFB from Brazil as raw material for biorefinery was explored by compositional analysis and pretreatment conditions optimization to produce ethanol and co-products. EFB from Brazil contains significant cellulose, hemicellulose, lignin and low ash content. The optimized dilute sulfuric acid pretreatment conditions for efficient cellulose and hemicellulose separation were 160°C temperature, 1.025% v/v acid concentration, 10.5min and 20% solid loading. Under optimum pretreatment process conditions, low enzyme loading (10FPU, 20IU cellulase and glucosidase enzyme/g glucan) and 15% solid loading, 51.1g ethanol, 344.1g solid residue (65% lignin and 24.87MJ/kg LHV) and 3.7l xylose rich liquid could be produced per kg dry EFB.

  15. SOYBEAN STEM LIGNIN CONCENTRATION RELATES TO RESISTANCE TO SCLEROTINIA SCLEROTIORUM

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sclerotinia stem rot (SSR), caused by Sclerotinia sclerotiorum (Lib.) de Bary, is an economically important disease of soybean (Glycine max L. Merr.) in the north central United States and other temperate regions throughout the world. The occurrence and severity of SSR in the field is highly depend...

  16. 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.

  17. Sub-Surface Carbon Dioxide Concentration Measurement Using a Fiber Based Sensor in a Call/Return Geometry for Carbon Sequestration Site Monitoring

    NASA Astrophysics Data System (ADS)

    Wicks, G. R.; Soukup, B.; Repasky, K. S.; Carlsten, J.; Barr, J. L.; Dobeck, L.

    2010-12-01

    Geologic carbon sequestration is a means to mitigate the increasing atmospheric concentration of carbon dioxide (CO2) by capturing the CO2 at a source such as a power generation facility and storing the captured CO2 in geologic formations. Many technologic advances will need to occur for successful carbon sequestration including near surface monitoring tools and techniques to ensure site integrity and public safety. Researchers at Montana State University (MSU) are developing a scalable fiber sensor array in a call/return configuration for monitoring near sub-surface CO2 concentrations. The low cost fiber sensor array being developed at MSU for sub-surface CO2 detection for monitoring carbon sequestration sites will utilize a series of fiber probes connected to a two detectors and a 1 x N fiber switch that can direct the light to one of N fiber probes. The fiber sensor array will utilize a single tunable distributed feedback (DFB) diode laser with a center wavelength of 2.004 μm to access CO2 absorption features. The output from the DFB laser is incident on an inline fiber splitter that directs part of the light to a reference detector while the remaining light is directed to a fiber probe where the laser light interacts with the CO2. The light from the fiber probe is directed back through the switch and is incident on a transmission detector. The transmission as a function of wavelength is measured and a CO2 concentration is calculated. The fiber sensor array can easily be reconfigured by simply moving the fiber probes. Low cost is achieved by using inexpensive passive components in the fiber probes while limiting the number of the more expensive components including the DFB laser, the two detectors, and the single fiber switch. The fiber sensor was tested over a thirty day period at the Zero Emission Research Technology (ZERT) facility that was developed for testing surface and near surface carbon sequestration monitoring instrumentation using a controlled

  18. Effect of the lignin type on the morphology and thermal properties of the xanthan/lignin hydrogels.

    PubMed

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

    2013-03-01

    This paper reports the morphological and thermal characterization of xanthan/lignin hydrogels. It has been emphasized the effect of the lignin type on the hydrogel properties. The hydrogels described here were obtained by chemical crosslinking, in the presence of epichlorohydrine as a cross-linker agent. The obtained materials were analyzed by AFM, TG/DTG, DSC, and FT-IR spectroscopy. It has been established that hydrogels have a porous morphology. The lignin type influences the hydrogel morphology which is either fibrilar as in case of hydrogel containing aspen wood lignin (which has the highest content of COOH groups and lowest content of phenolic OH groups) or smooth surface for other hydrogels. The specific intermolecular interactions are stronger in the case of 70 xanthan (X)/30 aspen wood lignin (AWL) hydrogel. The thermal properties of the hydrogels also depend on lignin type, the lowest thermal stability being found for the hydrogel containing lignin with the highest content of functional groups (AWL).

  19. The dual effects of lignin content on enzymatic hydrolysis using film composed of cellulose and lignin as a structure model.

    PubMed

    Zhang, Lu; Zhang, Liming; Zhou, Tian; Wu, Yuying; Xu, Feng

    2016-01-01

    The degree of delignification during pretreatment is a critical question for economic conversion of biomass to sugar platform. Many models have been used to study the optimum lignin content in biomass, but few of them are able to study without disturbances, such as the complex component and structure of biomass. A novel film model composed of only cellulose and lignin was used to investigate the effect of lignin on enzymatic hydrolysis. High lignin-cellulose proportion (10.00-31.25%) hindered enzymatic hydrolysis, whereas low lignin-cellulose proportion (2.00-8.00%) showed a notable potential to promote enzymatic hydrolysis. The enzymatic hydrolysis rate of lignin-cellulose (6.00%) film was 11.5% higher than that of pure cellulose films. Further study indicated that the promotion was due to the enhancement of film porosity and roughness by residual lignin. Thus, based on the biomimetic model, excessive delignification is not recommended in view of efficient conversion and economy.

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2014-07-23

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

  2. Characteristics of the Fiber Laser Sensor System Based on Etched-Bragg Grating Sensing Probe for Determination of the Low Nitrate Concentration in Water

    PubMed Central

    Pham, Thanh Binh; Bui, Huy; Le, Huu Thang; Pham, Van Hoi

    2016-01-01

    The necessity of environmental protection has stimulated the development of many kinds of methods allowing the determination of different pollutants in the natural environment, including methods for determining nitrate in source water. In this paper, the characteristics of an etched fiber Bragg grating (e-FBG) sensing probe—which integrated in fiber laser structure—are studied by numerical simulation and experiment. The proposed sensor is demonstrated for determination of the low nitrate concentration in a water environment. Experimental results show that this sensor could determine nitrate in water samples at a low concentration range of 0–80 ppm with good repeatability, rapid response, and average sensitivity of 3.5 × 10−3 nm/ppm with the detection limit of 3 ppm. The e-FBG sensing probe integrated in fiber laser demonstrates many advantages, such as a high resolution for wavelength shift identification, high optical signal-to-noise ratio (OSNR of 40 dB), narrow bandwidth of 0.02 nm that enhanced accuracy and precision of wavelength peak measurement, and capability for optical remote sensing. The obtained results suggested that the proposed e-FBG sensor has a large potential for the determination of low nitrate concentrations in water in outdoor field work. PMID:28025512

  3. Characteristics of the Fiber Laser Sensor System Based on Etched-Bragg Grating Sensing Probe for Determination of the Low Nitrate Concentration in Water.

    PubMed

    Pham, Thanh Binh; Bui, Huy; Le, Huu Thang; Pham, Van Hoi

    2016-12-22

    The necessity of environmental protection has stimulated the development of many kinds of methods allowing the determination of different pollutants in the natural environment, including methods for determining nitrate in source water. In this paper, the characteristics of an etched fiber Bragg grating (e-FBG) sensing probe-which integrated in fiber laser structure-are studied by numerical simulation and experiment. The proposed sensor is demonstrated for determination of the low nitrate concentration in a water environment. Experimental results show that this sensor could determine nitrate in water samples at a low concentration range of 0-80 ppm with good repeatability, rapid response, and average sensitivity of 3.5 × 10(-3) nm/ppm with the detection limit of 3 ppm. The e-FBG sensing probe integrated in fiber laser demonstrates many advantages, such as a high resolution for wavelength shift identification, high optical signal-to-noise ratio (OSNR of 40 dB), narrow bandwidth of 0.02 nm that enhanced accuracy and precision of wavelength peak measurement, and capability for optical remote sensing. The obtained results suggested that the proposed e-FBG sensor has a large potential for the determination of low nitrate concentrations in water in outdoor field work.

  4. Spatio-temporal measurement of indoor particulate matter concentrations using a wireless network of low-cost sensors in households using solid fuels.

    PubMed

    Patel, Sameer; Li, Jiayu; Pandey, Apoorva; Pervez, Shamsh; Chakrabarty, Rajan K; Biswas, Pratim

    2017-01-01

    Many households use solid fuels for cooking and heating purposes. There is currently a knowledge gap in our understanding of the variations in indoor air quality throughout the household as most of the studies focus on the areas in the close proximity of the cookstove. A low-cost wireless particulate matter (PM) sensor network was developed and deployed in households in Raipur, India to establish the spatio-temporal variation of PM concentrations. The data from multiple sensors were acquired in real-time with a wireless system. Data collected from the sensors agreed well (R(2) =0.713) with the reference data collected from a commercially available instrument. Low spatial variability was observed within the kitchen due to its small size and poor ventilation - a common feature of most rural Indian kitchens. Due to insufficient ventilation from open doors and windows, high PM concentrations similar to those found in the kitchen were also found in the adjoining rooms. The same household showed significantly different post-extinguished cookstove PM concentration decay rates (0.26mg/m(3)-min and 0.87mg/m(3)-min) on different days, owing to varying natural air exchange rates (7.68m(3)/min and 37.40m(3)/min).

  5. Fiber optic Raman sensor to monitor the concentration ratio of nitrogen and oxygen in a cryogenic mixture.

    PubMed

    Tiwari, Vidhu S; Kalluru, Rajamohan R; Yueh, Fang Y; Singh, Jagdish P; Cyr, William St; Khijwania, Sunil K

    2007-06-01

    A spontaneous Raman scattering optical fiber sensor was developed for a specific need of the National Aeronautics and Space Administration (NASA) for long-term detection and monitoring of the purity of liquid oxygen (LO(2)) in the oxidizer feed line during ground testing of rocket engines. The Raman peak intensity ratios for liquid nitrogen (LN(2)) and LO(2) with varied weight ratios (LN(2)/LO(2)) were analyzed for their applicability to impurity sensing. The study of the sensor performance with different excitation light sources has helped to design a miniaturized, cost-effective system for this application. The optimal system response time of this miniaturized sensor for LN(2)/LO(2) measurement was found to be in the range of a few seconds. It will need to be further reduced to the millisecond range for real-time, quantitative monitoring of the quality of cryogenic fluids in a harsh environment.

  6. Study of Halitosis-Substance Sensing at Low Concentration Using an Electrochemical Sensor Array Combined with a Preconcentrator

    NASA Astrophysics Data System (ADS)

    Sasaya, Yosuke; Nakamoto, Takamichi

    A method for quantitative detection and discrimination of volatile sulfur compounds (VSCs) using an electrochemical sensor array combined with a preconcentrator was proposed. Halitosis is due to VSCs produced by bacterial metabolism inside the oral cavity. An organoleptic test is typically performed by a dental clinician for the assessment of halitosis, although it is a subjective test. Thus, an objective evaluation of halitosis is required. In this study, it was possible to discriminate among the VSCs such as hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl sulfide ((CH3)2S) over the range of 200ppb to 1000ppb. Moreover, mixture of two VSC vapors (H2S and CH3SH) at various mixing ratios were measured. The results indicated that the sensor responses to mixed samples satisfied the linear superposition. The mixture compositions of VSCs were almost correctly obtained from the sensor responses using partial least squares (PLS) regression analysis.

  7. High-Throughput Synthesis of Lignin Particles (∼30 nm to ∼2 μm) via Aerosol Flow Reactor: Size Fractionation and Utilization in Pickering Emulsions.

    PubMed

    Ago, Mariko; Huan, Siqi; Borghei, Maryam; Raula, Janne; Kauppinen, Esko I; Rojas, Orlando J

    2016-09-07

    An aerosol flow reactor was used for the first time for high-throughput, high yield synthesis of spherical lignin particles with given inherent hydrophilicity, depending on the precursor biomolecule. In situ fractionation via Berner type impactor afforded populations with characteristic sizes ranging from ∼30 nm to 2 μm. The as-produced, dry lignin particles displayed excellent mechanical integrity, even after redispersion under high shear in either mineral oil or water. They were effective in the stabilization of oil-in-water (O/W) Pickering emulsions with tunable droplet size, depending on the dimension of the lignin particles used for emulsification. The emulsion stability correlated with particle concentration as well as the respective lignin type. For the O/W emulsions stabilized with the more hydrophilic lignin particles, negligible changes in phase separation via Ostwald ripening and coalescence were observed over a period of time of more than two months. Together with the fact that the lignin particle concentrations used in emulsification were as low as 0.1%, our results reveal a remarkable ability to endow emulsified systems with high colloidal stability. Overall, we offer a new, high-yield, scalable nanomanufacturing approach to producing dry spherical lignin particles with size control and high production capacity. A number of emerging applications for these organic particles can be envisioned and, as a proof-of-concept, we illustrate here surfactant-free emulsification.

  8. An Integrated Instrumentation System for Velocity, Concentration and Mass Flow Rate Measurement of Solid Particles Based on Electrostatic and Capacitance Sensors.

    PubMed

    Li, Jian; Kong, Ming; Xu, Chuanlong; Wang, Shimin; Fan, Ying

    2015-12-10

    The online and continuous measurement of velocity, concentration and mass flow rate of pneumatically conveyed solid particles for the high-efficiency utilization of energy and raw materials has become increasingly significant. In this paper, an integrated instrumentation system for the velocity, concentration and mass flow rate measurement of dense phase pneumatically conveyed solid particles based on electrostatic and capacitance sensorsis developed. The electrostatic sensors are used for particle mean velocity measurement in combination with the cross-correlation technique, while the capacitance sensor with helical surface-plate electrodes, which has relatively homogeneous sensitivity distribution, is employed for the measurement of particle concentration and its capacitance is measured by an electrostatic-immune AC-based circuit. The solid mass flow rate can be further calculated from the measured velocity and concentration. The developed instrumentation system for velocity and concentration measurement is verified and calibrated on a pulley rig and through static experiments, respectively. Finally the system is evaluated with glass beads on a gravity-fed rig. The experimental results demonstrate that the system is capable of the accurate solid mass flow rate measurement, and the relative error is within -3%-8% for glass bead mass flow rates ranging from 0.13 kg/s to 0.9 kg/s.

  9. An Integrated Instrumentation System for Velocity, Concentration and Mass Flow Rate Measurement of Solid Particles Based on Electrostatic and Capacitance Sensors

    PubMed Central

    Li, Jian; Kong, Ming; Xu, Chuanlong; Wang, Shimin; Fan, Ying

    2015-01-01

    The online and continuous measurement of velocity, concentration and mass flow rate of pneumatically conveyed solid particles for the high-efficiency utilization of energy and raw materials has become increasingly significant. In this paper, an integrated instrumentation system for the velocity, concentration and mass flow rate measurement of dense phase pneumatically conveyed solid particles based on electrostatic and capacitance sensorsis developed. The electrostatic sensors are used for particle mean velocity measurement in combination with the cross-correlation technique, while the capacitance sensor with helical surface-plate electrodes, which has relatively homogeneous sensitivity distribution, is employed for the measurement of particle concentration and its capacitance is measured by an electrostatic-immune AC-based circuit. The solid mass flow rate can be further calculated from the measured velocity and concentration. The developed instrumentation system for velocity and concentration measurement is verified and calibrated on a pulley rig and through static experiments, respectively. Finally the system is evaluated with glass beads on a gravity-fed rig. The experimental results demonstrate that the system is capable of the accurate solid mass flow rate measurement, and the relative error is within −3%–8% for glass bead mass flow rates ranging from 0.13 kg/s to 0.9 kg/s. PMID:26690434

  10. Systems biology-guided biodesign of consolidated lignin conversion

    DOE PAGES

    Lin, Lu; Cheng, Yanbing; Pu, Yunqiao; ...

    2016-07-12

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

  11. Systems biology-guided biodesign of consolidated lignin conversion

    SciTech Connect

    Lin, Lu; Cheng, Yanbing; Pu, Yunqiao; Sun, Su; Li, Xiao; Jin, Mingjie; Pierson, Elizabeth A.; Gross, Dennis C.; Dale, Bruce E.; Dai, Susie Y.; Ragauskas, Arthur J.; Yuan, Joshua S.

    2016-07-12

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

  12. Production and Application of Lignosulfonates and Sulfonated Lignin.

    PubMed

    Aro, Thomas; Fatehi, Pedram

    2017-03-02

    Lignin is the largest reservoir of aromatic compounds on earth and has great potential to be used in many industrial applications. Alternative methods to produce lignosulfonates from spent sulfite pulping liquors and kraft lignin from black liquor of kraft pulping process are critically reviewed herein. Furthermore, options to increase the sulfonate contents of lignin-based products are outlined and the industrial attractiveness of them is evaluated. This evaluation includes sulfonation and sulfomethylation of lignin. To increase the sulfomethylation efficiency of lignin, various scenarios, including hydrolysis, oxidation, and hydroxymethylation, were compared. The application of sulfonated lignin-based products is assessed and the impact of the properties of these products on the characteristics of their end-use application is critically evaluated. Sulfonated lignin-based products have been used as dispersants in cement admixtures and dye solutions more than other applications, and their molecular weight and degree of sulfonation were crucial in determining their efficiency. The use of lignin-based sulfonated products in composites may result in an increase in the hydrophilicity of some composites, but the sulfonated products may need to be desulfonated with an alkali and/or oxygen prior to their use in composites. To be used as a flocculant, sulfonated lignin-based products may need to be cross-linked to increase their molecular weight. The challenges associated with the use of lignin-based products in these applications are comprehensively discussed herein.

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  14. Bisphenol-A sensors on polyimide fabricated by laser direct writing for on-site river water monitoring at attomolar concentration

    SciTech Connect

    Cheng, Cheng; Wang, Shutong; Wu, Jayne; Yu, Yongchao; Li, Ruozhou; Eda, Shigetoshi; Feng, Guoying; Chen, Jiangang; Lawrie, Benjamin J.; Hu, Anming

    2016-06-28

    This work presents an aptamer-based, highly sensitive and specific sensor for atto- to femtomolar level detection of bisphenol A (BPA). Because of its widespread use in numerous products, BPA enters surface water from effluent discharges during its manufacture, use, and from waste landfill sites throughout the world. On-site measurement of BPA concentrations in water is important for evaluating compliance with water quality standards or environmental risk levels of the harmful compound in the environment. The sensor in this work is porous, conducting, interdigitated electrodes that are formed by laser-induced carbonization of flexible polyimide sheets. BPA-specific aptamer is immobilized on the electrodes as the probe, and its binding with BPA at the electrode surface is detected by capacitive sensing. The binding process is aided by ac electroosmotic effect that accelerates the transport of BPA molecules to the nanoporous graphene-like structured electrodes. The sensor achieved a limit of detection of 58.28 aM with a response time of 20 s. The sensor is further applied for recovery analysis of BPA spiked in surface water. In conclusion, this work provides an affordable platform for highly sensitive, real time, and field-deployable BPA surveillance critical to the evaluation of the ecological impact of BPA exposure.

  15. Bisphenol-A sensors on polyimide fabricated by laser direct writing for on-site river water monitoring at attomolar concentration

    DOE PAGES

    Cheng, Cheng; Wang, Shutong; Wu, Jayne; ...

    2016-06-28

    This work presents an aptamer-based, highly sensitive and specific sensor for atto- to femtomolar level detection of bisphenol A (BPA). Because of its widespread use in numerous products, BPA enters surface water from effluent discharges during its manufacture, use, and from waste landfill sites throughout the world. On-site measurement of BPA concentrations in water is important for evaluating compliance with water quality standards or environmental risk levels of the harmful compound in the environment. The sensor in this work is porous, conducting, interdigitated electrodes that are formed by laser-induced carbonization of flexible polyimide sheets. BPA-specific aptamer is immobilized on themore » electrodes as the probe, and its binding with BPA at the electrode surface is detected by capacitive sensing. The binding process is aided by ac electroosmotic effect that accelerates the transport of BPA molecules to the nanoporous graphene-like structured electrodes. The sensor achieved a limit of detection of 58.28 aM with a response time of 20 s. The sensor is further applied for recovery analysis of BPA spiked in surface water. In conclusion, this work provides an affordable platform for highly sensitive, real time, and field-deployable BPA surveillance critical to the evaluation of the ecological impact of BPA exposure.« less

  16. 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.

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

    PubMed

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

    2015-02-05

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

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

    SciTech Connect

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

    2013-01-01

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

  19. Fluorescent-dye-doped sol-gel sensor for highly sensitive carbon dioxide gas detection below atmospheric concentrations.

    PubMed

    Dansby-Sparks, Royce N; Jin, Jun; Mechery, Shelly J; Sampathkumaran, Uma; Owen, Thomas William; Yu, Bi Dan; Goswami, Kisholoy; Hong, Kunlun; Grant, Joseph; Xue, Zi-Ling

    2010-01-15

    Optical fluorescence sol-gel sensors have been developed for the detection of carbon dioxide gas in the 0.03-30% range with a detection limit of 0.008% (or 80 ppm) and a quantitation limit of 0.02% (or 200 ppm) CO(2). Sol-gels were spin-coated on glass slides to create an organically modified silica-doped matrix with the 1-hydroxypyrene-3,6,8-trisulfonate (HPTS) fluorescent indicator. The luminescence intensity of the HPTS indicator (513 nm) is quenched by CO(2), which protonates the anionic form of HPTS. An ion pair technique was used to incorporate the lipophilic dye into the hydrophilic sol-gel matrix. TiO(2) particles (<5 microm diameter) were added to induce Mie scattering and increase the incident light interaction with the sensing film, thus increasing the signal-to-noise ratio. Moisture-proof overcoatings have been used to maintain a constant level of water inside the sensor films. The optical sensors are inexpensive to prepare and can be easily coupled to fiber optics for remote sensing capabilities. A fiber-optic bundle was used for the gas detection and shown to work as part of a multianalyte platform for simultaneous detection of multiple analytes. The studies reported here resulted in the development of sol-gel optical fluorescent sensors for CO(2) gas with sensitivity below that in the atmosphere (ca. 387 ppm). These sensors are a complementary approach to current FT-IR measurements for real-time carbon dioxide detection in environmental applications.

  20. Increasing Pleurotus ostreatus laccase production by culture medium optimization and copper/lignin synergistic induction.

    PubMed

    Tinoco, Raunel; Acevedo, Abisaí; Galindo, Enrique; Serrano-Carreón, Leobardo

    2011-04-01

    Laccases have great biotechnological potential in diverse industries as they catalyze the oxidation of a broad variety of chemical compounds. Production of laccases by basidiomycetes has been broadly studied as they secrete the enzymes, grow on cheap substrates, and they generally produce more than one isoenzyme (constitutive and/or inducible). Laccase production and isoenzyme profile can be modified through medium composition and the use of inducers. The objective of this work was to increase laccase production by Pleurotus ostreatus CP-50 through culture medium optimization and the simultaneous use of copper and lignin as inducers. Increased fungal growth was obtained through the use of a factorial fractional experimental design 2⁶⁻² where the influence of the nature and concentration of carbon and nitrogen sources was assessed. Although specific laccase production (U/mg biomass) decreased when malt extract medium was supplemented with carbon and nitrogen sources, fungal growth and laccase volumetric activity increased four and sixfold, respectively. The effect of media supplementation with copper and/or lignin on laccase production by P. ostreatus CP-50 was studied. A positive synergistic effect between copper and lignin was observed on laccase production. Overall, the use of an optimized medium and the simultaneous addition of copper and lignin improved growth, laccase volumetric activity, and process productivity by 4-, 60-, and 10-fold, respectively.

  1. Investigation into the lignin decomposition mechanism by analysis of the pyrolysis product of Pinus radiata.

    PubMed

    Kim, Young-Min; Jae, Jungho; Myung, Soyoung; Sung, Bong Hyun; Dong, Jong-In; Park, Young-Kwon

    2016-11-01

    Lignin pyrolysis chemistry was investigated via the analysis of the products obtained from the fast pyrolysis of a pine wood at different temperatures. Methoxy phenols, such as guaiacols and eugenols, were produced mainly at 375 and 475°C, while non-methoxy phenols, such as alkyl phenols and pyrocatechols were dominant at 525 and 575°C. At 575°C, aromatic hydrocarbons were formed together with larger amounts of light hydrocarbon gases. When the temperature was increased from 375 and 475°C, the yield of pyrolytic lignin was increased, whereas its average molecular weight was decreased. At 525°C, smaller molecular pyrolytic lignin with a maximum concentration of phenolic hydroxyl groups was produced due to the increased secondary cracking of the reaction intermediates. On the other hand, at 575°C, larger molecular pyrolytic lignin with smaller amounts of phenolic hydroxyl groups was produced due to the increased condensation activity of the pyrolysis reaction intermediates.

  2. Recovery of kraft lignin from pulping wastewater via emulsion liquid membrane process.

    PubMed

    Ooi, Zing-Yi; Harruddin, Norlisa; Othman, Norasikin

    2015-01-01

    Kraft lignin (KL) is a renewable source of many valuable intermediate biochemical products currently derived from petroleum. An excessive of lignin comes from pulping wastewater caused an adverse pollution problems hence affecting human and aquatic life. A comprehensive study pertaining to emulsion liquid membrane (ELM) extraction of lignin from pulping wastewater was presented. ELM formulation contains Aliquat 336 as carrier, kerosene as diluent, sodium bicarbonate (NaHCO3 ) as stripping agent and Span 80 as surfactant. The emulsion stability was investigated at different surfactant concentrations, homogenizer speed and emulsification time. Modifier (2-ethyl-1-hexanol) was added to avoid segregation of third phase while improving the emulsion stability. At optimum conditions, 95% and 56% of lignin were extracted and recovered, respectively at 10 min of extraction time, 0.007 M of Aliquat 336, 0.1 M of NaHCO3 and 1:5 of treat ratio. Additional of modifier was contributed to highest recovery up to 98%. The ELM process was found to be equally feasible and quite effective in the recovery of KL from real pulping wastewater. Therefore, ELM process provides a promising alternative technology to recover KL from pulping wastewater while solving the environmental problems simultaneously.

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

    SciTech Connect

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

    1987-01-01

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

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

    PubMed

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

    2016-08-01

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

  5. Mechanism of lignin inhibition of enzymatic biomass deconstruction

    SciTech Connect

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

    2015-12-01

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

  6. Mechanism of lignin inhibition of enzymatic biomass deconstruction

    DOE PAGES

    Vermaas, Josh V.; Petridis, Loukas; Qi, Xianghong; ...

    2015-12-01

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

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

    SciTech Connect

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

    2012-01-01

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

  8. Selective flotation of PVC using gelatin and lignin alkali.

    PubMed

    Yenial, Unzile; Kangal, Olgaç; Güney, Ali

    2013-06-01

    Recycling has become one of the most important issues as a result of increasing waste mass in present day. This is especially important for polymer wastes as they are hard to degenerate in nature. Today, most of the practical methods used for the recycling of waste mass, such as hand sorting, gravity separation, etc., cannot be performed successfully owing to close densities of polymers. Froth flotation can be used successfully and economically for this purpose. The main objective of this study was to investigate the effect of plasticizer reagents and the success of froth flotation at plastic recycling. In this study, lignin alkali and gelatin were used as plasticizer reagents. The effect of these reagents was searched with the parameters of pH, concentration, conditioning and flotation time. In the case of post-consumed polyethylene terephthalate and polyvinyl chloride (PVC), 98.9% purity of PVC was obtained at optimum conditions.

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

    PubMed

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

    2016-03-08

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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2012-01-01

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

  12. Isolation and Characterization of Gramineae and Fabaceae Soda Lignins

    PubMed Central

    Domínguez-Robles, Juan; Sánchez, Rafael; Espinosa, Eduardo; Savy, Davide; Mazzei, Pierluigi; Piccolo, Alessandro; Rodríguez, Alejandro

    2017-01-01

    Some agricultural residues such as wheat or barley straw, as well as certain fast-growing plants like Leucaena leucocephala and Chamaecytisus proliferus, could be used as raw materials for the paper industry as an alternative to traditional plants (eucalyptus, pine, etc.). In the present study, four types of lignin obtained from the spent liquors produced by the pulping processes using the abovementioned feedstocks were isolated and characterized. Lignin samples were acquired through an acid precipitation from these spent liquors. The characterization of the precipitated lignin samples were performed using a Fourier transform infrared spectroscopy (FT-IR) and both liquid- and solid-state nuclear magnetic resonance spectroscopy (NMR) to analyse the chemical structure, and thermogravimetric analysis (TGA) for determining the thermal properties. Additionally, chemical composition of lignin fractions was also measured. Even though they were of different botanical origin, all the studied samples except for wheat straw lignin had a similar chemical composition and thermal behaviour, and identical chemical structure. Wheat straw lignin showed a greater amount of Klason lignin and lower carbohydrate content. Furthermore, this lignin sample showed a higher thermal stability and significantly different cross-peak patterns in the 2D-NMR experiments. The molecular structures corresponding to p-coumarate (PCA), ferulate (FA) and cinnamyl aldehyde end-groups (J) were only detected in wheat isolated lignin. PMID:28165411

  13. Changes in lignin content of leaf litters during mulching.

    PubMed

    Jin, Zhenfu; Akiyama, Takuya; Chung, Byung Yeoup; Matsumoto, Yuji; Iiyama, Kenji; Watanabe, Satomi

    2003-11-01

    Alkaline nitrobenzene oxidation, ozonation and methoxyl content determinations were applied to decomposing leaf litter of Ginkgo biloba L., Cinnamomum camphora sieb., Zelkova serrata Makino and Firmiana simplex W. F. Wight, respectively, during mulching to investigate the properties and estimate changes in lignin composition and content. Since the Klason lignin residue originated from components highly resistant to degradation by acid, the methoxyl content of Klason residue was used to estimate the lignin content of leaf litter. Quantitative analysis of presumed lignin-derived fragments, by use of alkaline nitrobenzene oxidation and ozonation methods, suggested that the estimated lignin content approximates that of the real lignin content of leaves, which is greatly overestimated by the Klason procedure. The estimated lignin contents ranged from 3.9 to 10.0% while the Klason lignan residue varied from 37.1 to 46.7% in un-mulched leaf litter. The absolute amounts of the measured lignin somewhat decreased during mulching, while the structure of lignin remaining in leaf litters after mulching was considered not to be very different from its original structure.

  14. Experimental Study of Mechanistic Acid Deconstruction of Lignin

    SciTech Connect

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

    2012-01-01

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

  15. 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.

  16. 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%)

  17. Enhancing the sensitivity of chemiresistor gas sensors based on pristine carbon nanotubes to detect low-ppb ammonia concentrations in the environment.

    PubMed

    Rigoni, Federica; Tognolini, Silvia; Borghetti, Patrizia; Drera, Giovanni; Pagliara, Stefania; Goldoni, Andrea; Sangaletti, Luigi

    2013-11-12

    The possibility of using novel architectures based on carbon nanotubes (CNTs) for a realistic monitoring of the air quality in an urban environment requires the capability to monitor concentrations of polluting gases in the low-ppb range. This limit has been so far virtually neglected, as most of the testing of new ammonia gas sensor devices based on CNTs is carried out above the ppm limit. In this paper, we present single-wall carbon nanotube (SWCNT) chemiresistor gas sensors operating at room temperature, displaying an enhanced sensitivity to NH3. Ammonia concentrations in air as low as 20 ppb have been measured, and a detection limit of 3 ppb is demonstrated, which is in the full range of the average NH3 concentration in an urban environment and well below the sensitivities so far reported for pristine, non-functionalized SWCNTs operating at room temperature. In addition to careful preparation of the SWCNT layers, through sonication and dielectrophoresis that improved the quality of the CNT bundle layers, the low-ppb limit is also attained by revealing and properly tracking a fast dynamics channel in the desorption process of the polluting gas molecules.

  18. 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

  19. 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

  20. Oil-in-Water Emulsions Stabilized by Carboxymethylated Lignins: Properties and Energy Prospects.

    PubMed

    Li, Shuai; Willoughby, Julie A; Rojas, Orlando J

    2016-09-08

    We take advantage of the amphiphilic properties of technical lignin macromolecules and their inherent high calorific values to formulate oil-in-water (O/W) fuel emulsions with high internal-phase ratios. For the oil phase, we used a combustible hydrocarbon (kerosene) with a measured equivalent alkane carbon number of 12. To adjust the balance of affinity with the oil and water phases and their surface activity, pine kraft lignins were carboxymethylated to different degrees, as quantified by (13) C NMR spectroscopy, potentiometric titrations, and zeta potential measurements. Carboxymethylated lignins (CMLs) with a degree of substitution of 30 % displayed a critical aggregation concentration of 3 %. The salinity and pH of the aqueous phase were chosen as formulation variables and adjusted within the Winsor framework. The O/W emulsions were produced by following standard protocols. The drop-size distributions of emulsions with varying pH, degree of substitution, and composition (water-to-oil ratio, WOR) were determined, and the long-term stabilities and rheological behavior of these emulsions were analyzed. Most of the obtained O/W fuel emulsions showed shear-thinning behavior with a drop size of approximately 2.5 μm and were stable for over 30 days. The combustion of the lignins and their respective emulsions was performed, and their higher heating values (HHVs) were quantified. The HHVs of CML and a high-internal-phase (WOR=30:70) O/W emulsion were 20 and 30 MJ kg(-1) , respectively. Overall, we propose the stabilization of O/W fuel emulsions by lignin as an important avenue in the utilization of this abundant biomacromolecule.

  1. 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.

  2. 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.

  3. Pathways for Biomass-Derived Lignin to Hydrocarbon Fuels

    SciTech Connect

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

    2013-09-01

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

  4. NASA team algorithm for sea ice concentration retrieval from Defense Meteorological Satellite Program special sensor microwave imager - Comparison with Landsat satellite imagery

    NASA Technical Reports Server (NTRS)

    Steffen, Konrad; Schweiger, Axel

    1991-01-01

    The present study describes the validation of the the NASA team algorithm for the determination of sea ice concentrations from the Defense Meteorological Satellite Program special sensor microwave imager (SSM/I). A total of 28 cloud-free Landsat scenes were selected to permit validation of the passive microwave ice concentration algorithm for a range of ice concentrations and ice types. The sensitivity of the NASA team algorithm to the selection of locally and seasonally adjusted algorithm parameters is discussed. Mean absolute differences between SSM/I and Landsat ice concentrations are within 1 percent during fall using local and global tie points (standard deviations of the difference are +/-3.1 and +/-6.2 percent, respectively). In areas with greater amounts of nilas and young ice, the NASA team algorithm was found to underestimate ice concentrations by as much as 9 percent. It is inferred that the standard deviation between SSM/I and Landsat ice concentrations decreases from +/-7 to +/-5 percent with local tie points compared to the global ones for spring and fall.

  5. A new highly sensitive method to assess respiration rates and kinetics of natural planktonic communities by use of the switchable trace oxygen sensor and reduced oxygen concentrations.

    PubMed

    Tiano, Laura; Garcia-Robledo, Emilio; Revsbech, Niels Peter

    2014-01-01

    Oxygen respiration rates in pelagic environments are often difficult to quantify as the resolutions of our methods for O2 concentration determination are marginal for observing significant decreases during bottle incubations of less than 24 hours. Here we present the assessment of a new highly sensitive method, that combine Switchable Trace Oxygen (STOX) sensors and all-glass bottle incubations, where the O2 concentration was artificially lowered. The detection limit of respiration rate by this method is inversely proportional to the O2 concentration, down to <2 nmol L(-1) h(-1) for water with an initial O2 concentration of 500 nmol L(-1). The method was tested in Danish coastal waters and in oceanic hypoxic waters. It proved to give precise measurements also with low oxygen consumption rates (∼7 nmol L(-1) h(-1)), and to significantly decrease the time required for incubations (≤14 hours) compared to traditional methods. This method provides continuous real time measurements, allowing for a number of diverse possibilities, such as modeling the rate of oxygen decrease to obtain kinetic parameters. Our data revealed apparent half-saturation concentrations (Km values) one order of magnitude lower than previously reported for marine bacteria, varying between 66 and 234 nmol L(-1) O2. Km values vary between different microbial planktonic communities, but our data show that it is possible to measure reliable respiration rates at concentrations ∼0.5-1 µmol L(-1) O2 that are comparable to the ones measured at full air saturation.

  6. 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.

  7. Nanoscale lignin particles as sources of dissolved iron to the ocean

    NASA Astrophysics Data System (ADS)

    Krachler, Regina; von der Kammer, Frank; Jirsa, Franz; Süphandag, Altan; Krachler, Rudolf F.; Plessl, Christof; Vogt, Margret; Keppler, Bernhard K.; Hofmann, Thilo

    2012-09-01

    Primary production in large areas of the open ocean is limited by low iron concentrations. Rivers are potential sources of iron to the ocean, however, riverine iron is prone to intense flocculation and sedimentation in the estuarine mixing zone. Here we report the detection of iron-rich nanoparticles in a typical peatland-draining creek which are resistant against salt-induced flocculation i.e., their behavior is in sharp contrast to the well-known behavior of Fe colloids in river waters. Sample fractionation by AsFlFFF (Asymmetric Flow Field Flow Fractionation) revealed that these powerful iron carriers are in the size range of only 0.5-3.0 nm hydrodynamic diameter. They were isolated from the water phase using solid phase extraction/gel permeation chromatography, and analyzed by a CuO oxidation/GC-MS method. Our results suggest that the particles consist mainly of lignin catabolites and that gymnosperm as well as angiosperm tissues are contributors to the seawater-resistant iron-bearing DOM. Lignin phenols, which have no autochthonous source in the ocean, have been nevertheless found in low concentrations throughout the entire Arctic, Atlantic, and Pacific oceans. It is therefore tempting to speculate that peatland-derived iron-bearing lignin particles may have a sufficiently long half-life in ocean waters to sustain iron concentration in extended regions of the ocean.

  8. 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.

  9. Activated effect of lignin on α-amylase.

    PubMed

    Zhang, Juan; Cui, Jun-Hui; Yin, Tingting; Sun, Lizhou; Li, Genxi

    2013-12-01

    This paper reports a new kind of activator of α-amylase, lignin, which can greatly increase α-amylase activity. The promoted ratio of lignin is even much higher than that of chloride ion, the traditional activator of α-amylase. Further experimental results reveal that lignin may interact with α-amylase to form a 1:1 complex with a binding constant of 4.47×10(5) M(-1). The binding is spontaneous and lignin/α-amylase complex formation is an exothermal reaction. Hydrogen bonding plays a key role and non-radiation energy transfers from α-amylase to lignin in the binding process. Lignin, combining with α-amylase, conforms to a first-order exponential decay function. The formation of the lignin/α-amylase complex results in the reduction of α-helical content from 57.7% to 53.9%, the increase of the polarity around tryptophan residues, the decrease of the hydrophobicity, and the enlargement of protein granule volume. This work will give a deeper insight into lignin as a kind of dietary fibre, known as an important food functional factor. Furthermore, it also contributes to the exploration of an activator of α-amylase, used in the food industry.

  10. Modification of lignin content and composition in plants

    DOEpatents

    Ye, Zheng-Hua

    2002-01-01

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

  11. Lignin-degrading enzyme from the hymenomycete Phanerochaete chrysosporium Burds

    SciTech Connect

    Tien, M.; Kirk, T.K.

    1983-08-12

    The extracellular fluid of ligninolytic cultures of the wood-decomposing basidiomycete Phanerochaete chrysosporium Burds contains an enzyme that degrades lignin substructure model compounds as well as spruce and birch lignins. It has a molecular size of 42,000 daltons and requires hydrogen peroxide for activity. (Refs. 24).

  12. 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

  13. 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.

  14. Lignin Degradation by Fusarium solani f. sp. glycines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sudden death syndrome (SDS), caused by the soilborne fungal pathogen Fusarium solani f. sp. glycines, is one of the most important diseases of soybean. Lignin degradation may play a role in the infection, colonization, and survival of the fungus in root tissue . Lignin degradation by F. solani f. sp...

  15. Metabolic engineering of novel lignin in biomass crops

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lignin, a phenolic polymer in the secondary-thickened plant cell wall, is the major cause of lignocellulosic biomass recalcitrance toward efficient industrial processing. From an applications perspective, it is desirable that secondary cell walls of second generation bioenergy crops have lignin that...

  16. Roles of lignin biosynthesis and regulatory genes in plant development.

    PubMed

    Yoon, Jinmi; Choi, Heebak; An, Gynheung

    2015-11-01

    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.

  17. Isolation of Bacillus sp. strains capable of decomposing alkali lignin and their application in combination with lactic acid bacteria for enhancing cellulase performance.

    PubMed

    Chang, Young-Cheol; Choi, Dubok; Takamizawa, Kazuhiro; Kikuchi, Shintaro

    2014-01-01

    Effective biological pretreatment method for enhancing cellulase performance was investigated. Two alkali lignin-degrading bacteria were isolated from forest soils in Japan and named CS-1 and CS-2. 16S rDNA sequence analysis indicated that CS-1 and CS-2 were Bacillus sp. Strains CS-1 and CS-2 displayed alkali lignin degradation capability. With initial concentrations of 0.05-2.0 g L(-1), at least 61% alkali lignin could be degraded within 48 h. High laccase activities were observed in crude enzyme extracts from the isolated strains. This result indicated that alkali lignin degradation was correlated with laccase activities. Judging from the net yields of sugars after enzymatic hydrolysis, the most effective pretreatment method for enhancing cellulase performance was a two-step processing procedure (pretreatment using Bacillus sp. CS-1 followed by lactic acid bacteria) at 68.6%. These results suggest that the two-step pretreatment procedure is effective at accelerating cellulase performance.

  18. Lignin depolymerization by fungal secretomes and a microbial sink

    SciTech Connect

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

    2016-08-25

    In Nature, powerful oxidative enzymes secreted by white rot fungi and some bacteria catalyze lignin depolymerization and some microbes are able to catabolize the resulting aromatic compounds as carbon and energy sources. Taken together, these two processes offer a potential route for microbial valorization of lignin. However, many challenges remain in realizing this concept, including that oxidative enzymes responsible for lignin depolymerization also catalyze polymerization of low molecular weight (LMW) lignin. Here, multiple basidiomycete secretomes were screened for ligninolytic enzyme activities in the presence of a residual lignin solid stream from a corn stover biorefinery, dubbed DMR-EH (Deacetylation, Mechanical Refining, and Enzymatic Hydrolysis) lignin. Two selected fungal secretomes, with high levels of laccases and peroxidases, were utilized for DMR-EH lignin depolymerization assays. The secretome from Pleurotus eryngii, which exhibited the highest laccase activity, reduced the lignin average molecular weight (Mw) 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. Altogether, this study demonstrates that

  19. A GIS-based assessment of the suitability of SCIAMACHY satellite sensor measurements for estimating reliable CO concentrations in a low-latitude climate.

    PubMed

    Fagbeja, Mofoluso A; Hill, Jennifer L; Chatterton, Tim J; Longhurst, James W S

    2015-02-01

    An assessment of the reliability of the Scanning Imaging Absorption Spectrometer for Atmospheric Cartography (SCIAMACHY) satellite sensor measurements to interpolate tropospheric concentrations of carbon monoxide considering the low-latitude climate of the Niger Delta region in Nigeria was conducted. Monthly SCIAMACHY carbon monoxide (CO) column measurements from January 2,003 to December 2005 were interpolated using ordinary kriging technique. The spatio-temporal variations observed in the reliability were based on proximity to the Atlantic Ocean, seasonal variations in the intensities of rainfall and relative humidity, the presence of dust particles from the Sahara desert, industrialization in Southwest Nigeria and biomass burning during the dry season in Northern Nigeria. Spatial reliabilities of 74 and 42 % are observed for the inland and coastal areas, respectively. Temporally, average reliability of 61 and 55 % occur during the dry and wet seasons, respectively. Reliability in the inland and coastal areas was 72 and 38 % during the wet season, and 75 and 46 % during the dry season, respectively. Based on the results, the WFM-DOAS SCIAMACHY CO data product used for this study is therefore relevant in the assessment of CO concentrations in developing countries within the low latitudes that could not afford monitoring infrastructure due to the required high costs. Although the SCIAMACHY sensor is no longer available, it provided cost-effective, reliable and accessible data that could support air quality assessment in developing countries.

  20. Biological effects of high molecular weight lignin derivatives.

    PubMed

    Pessala, Piia; Schultz, Eija; Kukkola, Jukka; Nakari, Tarja; Knuutinen, Juha; Herve, Sirpa; Paasivirta, Jaakko

    2010-10-01

    A number of high molecular weight (HMW) lignin derivatives possessing varied chemical properties were screened for their biological effects in order to obtain more information on the possible structural features of HMW lignin-related effects. The studied compounds were both commercial and in-house extracted lignin derivatives. Bioassays used include reverse electron transport (RET), Vibrio fischeri, Daphnia magna, and juvenile rainbow trout (Oncorhynchus mykiss) hepatocytes. The studied lignin derivatives inhibited the in vitro systems and luminescence of V. fischeri bacteria to some extent-daphnids were not affected. It seems that, at least in the RET assay, certain pH-dependent functional groups in lignin may be of importance regarding the biological effects.

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

    SciTech Connect

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

    2014-07-26

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

  2. Process for conversion of lignin to reformulated hydrocarbon gasoline

    DOEpatents

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

    1999-09-28

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

  3. Lignin-based cement fluid loss control additive

    SciTech Connect

    Schilling, P.

    1990-05-22

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

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

    SciTech Connect

    Petridis, Loukas; Smith, Jeremy C.

    2016-01-13

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

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

    PubMed

    Petridis, Loukas; Smith, Jeremy C

    2016-02-08

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

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

    DOE PAGES

    Petridis, Loukas; Smith, Jeremy C.

    2016-01-13

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

  7. Absence of microbial mineralization of lignin in anaerobic enrichment cultures.

    PubMed Central

    Odier, E; Monties, B

    1983-01-01

    The existence of anaerobic biodegradation of lignin was examined in mixed microflora. Egyptian soil samples, in which rapid mineralization of organic matter takes place in the presence of an important anaerobic microflora, were used to obtain the anaerobic enrichment cultures for this study. Specifically, 14CO2 or [14C]lignin wood was used to investigate the release of labeled gaseous or soluble degradation products of lignin in microbial cultures. No conversion of 14C-labeled lignin to 14CO2 or 14CH4 was observed after 6 months of incubation at 30 degrees C in anaerobic conditions with or without NO3-. A small increase in soluble radioactivity was observed in certain cultures, but it could not be related to the release of catabolic products during the anaerobic biodegradation of lignin. PMID:6639020

  8. Color reduction of sulfonated eucalyptus kraft lignin.

    PubMed

    Zhang, Hui; Bai, Youcan; Zhou, Wanpeng; Chen, Fangeng

    2017-04-01

    Several eucalyptus lignins named as HSL, SML and BSL were prepared by high temperature sulfonation, sulfomethylation, butane sultone sulfonation respectively. The color properties of samples were investigated. Under optimized conditions the sulfonic group (SO3H) content of HSL, SML and BSL reached 1.52, 1.60 and 1.58mmol/g, respectively. Samples were characterized by UV-vis spectroscopy, FTIR spectroscopy, (1)H NMR spectroscopy, GPC and brightness test, respectively. The results revealed that BSL performed a higher molecular weight and lighter color due to the phenolic hydroxyl blocking by 1,4-butane sultone (1,4-BS). The color reduction of sodium borohydride treated BSL (labeled as SBSL) was further enhanced and the brightness value was improved by 76.1% compared with the darkest HSL. SBSL process was much better than HSL and SML process. Hydroxyl blocking effect of 1,4-BS and reducibility of sodium borohydride played important roles in the color reduction of sulfonated eucalyptus kraft lignin.

  9. Bleaching with lignin-oxidizing enzymes.

    PubMed

    Bajpai, Pratima; Anand, Aradhna; Bajpai, Pramod K

    2006-01-01

    General concern about the environmental impact of chlorine bleaching effluents has led to a trend towards elementary chlorine-free or totally chlorine free bleaching methods. Considerable interest has been focused on the use of biotechnology in pulp bleaching, as large number of microbes and the enzymes produced by them are known to be capable of preferential degradation of native lignin and complete degradation of wood. Enzymes of the hemicellulolytic type, particularly xylan-attacking enzymes xylanases are now used commercially in the mills for pulp treatment and subsequent incorporation into bleach sequences. Certain white-rot fungi can delignify Kraft pulps increasing their brightness and their responsiveness to brightening with chemicals. The fungal treatments are too slow but the enzymes produced from the fungi can also delignify pulps and these enzymatic processes are likely to be easier to optimize and apply than the fungal treatments. This article presents an overview of the developments in the application of lignin-oxidizing enzymes in bleaching of chemical pulps. The present knowledge of the mechanisms on the action of enzymes as well as the practical results and advantages obtained on the laboratory and industrial scale are discussed.

  10. 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

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

    SciTech Connect

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

    1981-02-01

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

  12. Structure-property characteristics of pyrolytic lignins derived from fast pyrolysis of a lignin rich biomass extract

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this study, various fractions of pyrolytic lignin were isolated from the fast pyrolysis oil of Etek lignin, a residue of acidic processing of wood. Based on the solubility differences in selected solvents, the water insolubles of the pyrolysis oil were separated into various fractions (methanol-i...

  13. Cell wall fermentation kinetics are impacted more by lignin content and ferulate cross-linking than by lignin composition

    Technology Transfer Automated Retrieval System (TEKTRAN)

    BACKGROUND: We used a biomimetic model system to ascertain how reductions in ferulate-lignin cross-linking and shifts in lignin composition influence ruminal cell wall fermentation. Primary walls from maize cell suspensions with normal or reduced feruloylation were artificially lignified with variou...

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

    SciTech Connect

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

    2017-01-01

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

  15. Efficiency calibration and minimum detectable activity concentration of a real-time UAV airborne sensor system with two gamma spectrometers.

    PubMed

    Tang, Xiao-Bin; Meng, Jia; Wang, Peng; Cao, Ye; Huang, Xi; Wen, Liang-Sheng; Chen, Da

    2016-04-01

    A small-sized UAV (NH-UAV) airborne system with two gamma spectrometers (LaBr3 detector and HPGe detector) was developed to monitor activity concentration in serious nuclear accidents, such as the Fukushima nuclear accident. The efficiency calibration and determination of minimum detectable activity concentration (MDAC) of the specific system were studied by MC simulations at different flight altitudes, different horizontal distances from the detection position to the source term center and different source term sizes. Both air and ground radiation were considered in the models. The results obtained may provide instructive suggestions for in-situ radioactivity measurements of NH-UAV.

  16. On the propensity of lignin to associate: a size exclusion chromatography study with lignin derivatives isolated from different plant species.

    PubMed

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

    2007-10-01

    Despite evidence that lignin associates under both aqueous and organic media, the magnitude and nature of the underlying driving forces are still a matter of discussion. The present paper addresses this issue by examining both solution properties and size exclusion behaviour of lignins isolated from five different species of softwoods, as well as from the angiosperms Eucalyptus globulus and wheat straw. This investigation has used the recently described protocol for isolating enzymatic mild acidolysis lignin (EMAL), which offers lignin samples highly representative of the overall lignin present in the wood cell wall. The molecular weight distributions of these EMALs were found to be dependent upon the wood species from which they were isolated and upon the incubation conditions used prior to size exclusion chromatography. While the chromatograms of EMALs isolated from softwoods displayed a bimodal behaviour, the elution profiles of EMAL from E. globulus and straw were nearly unimodal. A marked tendency to dissociate prevailed under incubation at room temperature for all examined species with the exception of the straw lignin preparation; furthermore, lignin solutions incubated at 4 degrees C showed an associative behaviour manifested by an increase in the weight and number average molecular weights for some species. The extent of such association/dissociation, as well as the time needed for the process to reach completion, was also found to depend upon the wood species, i.e. lignins from softwoods were found to associate/dissociate to a greater extent than lignins from E. globulus and straw. The origin of such effects within the lignin structure is also discussed.

  17. 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.

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

    PubMed

    Pellerin, Brian A; Hernes, Peter J; Saraceno, JohnFranco; 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 (SUVA(254)) 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 SUVA(254) 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.

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

    PubMed

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

    2014-11-01

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

  20. A New Highly Sensitive Method to Assess Respiration Rates and Kinetics of Natural Planktonic Communities by Use of the Switchable Trace Oxygen Sensor and Reduced Oxygen Concentrations

    PubMed Central

    Tiano, Laura; Garcia-Robledo, Emilio; Revsbech, Niels Peter

    2014-01-01

    Oxygen respiration rates in pelagic environments are often difficult to quantify as the resolutions of our methods for O2 concentration determination are marginal for observing significant decreases during bottle incubations of less than 24 hours. Here we present the assessment of a new highly sensitive method, that combine Switchable Trace Oxygen (STOX) sensors and all-glass bottle incubations, where the O2 concentration was artificially lowered. The detection limit of respiration rate by this method is inversely proportional to the O2 concentration, down to <2 nmol L−1 h−1 for water with an initial O2 concentration of 500 nmol L−1. The method was tested in Danish coastal waters and in oceanic hypoxic waters. It proved to give precise measurements also with low oxygen consumption rates (∼7 nmol L−1 h−1), and to significantly decrease the time required for incubations (≤14 hours) compared to traditional methods. This method provides continuous real time measurements, allowing for a number of diverse possibilities, such as modeling the rate of oxygen decrease to obtain kinetic parameters. Our data revealed apparent half-saturation concentrations (Km values) one order of magnitude lower than previously reported for marine bacteria, varying between 66 and 234 nmol L−1 O2. Km values vary between different microbial planktonic communities, but our data show that it is possible to measure reliable respiration rates at concentrations ∼0.5–1 µmol L−1 O2 that are comparable to the ones measured at full air saturation. PMID:25127458

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

    PubMed

    Thakur, Vijay Kumar; Thakur, Manju Kumari

    2015-01-01

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

  2. Coagulation-flocculation for lignin removal from wastewater - a review.

    PubMed

    Nawaz, Arfa; Ahmed, Zaki; Shahbaz, Ali; Khan, Zahra; Javed, Mohsin

    2014-01-01

    Industrial discharge has tremendously increased inorganic pollutants in water bodies all over the world. Paper and pulp effluent is included in one of the most pollution generating discharges containing complex chemical compounds such as lignin. For clean and healthy water resources, the recovery of lignin from wastewater from the paper and pulp industry is of high importance. Available chemical and biological technologies for removal of lignin have certain drawbacks. Coagulation and flocculation is not only the economic but also the effective method for removal of lignin. The present review highlights available coagulants employed for removal of lignin from paper and pulp wastewater. Each coagulant is pH dependent and shows varied results with change in effluent characteristics. The hydrolysis products of aluminium-based coagulants, iron-based coagulants and copper sulphate have positive charges. These positive charges promote formation of flocs through charged neutralisation or sweep flocculation. In the case of titanium-based coagulants, hydrolysis product is negatively charged and mode is heterocoagulation. Ninety percent recovery of lignin is achieved by using a mixture of oxotitanium sulphate and aluminium sulphate and 80% with aluminium sulphate. Virtually complete recovery of lignin is observed with oxotitanium sulphate.

  3. Oxidation in Acidic Medium of Lignins from Agricultural Residues

    NASA Astrophysics Data System (ADS)

    Labat, Gisele Aparecida Amaral; Gonçalves, Adilson Roberto

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

  4. Reaction kinetics of the hydrothermal treatment of lignin.

    PubMed

    Zhang, Bo; Huang, Hua-Jiang; Ramaswamy, Shri

    2008-03-01

    Lignins derived from abundant and renewable resources are nontoxic and extremely versatile in performance, qualities that have made them increasingly important in many industrial applications. We have shown recently that liquefaction of lignin extracted from aspen wood resulted in a 90% yield of liquid. In this paper, the hydrothermal treatment of five types of lignin and biomass residues was studied: Kraft pine lignin provided by MeadWestvaco, Kraft pine lignin from Sigma-Aldrich, organosolv lignin extracted from oat hull, the residues of mixed southern hardwoods, and switchgrass after hydrolysis. The yields were found dependent on the composition or structure of the raw materials, which may result from different pretreatment processes. We propose a kinetic model to describe the hydrothermal treatment of Kraft pine lignin and compare it with another model from the literature. The kinetic parameters of the presented model were estimated, including the reaction constants, the pre-exponential factor, and the activation energy of the Arrhenius equations. Results show that the presented model is well in agreement with the experiments.

  5. Development of All-Solid-State Sensors for Measurement of Nitric Oxide and Ammonia Concentrations by Optical Absorption in Particle-Laden Combusion Exhaust Streams

    SciTech Connect

    Jerald A. Caton; Kalyan Annamalai

    2003-09-24

    An all-solid-state continuous-wave (cw) laser system for ultraviolet absorption measurements of the nitric oxide (NO) molecule has been developed and demonstrated. For the NO sensor, 250 nW of tunable cw ultraviolet radiation is produced by sum-frequency-mixing of 532-nm radiation from a diode-pumped Nd:YAG laser and tunable 395-nm radiation from an external cavity diode laser (ECDL). The sum-frequency-mixing process occurs in a beta-barium borate crystal. The nitric oxide absorption measurements are performed by tuning the ECDL and scanning the sum-frequency-mixed radiation over strong nitric oxide absorption lines near 226 nm. The nitric oxide sensor has been used for measurements in the exhaust of a coal-fired laboratory combustion facility. The Texas A&M University boiler burner facility is a 30 kW (100,000 Btu/hr) downward-fired furnace with a steel shell encasing ceramic insulation. Measurements of nitric oxide concentration in the exhaust stream were performed after modification of the facility for laser based NOx diagnostics. The diode-laser-based sensor measurements showed good agreement with the results from physical probe sampling of the combustion exhaust. The diode-laser-based ultraviolet absorption measurements were successful even when the beam was severely attenuated by particulate in the exhaust stream and window fouling. Single-laser-sweep measurements were demonstrated with an effective time resolution of 100 msec, limited at this time by the scan rate of our mechanically tuned ECDL system. Future planned modifications will lead to even faster response times at sensitivity levels at or below 1 ppm.

  6. Liquefaction of lignin by polyethyleneglycol and glycerol.

    PubMed

    Jin, Yanqiao; Ruan, Xuemin; Cheng, Xiansu; Lü, Qiufeng

    2011-02-01

    Enzymatic hydrolysis lignin (EHL), isolated from the enzymatic hydrolysis residues of the biomass, was liquefied using the mixed solvents of polyethyleneglycol (PEG) and glycerol at the temperature of 130-170°C with sulfuric acid as a catalyst. The influences of liquefaction parameters, such as the molecular weight of PEG, mass ratio of sulfuric acid to EHL, liquefaction temperature and time, and mass ratio of liquid (liquefying cosolvent) to solid (EHL) on the residue content and hydroxyl number were discussed. The FT-IR spectrum result showed that the liquefaction product of EHL was polyether polyol. The hydroxyl number of the liquefaction product was 80-120 mgKOH/g higher than that of PEG.

  7. Inline Measurement of Particle Concentrations in Multicomponent Suspensions using Ultrasonic Sensor and Least Squares Support Vector Machines

    PubMed Central

    Zhan, Xiaobin; Jiang, Shulan; Yang, Yili; Liang, Jian; Shi, Tielin; Li, Xiwen

    2015-01-01

    This paper proposes an ultrasonic measurement system based on least squares support vector machines (LS-SVM) for inline measurement of particle concentrations in multicomponent suspensions. Firstly, the ultrasonic signals are analyzed and processed, and the optimal feature subset that contributes to the best model performance is selected based on the importance of features. Secondly, the LS-SVM model is tuned, trained and tested with different feature subsets to obtain the optimal model. In addition, a comparison is made between the partial least square (PLS) model and the LS-SVM model. Finally, the optimal LS-SVM model with the optimal feature subset is applied to inline measurement of particle concentrations in the mixing process. The results show that the proposed method is reliable and accurate for inline measuring the particle concentrations in multicomponent suspensions and the measurement accuracy is sufficiently high for industrial application. Furthermore, the proposed method is applicable to the modeling of the nonlinear system dynamically and provides a feasible way to monitor industrial processes. PMID:26393611

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

    PubMed

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

    2013-01-01

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

  9. Chlorination and Cleavage of Lignin Structures by Fungal Chloroperoxidases

    PubMed Central

    Ortiz-Bermúdez, Patricia; Srebotnik, Ewald; Hammel, Kenneth E.

    2003-01-01

    Two fungal chloroperoxidases (CPOs), the heme enzyme from Caldariomyces fumago and the vanadium enzyme from Curvularia inaequalis, chlorinated 1-(4-ethoxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-1,3-dihydroxypropane, a dimeric model compound that represents the major nonphenolic structure in lignin. Both enzymes also cleaved this dimer to give 1-chloro-4-ethoxy-3-methoxybenzene and 1,2-dichloro-4-ethoxy-5-methoxybenzene, and they depolymerized a synthetic guaiacyl lignin. Since fungal CPOs occur in soils and the fungi that produce them are common inhabitants of plant debris, CPOs may have roles in the natural production of high-molecular-weight chloroaromatics and in lignin breakdown. PMID:12902304

  10. Chlorination and cleavage of lignin structures by fungal chloroperoxidases.

    PubMed

    Ortiz-Bermúdez, Patricia; Srebotnik, Ewald; Hammel, Kenneth E

    2003-08-01

    Two fungal chloroperoxidases (CPOs), the heme enzyme from Caldariomyces fumago and the vanadium enzyme from Curvularia inaequalis, chlorinated 1-(4-ethoxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-1,3-dihydroxypropane, a dimeric model compound that represents the major nonphenolic structure in lignin. Both enzymes also cleaved this dimer to give 1-chloro-4-ethoxy-3-methoxybenzene and 1,2-dichloro-4-ethoxy-5-methoxybenzene, and they depolymerized a synthetic guaiacyl lignin. Since fungal CPOs occur in soils and the fungi that produce them are common inhabitants of plant debris, CPOs may have roles in the natural production of high-molecular-weight chloroaromatics and in lignin breakdown.

  11. Influence of lignin, pentachlorophenol and heavy metal on antibiotic resistance of pathogenic bacteria isolated from pulp paper mill effluent contaminated river water.

    PubMed

    Chandra, Ram; Sankhwar, Monica

    2011-11-01

    Pulp paper mill pollutants are the major source of aquatic contamination having metals, lignin and chlorophenols. Study was conducted to see the effect of these contaminants on antibiotic resistance pattern of isolated bacteria. Pulp paper effluents were evaluated for its physico-chemical properties i.e, BOD 72143 +/- 164.81 to 22.32 +/- 2.48, COD 213136 +/- 583.59 to 60.40 +/- 6.34, total phenol 386 +/- 71.24 to 0.43 +/- 0.0, lignin 26312 +/- 258.59 to 73.67 +/- 31.81and microbial quality i.e. K. pneumonae, S. typhi, S. faecalis, P. aeruginosa, E. coli, Ent. faecalis, A. hydrophila, B. subtilis, S. aureus, Y enterolitica and V vulrificus. Antibiotic sensitivity (10-30 microg), heavy metal resistance (100-1000 microg ml(-1)), lignin (1000-10,000 ppm) and pentachlorophenol (100-1000 ppm) tolerance of bacterial strains were assessed by seven classes of antibiotics. Eleven bacterial isolates were found multidrug resistant towards antibiotics, heavy metal, lignin and PCP. Out of 11 isolates, 90.9% were found resistant against eleven antibiotics which acquired 100% resistant in presence of heavy metal, lignin and chlorophenols. Results also revealed that concentration of lignin (50-350 ppm) and PCP (5-30 ppm) induced maximum growth (273-8050 cfu ml(-1)) of pathogenic bacteria in river water.

  12. 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.

  13. Potential of lignin from Canna edulis ker residue in the inhibition of α-d-glucosidase: Kinetics and interaction mechanism merging with docking simulation.

    PubMed

    Xie, Fan; Gong, Shengxiang; Zhang, Wei; Wu, Jinhong; Wang, Zhengwu

    2017-02-01

    In this study, we extracted lignin from Canna edulis ker residue. Its chemical structure, inhibitory activity on α-d-glucosidase, and kinetics as well as interaction mechanism were investigated by using spectrum analysis and docking simulation. The isolated lignin was composed by guaiacyl and syringal units, and exhibited stronger inhibition on α-d-glucosidase than acarbose with the half maximal inhibitory concentration at 5.3±0.3μM. It was a non-competitive inhibitior with Km and Ki values of 0.53±0.02mM and 0.92±0.12μM, respectively. It could quench the intrinsic fluorescence of α-d-glucosidase through a static quenching mode. The calculated values of enthalpy and entropy change were 20.8±2.5kJmol(-1) and 172.7±0.8Jmol(-1)K(-1), respectively. There was a single binding site on α-d-glucosidase for lignin, and the binding distance was 3.2nm. The molecular docking analysis exhibited that the hydrogen bonds, hydropholic interaction, and van der Waals forces were the main forces for lignin bind to α-d-glucosidase. This work provides a new insight into the interaction between the lignin and α-d-glucosidase, which might be beneficial to type 2 diabetes with the application of lignin in functional food and pharmacy fields.

  14. Concentric and Eccentric Time-Under-Tension during Strengthening Exercises: Validity and Reliability of Stretch-Sensor Recordings from an Elastic Exercise-Band

    PubMed Central

    Skovdal Rathleff, Michael; Thorborg, Kristian; Bandholm, Thomas

    2013-01-01

    Background Total, single repetition and contraction-phase specific (concentric and eccentric) time-under-tension (TUT) are important exercise-descriptors, as they are linked to the physiological and clinical response in exercise and rehabilitation. Objective To investigate the validity and reliability of total, single repetition, and contraction-phase specific TUT during shoulder abduction exercises, based on data from a stretch-sensor attached to an elastic exercise band. Methods A concurrent validity and interrater reliability study with two raters was conducted. Twelve participants performed five sets of 10 repetitions of shoulder abduction exercises with an elastic exercise band. Exercises were video-recorded to assess concurrent validity between TUT from stretch-sensor data and from video recordings (gold standard). Agreement between methods was calculated using Limits of Agreement (LoA), and the association was assessed by Pearson correlation coefficients. Interrater reliability was calculated using intraclass correlation coefficients (ICC 2.1). Results Total, single repetition, and contraction-phase specific TUT – determined from video and stretch-sensor data – were highly correlated (r>0.99). Agreement between methods was high, as LoA ranged from 0.0 to 3.1 seconds for total TUT (2.6% of mean TUT), from -0.26 to 0.56 seconds for single repetition TUT (6.9%), and from -0.29 to 0.56 seconds for contraction-phase specific TUT (13.2-21.1%). Interrater reliability for total, single repetition and contraction-phase specific TUT was high (ICC>0.99). Interrater agreement was high, as LoA ranged from -2.11 to 2.56 seconds for total TUT (4.7%), from -0.46 to 0.50 seconds for single repetition TUT (9.7%) and from -0.41 to 0.44 seconds for contraction-phase specific TUT (5.2-14.5%). Conclusion Data from a stretch-sensor attached to an elastic exercise band is a valid measure of total and single repetition time-under-tension, and the procedure is highly reliable

  15. 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, Na2SO4, 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.

  16. 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

  17. State Estimation of the Time-Varying and Spatially Localized Concentration of Signal Molecules from the Stochastic Adsorption Dynamics on the Carbon Nanotube-Based Sensors and Its Application to Tumor Cell Detection.

    PubMed

    Jang, Hong; Lee, Jay H; Braatz, Richard D

    2015-01-01

    This paper addresses a problem of estimating time-varying, local concentrations of signal molecules with a carbon-nanotube (CNT)-based sensor array system, which sends signals triggered by monomolecular adsorption/desorption events of proximate molecules on the surfaces of the sensors. Such sensors work on nano-scale phenomena and show inherently stochastic non-Gaussian behavior, which is best represented by the chemical master equation (CME) describing the time evolution of the probabilities for all the possible number of adsorbed molecules. In the CME, the adsorption rate on each sensor is linearly proportional to the local concentration in the bulk phase. State estimators are proposed for these types of sensors that fully address their stochastic nature. For CNT-based sensors motivated by tumor cell detection, the particle filter, which is nonparametric and can handle non-Gaussian distributions, is compared to a Kalman filter that approximates the underlying distributions by Gaussians. In addition, the second-order generalized pseudo Bayesian estimation (GPB2) algorithm and the Markov chain Monte Carlo (MCMC) algorithm are incorporated into KF and PF respectively, for detecting latent drift in the concentration affected by different states of a cell.

  18. 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

  19. Direct Detection of Soil mRNAs using Targeted Microarrays for Genes Associated with Lignin Degradation

    SciTech Connect

    Bailey, Vanessa L.; Fansler, Sarah J.; Bandyopadhyay, Somnath; Smith, Jeff L.; Waters, Katrina M.; Bolton, Harvey

    2010-07-04

    Microarrays have become established tools for describing microbial systems, however the assessment of expression profiles for environmental microbial communities still presents unique challenges. Notably, the concentration of particular transcripts are likely very dilute relative to the pool of total RNA, and PCR-based amplification strategies are vulnerable to amplification biases and the appropriate primer selection. Thus, we apply a signal amplification approach, rather than template amplification, to analyze the expression of genes encoding selected lignin-degrading enzymes in soil. Controls in the form of known amplicons and cDNA from Phanerochaete chrysosporium were included and mixed with the soil cDNA both before and after the signal amplification in order to assess the dynamic range of the microarray. We demonstrate that restored prairie soil expresses a diverse range of genes encoding lignin-degrading enzymes following incubation with lignin substrate, while farmed agricultural soil does not. The mixed additions of control cDNA with soil cDNA does interfere with detection of the low abundance transcripts, nevertheless this microarray approach consistently reports the higher-abundance transcripts which present more robust signals.

  20. Complete genome sequence of the lignin-degrading bacterium Klebsiella sp. strain BRL6-2

    PubMed Central

    2014-01-01

    In an effort to discover anaerobic bacteria capable of lignin degradation, we isolated Klebsiella sp. strain BRL6-2 on minimal media with alkali lignin as the sole carbon source. This organism was isolated anaerobically from tropical forest soils collected from the Bisley watershed at the Ridge site in the El Yunque National Forest in Puerto Rico, USA, part of the Luquillo Long-Term Ecological Research Station. At this site, the soils experience strong fluctuations in redox potential and are characterized by cycles of iron oxidation and reduction. Genome sequencing was targeted because of its ability to grow on lignin anaerobically and lignocellulolytic activity via in vitro enzyme assays. The genome of Klebsiella sp. strain BRL6-2 is 5.80 Mbp with no detected plasmids, and includes a relatively small arsenal of genes encoding lignocellulolytic carbohydrate active enzymes. The genome revealed four putative peroxidases including glutathione and DyP-type peroxidases, and a complete protocatechuate pathway encoded in a single gene cluster. Physiological studies revealed Klebsiella sp. strain BRL6-2 to be relatively stress tolerant to high ionic strength conditions. It grows in increasing concentrations of ionic liquid (1-ethyl-3-methyl-imidazolium acetate) up to 73.44 mM and NaCl up to 1.5 M. PMID:25566348

  1. Characterization of two water-soluble lignin metabolites with antiproliferative activities from Inonotus obliquus.

    PubMed

    Wang, Qingjie; Mu, Haibo; Zhang, Lin; Dong, Dongqi; Zhang, Wuxia; Duan, Jinyou

    2015-03-01

    The chaga mushroom, Inonotus obliquus has long been recognized as a remedy for cancer, gastritis, ulcers, and tuberculosis of the bones since the 16th century. Herein we reported the identification of two homogenous biological macromolecules, designated as IOW-S-1 and IOW-S-2 with anti-tumor activities from the hot-water extract of I. obliquus. Their molecular weights were determined to be 37.9 and 24.5kDa by high performance gel permeation chromatography (HPGPC) respectively. Chemical and spectral analysis indicated that both IOW-S-1 and IOW-S-2 were predominant in lignin, along with ∼20% carbohydrates. Examination of cytotoxicity showed that these two lignin-carbohydrate complexes induced cell death in a concentration dependent manner, while this apoptosis induction was largely cell-cycle independent. Further investigation demonstrated that IOW-S-1 or IOW-S-2 inhibited the activation of the nuclear transcription factor in cancer cells. These findings implied that soluble lignin derivatives were one of bioactive components in I. obliquus, and further provided insights into the understanding of molecular basis for diverse medicinal and nutritional values of this mushroom.

  2. 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.

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

    SciTech Connect

    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 the 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.

  4. Lignin-modifying enzymes of the white rot basidiomycete Ganoderma lucidum

    SciTech Connect

    D 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 are 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.

  5. Connecting Lignin-Degradation Pathway with Pre-Treatment Inhibitor Sensitivity of Cupriavidus necator

    SciTech Connect

    Wang, W.; Yang, S.; Hunsinger, G. B.; Pienkos, P. T.; Johnson, D. K.

    2014-05-27

    In order to produce lignocellulosic biofuels economically, the complete release of monomers from the plant cell wall components, cellulose, hemicellulose, and lignin, through pre-treatment and hydrolysis (both enzymatic and chemical), and the efficient utilization of these monomers as carbon sources, is crucial. In addition, the identification and development of robust microbial biofuel production strains that can tolerate the toxic compounds generated during pre-treatment and hydrolysis is also essential. In this work, Cupriavidus necator was selected due to its capabilities for utilizing lignin monomers and producing polyhydroxylbutyrate (PHB), a bioplastic as well as an advanced biofuel intermediate. We characterized the growth kinetics of C. necator in pre-treated corn stover slurry as well as individually in the pre-sence of 11 potentially toxic compounds in the saccharified slurry. We found that C. necator was sensitive to the saccharified slurry produced from dilute acid pre-treated corn stover. Five out of 11 compounds within the slurry were characterized as toxic to C. necator, namely ammonium acetate, furfural, hydroxymethylfurfural (HMF), benzoic acid, and p-coumaric acid. Aldehydes (e.g., furfural and HMF) were more toxic than the acetate and the lignin degradation products benzoic acid and p-coumaric acid; furfural was identified as the most toxic compound. Although toxic to C. necator at high concentration, ammonium acetate, benzoic acid, and p-coumaric acid could be utilized by C. necator with a stimulating effect on C. necator growth. Consequently, the lignin degradation pathway of C. necator was reconstructed based on genomic information and literature. The efficient conversion of intermediate catechol to downstream products of cis,cis-muconate or 2-hydroxymuconate-6-semialdehyde may help improve the robustness of C. necator to benzoic acid and p-coumaric acid as well as improve PHB productivity.

  6. 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

  7. Solvated liquid-lignin fractions from a Kraft black liquor.

    PubMed

    Velez, Julian; Thies, Mark C

    2013-11-01

    A softwood Kraft black liquor was acidified with carbon dioxide at 115°C and 6.2 bar over a pH range of 13.6-9.5, resulting in the precipitation of liquefied-lignin fractions as a separate phase. Seven such "liquid-lignin" fractions were produced, with each fraction being phase-separated within a narrow pH band of 0.5 units. The fractions were found to be highly hydrated phases, containing 32.3-48.2 wt.% water; as a result, their measured melting points were quite low, 90.7-110.5°C. In contrast, no melting point was detected up to 375°C for any of the lignin fractions after drying. Significant reductions in metals content were observed for the lignin fractions compared to the original black-liquor feed.

  8. [Study on near-infrared absorption mechanism of alkali lignin].

    PubMed

    Wu, Xin-sheng; Xie, Yi-min; Liu, Huan-bin; Wu, Hong

    2006-06-01

    The results showed that o-quinone and q-quinone had strong absorption while vanillin had nearly no absorption in the 800-900 nm range of near-infrared spectroscopy through the comparison of their near-infrared absorption spectra. It was proved that quinone structure of alkali lignin had strong absorption in the 800-900 nm range of near-infrared spectroscopy. The change in the absorbency of oleander milled wood lignin treated with NaOH and Na2 S before and after is greater than that in the absorbency of ginkgo milled wood lignin treated with NaOH and Na2 S before and after because more quinone structure was formed in the process of oleander milled wood lignin treated with NaOH and Na2 S. The finding well explained that cooking liquor of hardwood was much stronger than that of softwood while their pulp kappa number was very near.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  10. Catalytic depolymerization of the hydrolyzed lignin over mesoporous catalysts.

    PubMed

    Chen, Pengru; Zhang, Qi; Shu, Riyang; Xu, Ying; Ma, Longlong; Wang, Tiejun

    2017-02-01

    In this work, the mesoporous SBA-15 and a series of modified catalysts based on it, such as Al-SBA-15 and Ni/Al-SBA-15, were synthesized and used for eliminating the char formation during the depolymerization of hydrolyzed lignin. The temperature, time and solvent effects on the lignin depolymerization were also investigated. Results showed that the repolymerization was effectively suppressed over SBA-15 due to its well-ordered pore structure and large pore size. The addition of Al and Ni elements in SBA-15 could improve the lignin depolymerization performance and saturate the instable intermediates. Ethanol was found to be more effective in suppressing repolymerization than other solvents. 81.4% liquefaction degree and 21.90wt% monomer yield was achieved, and no obvious char was observed after the depolymerization of hydrolyzed lignin in ethanol solvent at 300°C for 4h over Ni/Al-SBA-15(20) catalyst.

  11. Rheological behavior of Phanerochaete chrysosporium broth during lignin degradation.

    PubMed

    Hernández-Peñaranda, A M; Salazar-Montoya, J A; Rodriguez-Vázquez, R; Ramos-Ramirez, E G

    2001-01-01

    Rheological behavior of a lignin-degrading culture of Phanerochaete chrysosporium CDBB-H-298 was determined. Rheological characteristics revealed a Newtonian behavior in the culture medium without fungi, and a non-Newtonian dilatant behavior with fungi. In addition, the rheological behavior of the lignin-containing culture medium was complex, and changed from dilatant to pseudoplastic. During fungal growth without lignin in Kirk media rheological behavior exhibited a parabolic profile, and thixotropy showed a tendency to increase. Results indicated a small increase in the apparent viscosity in the presence of lignin; however, this may not affect the oxygen and mass transfer coefficients. The present findings can be applied to bioreactor desing for waste water treatment.

  12. On the formation of lignin polysaccharide networks in Norway spruce.

    PubMed

    Oinonen, Petri; Zhang, Liming; Lawoko, Martin; Henriksson, Gunnar

    2015-03-01

    In this study we were mirroring suggested in vivo phenomena of lignin-hemicellulose complex formation in vitro, by cross-linking Norway spruce (Picea abies) galactoglucomannans, xylans and lignin moieties to high molecular weight complexes by laccase treatment. We were able to observe the oxidation and cross-linking of non-condensed guaiacyl-type phenolic moieties attached to both of the hemicelluloses by (31)P NMR and size-exclusion chromatography. We suggest that hemicelluloses-lignin complexes form covalently linked structural units during the early stages of lignification via radical enzymatic cross-linking catalyzed by laccase. This work shows that the hemicellulose molecules in wood are covalently linked to two or more lignin units thereby making them suited for forming network structures.

  13. Calculation of IR-spectra of structural fragments of lignins

    NASA Astrophysics Data System (ADS)

    Derkacheva, O. Yu.; Ishankhodzhaeva, M. M.

    2016-12-01

    To study structure of softwood lignins the experimental and theoretical IR-spectra in middle IR-diapason were analyzed. To interpret these data the quantum chemical calculations of IR-spectra of general dimmer fragments of softwood lignins by method of density functional theory (DFT/B3LYP) with 6-31G(d,p) as basis set were carried out. These calculations showed that frequencies of normal vibrations of fragment with β-alkyl-aryl linkage are close to the experimental values of the IR absorption bands of lignin, and infrared spectrum of this structure is similar to the experimental spectrum of lignin. The calculations with accounting for the solvent showed a strong increase in the intensity of the majority of the bands and the solvent effect on the frequencies of vibrations.

  14. Fast Track to Molar-Mass Distributions of Technical Lignins.

    PubMed

    Sulaeva, Irina; Zinovyev, Grigory; Plankeele, Jean-Michel; Sumerskii, Ivan; Rosenau, Thomas; Potthast, Antje

    2017-02-08

    Technical lignins (waste products obtained from wood pulping or biorefinery processes) have so far required lengthy analysis procedures and different eluents for molar-mass analysis by gel permeation chromatography (GPC). This challenge has become more pressing recently since attempts to utilize lignins have increased, leading to skyrocketing numbers of samples to be analyzed. A new approach, which uses the eluent DMSO/LiBr (0.5 % w/v) and converts lignosulfonate salts into their acidic form before analysis, overcomes these limitations by enabling measurement of all kinds of lignins (kraft, organosolv, soda, lignosulfonates) in the same size-exclusion chromatography (SEC) system without the necessity of prior time-consuming derivatization steps. In combination with ultra-performance liquid chromatography (UPLC), analysis times are shortened to one tenth of classical lignin GPC. The new approach is presented, along with a comparison of GPC and UPLC methods and a critical discussion of the analytical parameters.

  15. Molecular simulation as a tool for studying lignin

    SciTech Connect

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

    2012-01-01

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

  16. Parameterization of gaseous constituencies concentration profiles in the planetary boundary layer as required in support of airborne and satellite borne sensors

    NASA Technical Reports Server (NTRS)

    Kindle, E. C.; Condon, E.; Casas, J.

    1976-01-01

    The research to develop the capabilities for sensing air pollution constituencies using satellite or airborne remote sensors is reported. Sensor evaluation and calibration are analyzed including data reduction. The proposed follow-on research is presented.

  17. Quantitative Measurement of cAMP Concentration Using an Exchange Protein Directly Activated by a cAMP-Based FRET-Sensor

    PubMed Central

    Salonikidis, Petrus S.; Zeug, André; Kobe, Fritz; Ponimaskin, Evgeni; Richter, Diethelm W.

    2008-01-01

    Förster resonance energy transfer (FRET)-based biosensors for the quantitative analysis of intracellular signaling, including sensors for monitoring cyclic adenosine monophosphate (cAMP), are of increasing interest. The measurement of the donor/acceptor emission ratio in tandem biosensors excited at the donor excitation wavelength is a commonly used technique. A general problem, however, is that this ratio varies not only with the changes in cAMP concentration but also with the changes of the ionic environment or other factors affecting the folding probability of the fluorophores. Here, we use a spectral FRET analysis on the basis of two excitation wavelengths to obtain a reliable measure of the absolute cAMP concentrations with high temporal and spatial resolution by using an “exchange protein directly activated by cAMP”. In this approach, FRET analysis is simplified and does not require additional calibration routines. The change in FRET efficiency (E) of the biosensor caused by [cAMP] changes was determined as ΔE = 15%, whereas E varies between 35% at low and 20% at high [cAMP], allowing quantitative measurement of cAMP concentration in the range from 150 nM to 15 μM. The method described is also suitable for other FRET-based biosensors with a 1:1 donor/acceptor stoichiometry. As a proof of principle, we measured the specially resolved cAMP concentration within living cells and determined the dynamic changes of cAMP levels after stimulation of the Gs-coupled serotonin receptor subtype 7 (5-HT7). PMID:18708470

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

    SciTech Connect

    Colberg, P.J.

    1983-01-01

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

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

    PubMed

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

    2009-11-11

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

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

    DOEpatents

    Zhao, Qiao; Chen, Fang; Dixon, Richard A.

    2014-08-05

    The invention provides methods for decreasing lignin content and for increasing the level of fermentable carbohydrates in plants by down-regulation of the NST transcription factor. Nucleic acid constructs for down-regulation of NST are described. Transgenic plants are provided that comprise reduced lignin content. Plants described herein may be used, for example, as improved biofuel feedstock and as highly digestible forage crops. Methods for processing plant tissue and for producing ethanol by utilizing such plants are also provided.

  1. Transcription factors for modification of lignin content in plants

    DOEpatents

    Wang, Huanzhong; Chen, Fang; Dixon, Richard A.

    2015-06-02

    The invention provides methods for modifying lignin, cellulose, xylan, and hemicellulose content in plants, and for achieving ectopic lignification and, for instance, secondary cell wall synthesis in pith cells, by altered regulation of a WRKY transcription factor. Nucleic acid constructs for altered WRKY-TF expression are described. Transgenic plants are provided that comprise modified pith cell walls, and lignin, cellulose, and hemicellulose content. Plants described herein may be used, for example, as improved biofuel feedstock and as highly digestible forage crops.

  2. Harvest impacts on alfalfa stem neutral detergent fiber concentration and digestibility and cell wall concentration and composition

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Alfalfa (Medicago sativa L.) stem fiber concentration and digestibility, lignin, and polysaccharide composition impact energy availability for livestock and biofuel conversion efficiency and are affected by maturity stage and environmental influences. We evaluated stem neutral detergent fiber (NDF) ...

  3. Investigating lignin key features in maize lignocelluloses using infrared spectroscopy.

    PubMed

    Chazal, Richard; Robert, Paul; Durand, Sylvie; Devaux, Marie-Françoise; Saulnier, Luc; Lapierre, Catherine; Guillon, Fabienne

    2014-01-01

    Lignins and their cross-linking to hemicelluloses detrimentally affect the cellulose-to-ethanol conversion of grass lignocelluloses. Screening appropriate grass cell walls and their compositional changes during the various steps of the process calls for a high-throughput analytical technique. Such a performance can be fulfilled by Fourier transform mid-infrared (FT-MIR) spectroscopy. In the present paper, a set of maize cell walls from mature stems were selected, including brown midrib samples. Lignin fractions were isolated by mild acidolysis to obtain a set of purified maize lignin standards. The lignin content and the percentage of lignin-derived p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) thioacidolysis monomers were determined. In addition, the composition of cell wall polysaccharides, as well as the amount of ester-linked p-coumaric (CA) and ferulic (FA) acids, was measured by wet chemistry. Partial least square (PLS) analyses were applied to infrared and chemical data of cell walls. The resulting models showed a good predictive ability with regard to the lignin content, to the frequency of S (or G) thioacidolysis monomers, and to the level of ester-linked CA of maize cell walls. The loading plots and regression coefficients revealed relevant infrared absorption bands.

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

    PubMed

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

    2014-12-01

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

  5. A radioimmunoassay for lignin in plant cell walls

    SciTech Connect

    Dawley, R.M.

    1989-01-01

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

  6. Lignin structural alterations in thermochemical pretreatments with limited delignification

    SciTech Connect

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

    2015-08-02

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

  7. Lignin structural alterations in thermochemical pretreatments with limited delignification

    DOE PAGES

    Pu, Yunqiao; Hu, Fan; Huang, Fang; ...

    2015-08-02

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

  8. Evaluation of pristine lignin for hazardous-waste treatment

    SciTech Connect

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

    1987-05-01

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

  9. Biochemical transformation of lignin for deriving valued commodities from lignocellulose.

    PubMed

    Gall, Daniel L; Ralph, John; Donohue, Timothy J; Noguera, Daniel R

    2017-03-24

    The biochemical properties of lignin present major obstacles to deriving societally beneficial entities from lignocellulosic biomass, an abundant and renewable feedstock. Similar to other biopolymers such as polysaccharides, polypeptides, and ribonucleic acids, lignin polymers are derived from multiple types of monomeric units. However, lignin's renowned recalcitrance is largely attributable to its racemic nature and the variety of covalent inter-unit linkages through which its aromatic monomers are linked. Indeed, unlike other biopolymers whose monomers are consistently inter-linked by a single type of covalent bond, the monomeric units in lignin are linked via non-enzymatic, combinatorial radical coupling reactions that give rise to a variety of inter-unit covalent bonds in mildly branched racemic polymers. Yet, despite the chemical complexity and stability of lignin, significant strides have been made in recent years to identify routes through which valued commodities can be derived from it. This paper discusses emerging biological and biochemical means through which degradation of lignin to aromatic monomers can lead to the derivation of commercially valuable products.

  10. Characterization of anaerobic consortia coupled lignin depolymerization with biomethane generation.

    PubMed

    Wu, Yi-Rui; He, Jianzhong

    2013-07-01

    Two sediment-free microbial consortia (LI3 and LP3) were established to depolymerize lignin under anaerobic conditions. During depolymerizing high molecular weight lignin to low molecular weight molecules, the two cultures produced biomethane up to 151.7 and 113.0 mL g(-1) total lignin. Furthermore, LI3 and LP3 could also utilize the biomass - oil palm empty fruit bunch fiber (OPEFB) to produce 190.6 and 195.6 mL methaneg(-1) total lignin in OPEFB, and at the same time improve the bioavailability of lignocellulosic matters for further enzymatic hydrolysis. The microbial community analysis by denature gradient gel electrophoresis (DGGE) and the high-density 16S rDNA gene microarray (PhyloChip) exhibited that Methanomethylovorans sp. (LI3) and Methanoculleus sp. (LP3) were the main methanogens present, and phylum Firmicutes and Bacteroidetes were mainly involved in the lignin depolymerization. The established microbial consortia with both lignin depolymerization and biomethane production provide profound application on the environmental friendly pretreatment of lignocellulosic materials.

  11. Real-time investigation of human topoisomerase I reaction kinetics using an optical sensor: a fast method for drug screening and determination of active enzyme concentrations

    NASA Astrophysics Data System (ADS)

    Kristoffersen, Emil L.; Jørgensen, Line A.; Franch, Oskar; Etzerodt, Michael; Frøhlich, Rikke; Bjergbæk, Lotte; Stougaard, Magnus; Ho, Yi-Ping; Knudsen, Birgitta R.

    2015-05-01

    Human DNA topoisomerase I (hTopI) is a nuclear enzyme that catalyzes relaxation of super helical tension that arises in the genome during essential DNA metabolic processes. This is accomplished through a common reaction mechanism shared among the type IB topoisomerase enzymes, including eukaryotic and poxvirus topoisomerase I. The mechanism of hTopI is specifically targeted in cancer treatment using camptothecin derivatives. These drugs convert the hTopI activity into a cellular poison, and hence the cytotoxic effects of camptothecin derivatives correlate with the hTopI activity. Therefore, fast and reliable techniques for high throughput measurements of hTopI activity are of high clinical interest. Here we demonstrate potential applications of a fluorophore-quencher based DNA sensor designed for measurement of hTopI cleavage-ligation activities, which are the catalytic steps affected by camptothecin. The kinetic analysis of the hTopI reaction with the DNA sensor exhibits a characteristic burst profile. This is the result of a two-step ping-pong reaction mechanism, where a fast first reaction, the one creating the signal, is followed by a slower second reaction necessary for completion of the catalytic cycle. Hence, the burst profile holds information about two reactions in the enzymatic mechanism. Moreover, it allows the amount of active enzyme in the reaction to be determined. The presented results pave the way for future high throughput drug screening and the potential of measuring active hTopI concentrations in clinical samples for individualized treatment.Human DNA topoisomerase I (hTopI) is a nuclear enzyme that catalyzes relaxation of super helical tension that arises in the genome during essential DNA metabolic processes. This is accomplished through a common reaction mechanism shared among the type IB topoisomerase enzymes, including eukaryotic and poxvirus topoisomerase I. The mechanism of hTopI is specifically targeted in cancer treatment using

  12. Composition of Lignin-to-Liquid Solvolysis Oils from Lignin Extracted in a Semi-Continuous Organosolv Process

    PubMed Central

    Løhre, Camilla; Vik Halleraker, Hilde; Barth, Tanja

    2017-01-01

    The interest and on-going research on utilisation of lignin as feedstock for production of renewable and sustainable aromatics is expanding and shows great potential. This study investigates the applicability of semi-continuously organosolv extracted lignin in Lignin-to-Liquid (LtL) solvolysis, using formic acid as hydrogen donor and water as solvent under high temperature–high pressure (HTHP) conditions. The high purity of the organosolv lignin provides high conversion yields at up to 94% based on lignin mass input. The formic acid input is a dominating parameter in lignin conversion. Carbon balance calculations of LtL-solvolysis experiments also indicate that formic acid can give a net carbon contribution to the bio-oils, in addition to its property as hydrogenation agent. Compound specific quantification of the ten most abundant components in the LtL-oils describe up to 10% of the bio-oil composition, and reaction temperature is shown to be the dominating parameter for the structures present. The structural and quantitative results from this study identify components of considerable value in the LtL-oil, and support the position of this oil as a potentially important source of building blocks for the chemical and pharmaceutical industry. PMID:28124994

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

    PubMed

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

    2015-04-01

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

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

    SciTech Connect

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

    2015-04-17

    Lignin has been investigated as a carbon fiber precursor since the 1960s. Although there have been a number of reports of successful lignin-based carbon fiber production at the lab scale, lignin-based carbon fibers are not currently commercially available. This review will highlight some of the known challenges, and also the reported methods for purifying and modifying lignin to improve it as a precursor. Lignin can come from different sources (e.g. hardwood, softwood, grasses) and extraction methods (e.g. organosolv, kraft), meaning that lignin can be found with a diversity of purity and structure. The implication of these conditions on lignin as carbon fiber precursor is not comprehensively known, especially as the lignin landscape is evolving. The work presented in this review will help guide the direction of a project between GrafTech and ORNL to develop lignin carbon fiber technology, as part of a cooperative agreement with the DOE Advanced Manufacturing Office.

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

    PubMed

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

    2016-08-01

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

  16. Influence of Mn concentration on magnetic topological insulator MnxBi2−xTe3 thin-film Hall-effect sensor

    SciTech Connect

    Ni, Y.; Zhang, Z.; Nlebedim, I. C.; Hadimani, R. L.; Jiles, D. C.

    2015-06-11

    Hall-effect (HE) sensors based on high-quality Mn-doped Bi2Te3 topological insulator (TI) thin films have been systematically studied in this paper. Improvement of Hall sensitivity is found after doping the magnetic element Mn into Bi2Te3. The sensors with low Mn concentrations, MnxBi2-xTe3, x = 0.01 and 0.08 show the linear behavior of Hall resistance with sensitivity about 5 Ω/T. And their Hall sensitivity shows weak dependence on temperature. For sensors with high Mn concentration (x = 0.23), the Hall resistance with respect to magnetic field shows a hysteretic behavior. Moreover, its sensitivity shows almost eight times as high as that of the HE sensors with low Mn concentration. The highest sensitivity can reach 43 Ω/T at very low magnetic field. This increase of Hall sensitivity is caused by the occurrence of anomalous HE (AHE) after ferromagnetic phase transition. Our work indicates that the magnetic-element-doped TIs with AHE are good candidates for HE sensors.

  17. Evaluation of spray-dried lignin-based formulations and adjuvants as solar protectants for the granulovirus of the codling moth, Cydia pomonella (L).

    PubMed

    Arthurs, S P; Lacey, L A; Behle, R W

    2006-10-01

    Commercial formulations of the codling moth, Cydia pomonella L., granulovirus (CpGV) are limited by their short residual activity under orchard conditions in the Pacific Northwest. We evaluated spray-dried lignin-encapsulated formulations of CpGV for improved solar stability based on laboratory bioassays with a solar simulator and in field tests in an infested apple orchard. In laboratory tests, aqueous lignin formulations containing a high dosage of 3 x 10(10) occlusion bodies (OB)/L, with and without the additives titanium dioxide (TiO(2)) and sugar, provided significant solar protection of virus, i.e., mortality of codling moth exposed to lignin formulations that had been irradiated with 9.36 x 10(6) joules/m(2) was 92-94%, compared with 66-67% from a glycerin-stabilized product (Cyd-X) or suspension of pure unformulated virus at the same rates. By comparison, a lower dosage of the lignin formulation (3 x 10(8)OB/L) did not provide significant solar protection. Equivalent dosage-dependent patterns in solar protection were observed in further tests with the lignin formulation, when an intermediate (3 x 10(9)OB/L) as well as the low dosage provided no solar protection. Equivalent rates of a blank lignin formulation (containing no virus) did not affect larval mortality, suggesting a protective effect of the lignin on the virus at the high rate. The use of several spray adjuvants, 'NuFilm-17' and 'Organic Biolink' (sticker-spreaders at 0.06% v/v), 'Raynox' (sunburn protectant at 5% v/v), and 'Trilogy'(neem oil at 1% v/v) did not provide solar protection of a commercial CpGV preparation in laboratory tests. In season long orchard tests (Golden Delicious), the lignin formulation of CpGV applied at 6.57 x 10(12)OB/ha did not significantly improve control of codling moth or protection of fruit compared with Cyd-X at equivalent rates. Our studies show that lignin-based CpGV formulations provided solar protection at relatively high virus dosages. The testing of lignin

  18. Nondestructive, real-time determination and visualization of cellulose, hemicellulose and lignin by luminescent oligothiophenes

    PubMed Central

    Choong, Ferdinand X.; Bäck, Marcus; Steiner, Svava E.; Melican, Keira; Nilsson, K. Peter R.; Edlund, Ulrica; Richter-Dahlfors, Agneta

    2016-01-01

    Enabling technologies for efficient use of the bio-based feedstock are crucial to the replacement of oil-based products. We investigated the feasibility of luminescent conjugated oligothiophenes (LCOs) for non-destructive, rapid detection and quality assessment of lignocellulosic components in complex biomass matrices. A cationic pentameric oligothiophene denoted p-HTEA (pentamer hydrogen thiophene ethyl amine) showed unique binding affinities to cellulose, lignin, hemicelluloses, and cellulose nanofibrils in crystal, liquid and paper form. We exploited this finding using spectrofluorometric methods and fluorescence confocal laser scanning microscopy, for sensitive, simultaneous determination of the structural and compositional complexities of native lignocellulosic biomass. With exceptional photostability, p-HTEA is also demonstrated as a dynamic sensor for real-time monitoring of enzymatic cellulose degradation in cellulolysis. These results demonstrate the use of p-HTEA as a non-destructive tool for the determination of cellulose, hemicellulose and lignin in complex biomass matrices, thereby aiding in the optimization of biomass-converting technologies. PMID:27759105

  19. Nondestructive, real-time determination and visualization of cellulose, hemicellulose and lignin by luminescent oligothiophenes

    NASA Astrophysics Data System (ADS)

    Choong, Ferdinand X.; Bäck, Marcus; Steiner, Svava E.; Melican, Keira; Nilsson, K. Peter R.; Edlund, Ulrica; Richter-Dahlfors, Agneta

    2016-10-01

    Enabling technologies for efficient use of the bio-based feedstock are crucial to the replacement of oil-based products. We investigated the feasibility of luminescent conjugated oligothiophenes (LCOs) for non-destructive, rapid detection and quality assessment of lignocellulosic components in complex biomass matrices. A cationic pentameric oligothiophene denoted p-HTEA (pentamer hydrogen thiophene ethyl amine) showed unique binding affinities to cellulose, lignin, hemicelluloses, and cellulose nanofibrils in crystal, liquid and paper form. We exploited this finding using spectrofluorometric methods and fluorescence confocal laser scanning microscopy, for sensitive, simultaneous determination of the structural and compositional complexities of native lignocellulosic biomass. With exceptional photostability, p-HTEA is also demonstrated as a dynamic sensor for real-time monitoring of enzymatic cellulose degradation in cellulolysis. These results demonstrate the use of p-HTEA as a non-destructive tool for the determination of cellulose, hemicellulose and lignin in complex biomass matrices, thereby aiding in the optimization of biomass-converting technologies.

  20. Nondestructive, real-time determination and visualization of cellulose, hemicellulose and lignin by luminescent oligothiophenes.

    PubMed

    Choong, Ferdinand X; Bäck, Marcus; Steiner, Svava E; Melican, Keira; Nilsson, K Peter R; Edlund, Ulrica; Richter-Dahlfors, Agneta

    2016-10-19

    Enabling technologies for efficient use of the bio-based feedstock are crucial to the replacement of oil-based products. We investigated the feasibility of luminescent conjugated oligothiophenes (LCOs) for non-destructive, rapid detection and quality assessment of lignocellulosic components in complex biomass matrices. A cationic pentameric oligothiophene denoted p-HTEA (pentamer hydrogen thiophene ethyl amine) showed unique binding affinities to cellulose, lignin, hemicelluloses, and cellulose nanofibrils in crystal, liquid and paper form. We exploited this finding using spectrofluorometric methods and fluorescence confocal laser scanning microscopy, for sensitive, simultaneous determination of the structural and compositional complexities of native lignocellulosic biomass. With exceptional photostability, p-HTEA is also demonstrated as a dynamic sensor for real-time monitoring of enzymatic cellulose degradation in cellulolysis. These results demonstrate the use of p-HTEA as a non-destructive tool for the determination of cellulose, hemicellulose and lignin in complex biomass matrices, thereby aiding in the optimization of biomass-converting technologies.

  1. In vitro degradation of carbamazepine and diclofenac by crude lignin peroxidase.

    PubMed

    Zhang, Yongjun; Geissen, Sven-Uwe

    2010-04-15

    Carbamazepine and diclofenac were frequently detected in water bodies. In this study, crude lignin peroxidase, produced from a white rot fungus Phanerochaete chrysosporium, was studied on its in vitro degradation of both drugs. The influencing parameters were studied, including pH, the hydrogen peroxide concentration, veratryl alcohol and the temperature. It was found that LiP completely degraded diclofenac at pH 3.0-4.5 and 3-24 ppm H(2)O(2) while the degradation efficiency of carbamazepine was mostly below 10%. The addition of veratryl alcohol and the increased temperature did not enhance the degradation of carbamazepine.

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

    SciTech Connect

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

    1986-01-01

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

  3. Development of All-Solid-State Sensors for Measurement of Nitric Oxide and Ammonia Concentrations by Optical Absorption in Particle-Laden Combustion Exhaust Streams

    SciTech Connect

    Jerald A. Caton; Kalyan Annamalai; Robert P. Lucht

    2005-09-30

    An all-solid-state continuous-wave (cw) laser system for ultraviolet absorption measurements of the nitric oxide (NO) molecule has been developed and demonstrated. For the NO sensor, 250 nW of tunable cw ultraviolet radiation is produced by sum-frequency-mixing of 532-nm radiation from a diode-pumped Nd:YAG laser and tunable 395-nm radiation from an external cavity diode laser (ECDL). The sum-frequency-mixing process occurs in a beta-barium borate crystal. The nitric oxide absorption measurements are performed by tuning the ECDL and scanning the sum-frequency-mixed radiation over strong nitric oxide absorption lines near 226 nm. In Year 1 of the research, the nitric oxide sensor was used for measurements in the exhaust of a coal-fired laboratory combustion facility. The Texas A&M University boiler burner facility is a 30 kW (100,000 Btu/hr) downward-fired furnace with a steel shell encasing ceramic insulation. Measurements of nitric oxide concentration in the exhaust stream were performed after modification of the facility for laser based NOx diagnostics. The diode-laser-based ultraviolet absorption measurements were successful even when the beam was severely attenuated by particulate in the exhaust stream and window fouling. Single-laser-sweep measurements were demonstrated with an effective time resolution of 100 msec, limited at this time by the scan rate of our mechanically tuned ECDL system. In Year 2, the Toptica ECDL in the original system was replaced with a Sacher Lasers ECDL. The mode-hop-free tuning range and tuning rate of the Toptica ECDL were 25 GHz and a few Hz, respectively. The mode-hop-free tuning range and tuning rate of the Sacher Lasers ECDL were 90 GHz and a few hundred Hz, respectively. The Sacher Lasers ECDL thus allows us to scan over the entire NO absorption line and to determine the absorption baseline with increased accuracy and precision. The increased tuning rate is an advantage in that data can be acquired much more rapidly and the

  4. Chemical sensors

    DOEpatents

    Lowell, Jr., James R.; Edlund, David J.; Friesen, Dwayne T.; Rayfield, George W.

    1991-01-01

    Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising (a) a mechanochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, operatively coupled to (b) a transducer capable of directly converting said expansion or contraction to a measurable electrical response.

  5. Acetylene black paste electrode modified with graphene as the voltammetric sensor for selective determination of tryptophan in the presence of high concentrations of tyrosine.

    PubMed

    Deng, Peihong; Xu, Zhifeng; Feng, Yonglan

    2014-02-01

    A reliable sensor was fabricated by modifying an acetylene black paste electrode with graphene (denoted as GR/ABPE) for sensitive and selective determination of tryptophan (Trp). Due to the high sorption ability, large surface area and numerous active sites, the GR/ABPE showed a strong enhancement effect on the oxidation of Trp, and greatly increased the peak current. The parameters affecting the Trp determination were investigated. In 1.0 M H2SO4 the voltammetric responses of Trp and tyrosine (Tyr) were well separated into two distinct peaks with peak potential difference (ΔE(pa)) of 115 mV. Under the optimized conditions, in the presence of 0.1 mM Tyr, the oxidation peak current of Trp was proportional to its concentration in the range between 0.1 μM and 0.1 mM, with the limit of detection of 60 nM (S/N=3). The GR/ABPE was applied to the direct detection of Trp in pharmaceutical and biological samples with satisfactory results. This work provides a simple and easy approach to selective detection of Trp in the presence of Tyr.

  6. 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

  7. 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

  8. Degradation of carbohydrates and lignins in buried woods

    NASA Astrophysics Data System (ADS)

    Hedges, John I.; Cowie, Gregory L.; Ertel, John R.; James Barbour, R.; Hatcher, Patrick G.

    1985-03-01

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

  9. Degradation of carbohydrates and lignins in buried woods

    USGS Publications Warehouse

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

    1985-01-01

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

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

    PubMed

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

    2016-06-15

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

  11. Structural characterization of a serendipitously discovered bioactive macromolecule, lignin sulfate.

    PubMed

    Raghuraman, Arjun; Tiwari, Vaibhav; Thakkar, Jay N; Gunnarsson, Gunnar T; Shukla, Deepak; Hindle, Michael; Desai, Umesh R

    2005-01-01

    The herpes simplex virus-1 (HSV-1) utilizes cell-surface glycosaminoglycan, heparan sulfate, to gain entry into cells and cause infection. In a search for synthetic mimics of heparan sulfate to prevent HSV infection, we discovered potent inhibitory activity arising from sulfation of a monomeric flavonoid. Yet, detailed screening indicated that the sulfated flavonoid was completely inactive and the potent inhibitory activity arose from a macromolecular substance present in the parent flavonoid. The active principle was identified through a battery of biophysical and chemical analyses as a sulfated form of lignin, a three-dimensional network polymer composed of substituted phenylpropanoid monomers. Mass spectral analysis of the parent lignin and its sulfated derivative indicates the presence of p-coumaryl monomers interconnected through uncondensed beta-O-4-linkages. Elemental analysis of lignin sulfate correlates primarily with a polymer of p-coumaryl alcohol containing one sulfate group. High-performance size exclusion chromatography shows a wide molecular weight distribution from 1.5 to 40 kDa suggesting significant polydispersity. Polyacrylamide gel electrophoresis (PAGE) analysis indicates a highly networked polymer that differs significantly from linear charged polymers with respect to its electrophoretic mobility. Overall, macromolecular lignin sulfate presents a multitude of substructures that can interact with biomolecules, including viral glycoproteins, using hydrophobic, hydrogen-bonding, and ionic forces. Thus, lignin sulfate represents a large number of interesting structures with potential medicinal benefits.

  12. Cinnamic Acid Increases Lignin Production and Inhibits Soybean Root Growth

    PubMed Central

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

    2013-01-01

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

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

    SciTech Connect

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

    2016-05-28

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

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

    DOE PAGES

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

    2016-05-28

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

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

    PubMed

    Moxley, Geoffrey; Gaspar, Armindo Ribeiro; Higgins, Don; Xu, Hui

    2012-09-01

    In this study, raw corn stover was subjected to dilute acid pretreatments over a range of severities under conditions similar to those identified by the National Renewable Energy Laboratory (NREL) in their techno-economic analysis of biochemical conversion of corn stover to ethanol. The pretreated corn stover then underwent enzymatic hydrolysis with yields above 70 % at moderate enzyme loading conditions. The enzyme exhausted lignin residues were characterized by ³¹P NMR spectroscopy and functional moieties quantified and correlated to enzymatic hydrolysis yields. Results from this study indicated that both xylan solubilization and lignin degradation are important for improving the enzyme accessibility and digestibility of dilute acid pretreated corn stover. At lower pretreatment temperatures, there is a good correlation between xylan solubilization and cellulose accessibility. At higher pretreatment temperatures, lignin degradation correlated better with cellulose accessibility, represented by the increase in phenolic groups. During acid pretreatment, the ratio of syringyl/guaiacyl functional groups also gradually changed from less than 1 to greater than 1 with the increase in pretreatment temperature. This implies that more syringyl units are released from lignin depolymerization of aryl ether linkages than guaiacyl units. The condensed phenolic units are also correlated with the increase in pretreatment temperature up to 180 °C, beyond which point condensation reactions may overtake the hydrolysis of aryl ether linkages as the dominant reactions of lignin, thus leading to decreased cellulose accessibility.

  16. 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

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

    PubMed

    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.

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

    SciTech Connect

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

    2016-05-05

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

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

    DOE PAGES

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

    2016-05-05

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

  20. Elucidation of the structures of residual and dissolved pine kraft lignins using an HMQC NMR technique.

    PubMed

    Balakshin, Mikhail Yu; Capanema, Ewellyn A; Chen, Chen-Loung; Gracz, Hanna S

    2003-10-08

    Comparative studies on the structures of residual and dissolved lignins isolated from pine kraft pulp and pulping liquor have been undertaken using the (1)H-(13)C HMQC NMR technique, GPC, and sugar analysis to elucidate the reaction mechanisms in kraft pulping and the lignin reactivity. A modified procedure for the isolation of enzymatic residual lignins has resulted in an appreciable decrease in protein contaminants in the residual lignin preparations (N content < 0.2%). The very high dispersion of HMQC spectra allows identification of different lignin moieties, which signals appear overlapped in 1D (13)C NMR spectra. Elucidation of the role of condensation reactions indicates that an increase in the degree of lignin condensation during pulping results from accumulation of original condensed lignin moieties rather than from the formation of new alkyl-aryl structures. Among aryl-vinyl type moieties, only stilbene structures are accumulated in lignin in appreciable amounts. Benzyl ether lignin-carbohydrate bonds involving primary hydroxyl groups of carbohydrates have been detected in residual and dissolved lignin preparations. Structures of the alpha-hydroxyacid type have been postulated to be among the important lignin degradation products in kraft pulping. The effect of the isolation method on the lignin structure and differences between the residual and dissolved lignins are discussed.

  1. Evolution of a biomass-fermenting bacterium to resist lignin phenolics.

    PubMed

    Cerisy, Tristan; Souterre, Tiffany; Torres-Romero, Ismael; Boutard, Magali; Dubois, Ivan; Patrouix, Julien; Labadie, Karine; Berrabah, Wahiba; Salanoubat, Marcel; Doring, Volker; Tolonen, Andrew

    2017-03-31

    Increasing the resistance of plant-fermenting bacteria to lignocellulosic inhibitors is useful to understand microbial adaptation and to develop candidate strains for consolidated bioprocessing. Here we study and improve inhibitor resistance in Clostridium phytofermentans (also called Lachnoclostridium phytofermentans), a model anaerobe that ferments lignocellulosic biomass. We survey the resistance of this bacterium to a panel of biomass inhibitors, and then evolve strains that grow in increasing concentrations of the lignin phenolic, ferulic acid, by automated, long-term growth selection in an anaerobic GM3 automat. Ultimately, strains resist multiple inhibitors and grow robustly at the solubility limit of ferulate while retaining the ability to ferment cellulose. We analyze genome-wide transcription patterns during ferulate stress and genomic variants that arose along the ferulate growth selection, revealing how cells adapt to inhibitors by changes in gene dosage and regulation, membrane fatty acid structure, and the surface layer. Collectively, this study demonstrates an automated framework for evolution of anaerobes and gives insight into the genetic mechanisms by which bacteria survive exposure to chemical inhibitors.Importance Fermentation of plant biomass is a key part of carbon cycling in diverse ecosystems. Further, industrial biomass fermentation could provide a renewable alternative to fossil fuels. Plants are primarily composed of lignocellulose, a matrix of polysaccharides and polyphenolic lignin. Thus, when microorganisms degrade lignocellulose to access sugars, they also release phenolic and acidic inhibitors. Here, we study how the plant-fermenting bacterium Clostridium phytofermentans resists plant inhibitors using the lignin phenolic, ferulic acid. We examine how the cell responds to abrupt ferulate stress by measuring changes in gene expression. We evolve increasingly resistant strains by automated, long-term cultivation at progressively higher

  2. Monolignol ferulate conjugates are naturally incorporated into plant lignins

    PubMed Central

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

    2016-01-01

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

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

    PubMed Central

    Strassberger, Zea; Tanase, Stefania; Rothenberg, Gadi

    2011-01-01

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

  4. Monolignol ferulate conjugates are naturally incorporated into plant lignins.

    PubMed

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

    2016-10-01

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

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

    PubMed

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

    2014-12-01

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

  6. Hydrothermal conversion of lignin to substituted phenols and aromatic ethers.

    PubMed

    Singh, Rawel; Prakash, Aditya; Dhiman, Shashi Kumar; Balagurumurthy, Bhavya; Arora, Ajay K; Puri, S K; Bhaskar, Thallada

    2014-08-01

    Hydrothermal liquefaction of lignin was performed using methanol and ethanol at various temperatures (200, 250 and 280°C) and residence times of 15, 30 and 45min. Maximum liquid product yield (85%) was observed at 200°C and 15min residence time using methanol. Increase in temperature was seen to decrease the liquid products yield. With increase in residence time, liquid yields first increased and then decreased. FTIR and (1)H NMR showed the presence of substituted phenols and aromatic ethers in liquid products and breakage of β-O-4 or/and α-O-4 ether bonds present in lignin during hydrothermal liquefaction was confirmed through FTIR of bio-residue. In comparison to the existing literature information, higher lignin conversion to liquid products and maximum carbon conversion (72%) was achieved in this study.

  7. Independent origins of syringyl lignin in vascular plants

    PubMed Central

    Weng, Jing-Ke; Li, Xu; Stout, Jake; Chapple, Clint

    2008-01-01

    Lycophytes arose in the early Silurian (≈400 Mya) and represent a major lineage of vascular plants that has evolved in parallel with the ferns, gymnosperms, and angiosperms. A hallmark of vascular plants is the presence of the phenolic lignin heteropolymer in xylem and other sclerified cell types. Although syringyl lignin is often considered to be restricted in angiosperms, it has been detected in lycophytes as well. Here we report the characterization of a cytochrome P450-dependent monooxygenase from the lycophyte Selaginella moellendorffii. Gene expression data, cross-species complementation experiments, and in vitro enzyme assays indicate that this P450 is a ferulic acid/coniferaldehyde/coniferyl alcohol 5-hydroxylase (F5H), and is capable of diverting guaiacyl-substituted intermediates into syringyl lignin biosynthesis. Phylogenetic analysis indicates that the Selaginella F5H represents a new family of plant P450s and suggests that it has evolved independently of angiosperm F5Hs. PMID:18505841

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

    PubMed

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

    2016-11-01

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

  9. Rapid room temperature solubilization and depolymerization of polymeric lignin at high loadings

    SciTech Connect

    Sun, Jian; Dutta, Tanmoy; Parthasarathi, Ramakrishnan; Kim, Kwang Ho; Tolic, Nikola; Chu, Rosalie K.; Isern, Nancy G.; Cort, John R.; Simmons, Blake A.; Singh, Seema

    2016-01-01

    The relatively poor solubility of lignin in most pretreatment solvents remains one of the biggest challegnes in lignin valorization to improve overall biorefinery economics. In this work, rapid room temperature solubilization of lignin at high solid loadings (>30 wt%) can be easily achieved in a single step using ethylene glycol (EG). The solubilized lignin can be rapidly and quantitively recovered with the addtion of ethanol. The computational and nuclear magnetic resonance (NMR) spectroscopic studies confirm that strong hydrogen bond interactions between EG and the free hydroxyl groups present in lignin contribute to the lignin dissolution. In addition, hydrogen peroxide mediated depolymerization of dissolved lignin at low temperature (80 oC) was tested and the effect of EG molecules on depolymerization of ligin was also theoritically studied. The findings of this work provide mechanistic insights of hydrogen bond interactions in high lignin solubilization and valorization.

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

    PubMed

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

    2012-08-01

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

  11. 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.

  12. 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.

  13. Advanced process for precipitation of lignin from ethanol organosolv spent liquors.

    PubMed

    Schulze, Peter; Seidel-Morgenstern, Andreas; Lorenz, Heike; Leschinsky, Moritz; Unkelbach, Gerd

    2016-01-01

    An advanced process for lignin precipitation from organosolv spent liquors based on ethanol evaporation was developed. The process avoids lignin incrustations in the reactor, enhances filterability of the precipitated lignin particles and significantly reduces the liquor mass in downstream processes. Initially, lignin solubility and softening properties were understood, quantified and exploited to design an improved precipitation process. Lignin incrustations were avoided by targeted precipitation of solid lignin at specific conditions (e.g. 1