CHEMICAL AND PHYSICO-CHEMICAL CHARACTERIZATION OF LIGNINS OBTAINED FROM ETHANOL-WATER FRACTIONATION OF BAGASSE

Organosolv lignins can replace petroleum chemicals such as phenol either partially or totally in various applications. Eight lignins, seven of which corresponded to the ethanol-water fractionation of bagasse and the other to a reference lignin (Alcell (R)) were analyzed with the aim to evaluate their chemical and physicochemical characteristics. The purity of the lignin fractions was determined by high pressure liquid chromatography (HPLC) and by ash content. Fourier Transform-Infrared Spectroscopy (FTIR) techniques and differential UV spectroscopy were applied to identify the chemical groups in the lignin samples. The molecular weight distribution was determined by size exclusion chromatography (HPSEC). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to determine the mass loss due to the high temperature treatment. The lignins studied showed the presence of p-hydroxyphenyl (H unit) and a greater proportion of guaiacyl (G unit) moieties, lower purity, similar or greater amount of phenolic hydroxyl groups, and higher degradation temperatures, than the Alcell (R) lignin.

Characterization of alkaline lignins for use in penol-formaldehyde and epoxy resins

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

Photocatalytic oxidation of humic substances and lignins in aqueous solutions

Tässä tutkimuksessa tarkastellaan kahden yleisen, veden ympäristökuormitusta aiheuttavan kemikaaliryhmän, ligniinin ja humusaineiden, fotokatalyyttistahapetusta (photocatalytic oxidation, PCO) vesiliuoksessa. Fotokatalyyttina käytettiin titaanidioksidia, jota säteilytettiin ultraviolettivalolla. Työssä selvitettiin useiden eri olosuhdeparametrien vaikutusta fotokatalyysiin. Tutkittavia parametreja olivat mm. kontaminanttien alkukonsentraatio, pH, vetyperoksidilisäys, rauta-ionien lisäys, fotokatalyysimenetelmä, fotokatalyytin pintakonsentraatioja titaanidioksidin määrä lasisissa mikropartikkeleissa. Ultraviolettivalon lähteinä käytettiin sekä keinovaloa että auringonvaloa. Katalyytin kantoaineena käytettiin huokoisia lasisia mikropartikkeleita, joiden pintaan kiinnittynyt titaanidioksidi pystyi hyvin vähentämään kontaminanttien määrää vedessä. Fotokatalyysin tehokkuus kasvoi humusaine- ja ligniinikonsentraatioiden kasvaessa. Korkeimmat hapetustehokkuudet kumallakin kontaminantilla saavutettiin neutraaleissa jalievästi emäksisissä olosuhteissa huolimatta siitä, että paras adsorboituminen tapahtui happamissa olosuhteissa. Tämän perusteella voidaan olettaa, että humusaineiden ja ligniinin hapetus tapahtuu pääosin radikaalimekanismilla. Vetyperoksidin lisääminen humusaineliuokseen lisäsi hapettumisnopeutta, vaikka näennäinen hapetustehokkuus ei muuttunut. Tämän perusteella vetyperoksidi hapetti myös humusaineita referenssinäytteessä. Ligniinin fotokatalyyttinen hapettuminen parani vetyperoksidilisäyksellä happamissa olosuhteissa johtuen lisääntyneestä OH-radikaalien muodostumisesta. Ligniini ei hapettunut vetyperoksidilla, jos fotokatalyyttiä ei¿ollut läsnä. Rauta-ionit eivät lisänneet humushappojen fotokatalyyttistähapettumista, mutta Fe2+-ionien lisäys aina konsentraatioon 0.05 mM johti ligniinin hapettumistehokkuuden voimakkaaseen kasvuun. Rauta-ionikonsentraation kasvattaminen edelleen johti ligniinin hapetustehokkuuden alenemiseen.

Sisal chemically modified with lignins: Correlation between fibers and phenolic composites properties

Sisal fibers have been chemically modified by reaction with lignins, extracted from sugarcane bagasse and Pinus-type wood and then hydroxymethylated, to increase adhesion in resol-type phenolic thermoset matrices. Inverse gas chromatography (IGC) results showed that acidic sites predominate for unmodified/modified sisal fibers and for phenolic thermoset, indicating that the phenolic matrix has properties that favor the interaction with sisal fibers. The IGC results also showed that the phenolic thermoset has a dispersive component closer to those of the modified fibers suggesting that thermoset interactions with the less polar modified fibers are favored. Surface SEM images of the modified fibers showed that the fiber bundle deaggregation increased after the treatment, making the interfibrillar structure less dense in comparison with that of unmodified fibers, which increased the contact area and encouraged microbial biodegradation in simulated soil. Water diffusion was observed to be faster for composites reinforced with modified fibers, since the phenolic resin penetrated better into modified fibers, thereby blocking water passage through their channels. Overall, composites` properties showed that modified fibers promote a significant reduction in the hydrophilic character, and consequently of the reinforced composite without a major effect on impact strength and with increased storage modulus. (c) 2008 Elsevier Ltd. All rights reserved.

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 x 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan delta of 3.9 x 10(-3)) and conductivity of 1.75 x 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ultrathin films of lignins as a potential transducer in sensing applications involving heavy metal ions

Lignins extracted from sugar cane bagasse using different alcohols in the organosolv-CO(2) supercritical pulping process have been applied in the fabrication of ultrathin films through the Langmuir-Blodgett technique. Langmuir films were characterized by surface pressure versus mean molecular area (Pi-A) isotherms to exploit the sensitivity of nanostructured lignin films to metallic ions (Cu(2+), Cd(2+) and Pb(2+)). The Pi-A isotherms were shifted to larger molecular areas when heavy metal ions are present into the subphase, which might be related to electrostatic repulsions between metallic ions entrapped within the lignin molecular structure. Taking the advantage of metal incorporation, Langmuir monolayers were transferred onto solid substrates forming Langmuir-Blodgett (LB) films to be used as a transducer in an "electronic tongue" system to detect Cu(2+) in aqueous solution below threshold standard established by the Brazilian regulation. Both techniques impedance spectroscopy and electrochemistry have been used in these experiments. Complementary, Fourier transform infrared (FTIR) spectroscopy recorded for LB films before and after soaking into Cu(2+) aqueous solution revealed an interaction between the lignin phenyl groups and the metallic ion. (C) 2007 Elsevier B.V.. All rights reserved.

Surface morphology and molecular organization of lignins in Langmuir-Blodgett films

Atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR) are used to investigate molecular organization in Langmuir-Blodgett (LB) films of two kinds of lignins. The lignins were extracted from sugar cane bagasse using distinct extraction processes and are referred to here as ethanol lignin (EL) and saccharification lignin (SAC). AFM images show that LB films from EL have a flat surface in comparison with those from SAC. For the latter, ellipsoidal aggregates are seen oriented perpendicularly to the substrate. This result is confirmed by a combination of transmission and reflection FTIR measurements, which also point to lignin aggregates preferentially oriented perpendicularly to the substrate. For LB films from EL, on the other hand, aggregates are preferentially oriented parallel to the substrate, again consistent with the flat surface observed in AFM data. The vibrational spectroscopy data for cast films from both lignins show random molecular organization, as one should expect.

NMR characterization of lignins in Arabidopsis altered in the activity of ferulate 5-hydroxylase

Nuclear magnetic resonance (NMR) of isolated lignins from an Arabidopsis mutant deficient in ferulate 5-hydroxylase (F5H) and transgenic plants derived from the mutant by overexpressing the F5H gene has provided detailed insight into the compositional and structural differences between these lignins. Wild-type Arabidopsis has a guaiacyl-rich, syringyl-guaiacyl lignin typical of other dicots, with prominent β-aryl ether (β–O–4), phenylcoumaran (β–5), resinol (β–β), biphenyl/dibenzodioxocin (5–5), and cinnamyl alcohol end-group structures. The lignin isolated from the F5H-deficient fah1–2 mutant contained only traces of syringyl units and consequently enhanced phenylcoumaran and dibenzodioxocin levels. In fah1–2 transgenics in which the F5H gene was overexpressed under the control of the cauliflower mosaic virus 35S promoter, a guaiacyl-rich, syringyl/guaiacyl lignin similar to the wild type was produced. In contrast, the isolated lignin from the fah1–2 transgenics in which F5H expression was driven by the cinnamate 4-hydroxylase promoter was almost entirely syringyl in nature. This simple lignin contained predominantly β-aryl ether units, mainly with erythro-stereochemistry, with some resinol structures. No phenylcoumaran or dibenzodioxocin structures (which require guaiacyl units) were detectable. The overexpression of syringyl units in this transgenic resulted in a lignin with a higher syringyl content than that in any other plant we have seen reported.

NMR characterization of altered lignins extracted from tobacco plants down-regulated for lignification enzymes cinnamylalcohol dehydrogenase and cinnamoyl-CoA reductase

Homologous antisense constructs were used to down-regulate tobacco cinnamyl-alcohol dehydrogenase (CAD; EC 1.1.1.195) and cinnamoyl-CoA reductase (CCR; EC 1.2.1.44) activities in the lignin monomer biosynthetic pathway. CCR converts activated cinnamic acids (hydroxycinnamoyl–SCoAs) to cinnamaldehydes; cinnamaldehydes are then reduced to cinnamyl alcohols by CAD. The transformations caused the incorporation of nontraditional components into the extractable tobacco lignins, as evidenced by NMR. Isolated lignin of antisense-CAD tobacco contained fewer coniferyl and sinapyl alcohol-derived units that were compensated for by elevated levels of benzaldehydes and cinnamaldehydes. Products from radical coupling of cinnamaldehydes, particularly sinapaldehyde, which were barely discernible in normal tobacco, were major components of the antisense-CAD tobacco lignin. Lignin content was reduced in antisense-CCR tobacco, which displayed a markedly reduced vigor. That lignin contained fewer coniferyl alcohol-derived units and significant levels of tyramine ferulate. Tyramine ferulate is a sink for the anticipated build-up of feruloyl–SCoA, and may be up-regulated in response to a deficit of coniferyl alcohol. Although it is not yet clear whether the modified lignins are true structural components of the cell wall, the findings provide further indications of the metabolic plasticity of plant lignification. An ability to produce lignin from alternative monomers would open new avenues for manipulation of lignin by genetic biotechnologies.

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

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

An alternative application to the Portuguese agro-industrial residue: Wheat straw

The effects of alkaline treatments of the wheat straw with sodium hydroxide were investigated. The optimal condition for extraction of hemicelluloses was found to be with 0.50 mol/l sodium hydroxide at 55C for 2 h. This resulted in the release of 17.3% of hemicellulose (% dry starting material), corresponding to the dissolution of 49.3% of the original hemicellulose. The yields were determined by gravimetric analysis and expressed as a proportion of the starting material. Chemical composition and physico-chemical properties of the samples of hemicelluloses were elucidated by a combination of sugar analyses, Fourier transform infrared (FTIR), and thermal analysis. The results showed that the treatments were very effective on the extraction of hemicelluloses from wheat straw and that the extraction intensity (expressed in terms of alkali concentration) had a great influence on the yield and chemical features of the hemicelluloses. The FTIR analysis revealed typical signal pattern for the hemicellulosic fraction in the 1,200-1,000 cm(-1) region. Bands between 1,166 and 1,000 cm(-1) are typical of xylans.

Composites from Brazilian natural fibers with polypropylene: mechanical and thermal properties

Brazil has a well established ethanol production program based on sugarcane. Sugarcane bagasse and straw are the main by-products that may be used as reinforcement in natural fiber composites. Current work evaluated the influence of fiber insertion within a polypropylene (PP) matrix by tensile, TGA and DSC measurements. Thus, the mechanical properties, weight loss, degradation, melting and crystallization temperatures, heat of melting and crystallization and percentage of crystallinity were attained. Fiber insertion in the matrix improved the tensile modulus and changed the thermal stability of composites (intermediary between neat fibers and PP). The incorporation of natural fibers in PP promoted also apparent T(c) and Delta H(c) increases. As a Conclusion, the fibers added to polypropylene increased the nucleating ability, accelerating the crystallization process, improving the mechanical properties and consequently the fiber/matrix interaction.

Obtaining polymeric composite membranes from lignocellulosic components of sugarcane bagasse for use in wastewater treatment

Currently, several research groups and industries are studying applications for the residues from agrobusiness, other than burning them. Thinking about a better use for the sugarcane bagasse, this study aims to obtain membranes of cellulose acetate composite with oxidized lignin, both isolated from sugarcane bagasse. Thus, we obtain a product with higher commercial value, from a natural fiber, which has applications in water and effluent treatment, and further contributes to the maintenance of the environment. Macromolecular components of bagasse were separated by steam explosion pre-treatment and a basic treatment with NaOH. The pulp obtained was bleached and acetylated, and subsequently membranes of this cellulose acetate were synthesized, incorporating oxidized lignin to these membranes in order to increase the metal retention capacity of them. The acetylated material was analyzed by IR, confirming acetylation. Degree of substitution was determined by volumetry, resulting in a diacetate to the MA I condition and a triacetate to MA II condition. It was observed that for the material with a lower degree of acetylation, it has better incorporation of oxidized lignins. SEM, showed membranes with dense structure. Tests were conducted to evaluate metal retention, and the average capacity of removal was 16% Cu(+2) in steady-state experiments.

Behavior of Ceriporiopsis subvermispora during Pinus taeda biotreatment in soybean-oil-amended cultures

Pinus taeda wood chips were treated with the biopulping fungus Ceriporiopsis subvermispora in soybean-oil-amended cultures The secretion of oxalic acid and the accumulation of thiobarbituric acid reactive substances were significantly increased in soybean-oil-amended cultures By contrast the secretion of hydrolytic and oxidative enzymes was not altered in the cultures Biotreated wood samples were characterized for weight and component losses as well as by in-situ thioacidolysis Residual lignins were also extracted from biotreated wood using a mild-non-razing extraction procedure The lignins were characterized by (31)P nuclear magnetic resonance ((31)P-NMR) spectroscopy Soybean oil amendment in the cultures was found to affect lignin degradation routes however it inhibited depolymerization reactions detectable in the residual lignin that was retained in the biotreated wood As a consequence chemithermomechanical pulping of the biotreated samples was not improved by soybean oil amendment in the cultures Crown Copyright (C) 2010 Published by Elsevier Ltd All rights reserved