Ionic Liquid Lignosulfonate: Dispersant and Binder for Preparation of Biocomposite Materials

Ionic liquid lignins are prepared from sodium lignosulfonate by a cation exchange reaction and display glass transition temperatures as low as ?13 °C. Diethyleneglycol‐functionalized protic cations inhibit lignin aggregation to produce a free‐flowing “ionic liquid lignin”, despite it being a high‐molecular‐weight polyelectrolyte. Through this approach, the properties of both lignin and ionic liquids are combined to create a dispersant and binder for cellulose+gluten mixtures to produce small microphases. Biocomposite testing pieces are produced by hot‐pressing this mixture, yielding a material with fewer defects and improved toughness in comparison to other lignins. The use of unmodified lignosulfonate, acetylated lignosulfonate, or free ionic liquid for similar materials production yields poorer substances because of their inability to maximize interfacial contact and complexation with cellulose and proteins.     

Peroxodicarbonate as a Green Oxidizer for the Selective Degradation of Kraft Lignin into Vanillin

Lignin, the world's largest resource of renewable aromatics, with annually roughly 50 million tons of accruing technical lignin, mainly Kraft lignin, is highly underdeveloped regarding the production of monoaromatics. We demonstrate the oxidative depolymerization of Kraft lignin at 180 °C to produce vanillin 1 in yields up to 6.2 wt % and 92 % referred to the maximum yield gained from the quantification reaction utilizing nitrobenzene. Using peroxodicarbonate (C₂O₆²⁻) as “green” oxidizer for the degradation, toxic and/or harmful reagents are prevented. Also, the formed waste can serve as makeup chemical in the pulping process. Na₂C₂O₆ is synthesized in an ex-cell electrolysis of aqueous Na₂CO₃ at BDD anodes, achieving a yield of Na₂C₂O₆ with 41 %. At least, the oxidation and degradation of Kraft lignin is analysis via UV/Vis and NMR spectroscopy.     

Blue-LED Synthesis of Pummerer's Ketones by Peroxidase-Lignin-Catalyzed Oxidative Coupling of Substituted Phenols

Pummerer's ketones resembling the tricyclic scaffold of bioactive natural substances were synthesized by blue-LED driven Horseradish Peroxidase oxidative coupling of substituted phenols in 2-methyltetrahydrofuran by using meso-tetraphenylporphyrin as photosensitizer and dioxygen as primary oxidant. The application of functionalized lignin nanoparticles as a renewable and efficient platform for the immobilization of the enzyme extended the effectiveness of the overall process to heterogeneous catalysis under buffer limiting conditions.     

Anti-atherosclerotic activity of Betulinic acid loaded polyvinyl alcohol/methylacrylate grafted Lignin polymer in high fat diet induced atherosclerosis model rats

Betulinic acid is one such natural pentacyclic triterpenoid compound, holding various pharmacological properties but its poor bioavailability is the only limitation. One of the biological macromolecules such as Lignin is a plant-derived aromatic, eco-friendly and low-cost polymer that certainly self-assembles into nano-sized colloids. Therefore, onto the current investigation, we increased the bioavailability of betulinic acid by coating on to a nanopolymer prepared with poly vinyl alcohol, lignins and methyl acrylate. Betulinic acid loaded polyvinyl alcohol/ethylacrylate grafted Lignin polymer (PVA/Lig-g-MA) nanoformulation was characterized using FTIR, XRD, SEM and TEM analysis and also the drug entrapment, in vitro drug releasing capacity was done to examine the efficiency of the nanoformulation of a drug. The MTT assay was evaluated the cytotoxicity of synthesized nanoformulation against normal endothelial cells HUVEC and HAPEC to confirm the side effects of the drug. The anti-atherosclerotic property of the nanoformulation was ascertained in both in vitro condition (with HUVEC and HPAEC) and in vivo studies (with Wistar rats). As a result, the characterization studies and in vitro studies clearly confirmed the Betulinic acid loaded PVA/Lig-g-MA nanoformulation is an ideal nanopolymer and it doesn’t cause any cytotoxic effect in normal endothelial cells. It also decreased the lipopolysaccharides induced inflammation through the down-regulation of NFκB and MAP/JNK signaling molecule expressions. Following in vivo results confirmed the synthesized nanoformulation effectively decreased the hyperchlostremia, inflammation and vasoconstriction, which induced over high fat diet. The results of histopathological analysis of cardiac tissues also confirmed the cardioprotective role of synthesized nanoformulation. Overall, both the in vitro and in vivo studies authentically proven the Betulinic acid loaded PVA/Lig-g-MA nanoformulation would be a potent cost effective anti-atherosclerotic nanodrug.     

Ruthenium‐Catalyzed C?C Bond Cleavage in Lignin Model Substrates

Ruthenium–triphos complexes exhibited unprecedented catalytic activity and selectivity in the redox‐neutral C C bond cleavage of the β‐O‐4 lignin linkage of 1,3‐dilignol model compounds. A mechanistic pathway involving a dehydrogenation‐initiated retro‐aldol reaction for the C C bond cleavage was proposed in line with experimental data and DFT calculations.     

A model of the chemical composition and pyrolysis kinetics of lignin

This study presents a novel approach for the chemical representation of lignin for modelling the reaction kinetics of lignin in lignocellulosic biomass. This methodology relies on the definition of dimeric pseudo-components containing phenolic functionalities, i.e., p-hydroxyphenyl, guaiacyl and syringyl groups, as measured in real biomass and native lignin through wet chemistry and spectroscopic techniques. The reactivities of the lignin pseudo-components are modelled through a series of lumped unidirectional reactions, whose product formation and reaction rate constants are optimised to replicate a comprehensive experimental dataset gathered from several works available in the literature. The new kinetic model contributes to the state-of-the-art by providing a more accurate depiction of the conversion rates, selectivity of char vs. volatiles, and aromatic composition in condensable products in line with the inherent reactivity of lignin functionalities and the empirical observations of lignin depolymerisation and thermal degradation at low (<1?K/s) and high heating rates (>50?K/s).     

Gas Chromatographic Analysis of Phenolic Compounds from Lignin

Abstract

This paper describes the separation and identification of phenolics derived from lignin, a major component of wood, by gas chromatography (G.C.) using a Tenax GC column.     

Characterisation of archaeological waterlogged wood by pyrolytic and mass spectrometric techniques

Two techniques based on analytical pyrolysis and mass spectrometry, direct exposure-MS (DE-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), were used to characterise waterlogged archaeological wood and to study degradation patterns of wood in aqueous environments. The two techniques were applied to samples from the excavation of the Site of the Ancient Ships of Pisa San Rossore in Pisa (Italy), and data were compared to those relative to native sound wood of the same species (pine, elm, beech). Both the methods result valuable in the analysis of ancient wood artefacts, avoiding the long wet-chemical procedures that are commonly used in wood analysis, and allowing us to use a minimal sample size. DE-MS achieves a global mass spectral fingerprint of lignin and polysaccharides pyrolysis compounds in few minutes, and the results have been interpreted with the support of principal component analysis (PCA) of mass spectra. Py-GC/MS permits detailed molecular analysis of pyrolysis compounds and highlights some chemical modifications of lignin in archaeological samples, as demethylation of both guaiacyl and syringyl lignin units. Both the techniques demonstrate consistent loss of polysaccharides in archaeological wood.     

Synthesis of phenol-formaldehyde resol resins using organosolv pine lignins

Lignin was extracted from white pine sawdust by organosolv-extraction using hot-compressed ethanol-water co-solvent. The optimum conditions for extracting lignin from the pine sawdust were found to be at 180 °C with ethanol-water solvent (1:1 wt/wt), where the lignin yield attained ca. 26% with a purity of ca. 83%. The lignin under such conditions was oligomers with a broad molecular weights distribution: M_n of 537, M_w of 1150 and polydispersity of 2.14. Bio-based phenol-formaldehyde resol resins were synthesized using the resultant lignin as the replacement of petroleum-based phenol at varying ratios from 25 to 75 wt.% by condensation polymerization catalyzed by sodium hydroxide. Upon heating the lignin-phenol-formaldehyde resols could solidify with a main exothermic peak at around 150-175 °C, typical of the conventional phenolic resol resins, and a secondary peak at 135-145 °C, likely due to the exothermic reactions between the free formaldehyde with phenol or lignin to form methylophenols. The replacement of phenol with lignin at a large ratio deferred the curing process, and the introduction of lignin in the resin formula decreased the thermal stability of the resin, leading to a lowered decomposition temperature and a reduced amount of carbon residue at elevated temperatures. For practical applications, it is suggested that the replacement ratio of phenol with lignin be less than 50 wt.%. The thermal stability can however be improved by purifying the lignin feedstock before the resin synthesis.