Role of paramagnetic polyconjugated clusters in lignin antioxidant activity (in vitro)

Using physico-chemical methods (EPR, SEC, Py-GC/MS and UV/VIS spectroscopy) and wet chemical analysis, the characteristics of 6 hardwood lignins in terms of functionality, molecular weight and composition of lignin substructures were determined and considered together with the results of DPPH•, ABTS •+ and O2•- antioxidant assays with the aim to understand the relationships governing antioxidant properties of lignin. The strong positive linear correlation between lignin antioxidant capacity in the three assays used and the extent of conjugation of paramagnetic polyconjugated clusters in lignin macromolecules was found. The biological activity of the most active alkaline lignins was assessed by in vitro experiment with human blood.publishersversionPeer reviewe

Applications of lignin in the agri-food industry

Of late, valorization of agri-food industrial by-products and their sustainable utilization is gaining much contemplation world-over. Globally, 'Zero Waste Concept' is promoted with main emphasis laid towards generation of minimal wastes and maximal utilization of plantbased agri-food raw materials. One of the wastes/by-products in the agri-food industry are the lignin, which occurs as lignocellulosic biomass. This biomass is deliberated to be an environmental pollutant as they offer resistance to natural biodegradation. Safe disposal of this biomass is often considered a major challenge, especially in low-income countries. Hence, the application of modern technologies to effectively reduce these types of wastes and maximize their potential use/applications is vital in the present day scenario. Nevertheless, in some of the high-income countries, attempts have been made to efficiently utilize lignin as a source of fuel, as a raw material in the paper industry, as a filler material in biopolymer based packaging and for producing bioethanol. However, as of today, agri-food industrial applications remains significantly underexplored. Chemically, lignin is heterogeneous, bio-polymeric, polyphenolic compound, which is present naturally in plants, providing mechanical strength and rigidity. Reports are available wherein purified lignin is established to possess therapeutic values; and are rich in antioxidant, anti-microbial, anti-carcinogenic, antidiabetic properties, etc. This chapter is divided into four sub-categories focusing on various technological aspects related to isolation and characterization of lignin; established uses of lignin; proved bioactivities and therapeutic potentials of lignin, and finally on identifying the existing research gaps followed by future recommendations for potential use from agri-food industrial wastes.Theme of this chapter is based on our ongoing project- Valortech, which has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 810630

Production of nanoporous carbons from wood processing wastes and their use in supercapacitors and CO2 capture

Highly porous carbons were obtained from solid wastes generated in the chemical and the mechanical processing of birch wood (substandard kraft cellulose, hydrolysis lignin, chips and bark). NaOH-chemical activation of these residues at 575–800 °C resulted in an efficient process to produce carbons with specific surface areas well above 1000 m2 g−1 and average pore widths of 1–1.7 nm. Comparative evaluations have shown the potentiality of wood wastes-based carbons in applications related to environmental protection. Activated carbons derived from chips- and bark-birch wood displayed specific capacitances as high as 308 F g−1 in the H2SO4 aqueous electrolyte and 200 F g−1 in the (C2H5)4NBF4/acetonitrile organic medium. Moreover, their capacitive performance at high current density competed well with that found for commercial carbons used in supercapacitors. Wood-derived carbons also proved to be highly promising for CO2 capture in power stations, achieving uptakes under post- and pre-combustion conditions of 11–16 wt.% and 49–91 wt.%, respectively.The research leading to these results has received funding support of the European Community’s Service Framework Programme (FP7/2007-2011,203459), from the Latvian Budget (Grant 1546), and the Latvian National Programme VPP-2,2.4,1.1.Peer reviewe

Characterisation of non-hydrolyzed residues from bioethanol production from softwood and wheat straw

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Functionality and physico-chemical characteristics of wheat straw lignin, BioligninTM, derivatives formed in the oxypropylation process

The new organosolv process of wheat straw fractionation elaborated by Compagnie Industrielle de la matiere Vegetale (France) corresponds to the biorefinery approach, which allows separating cellulose, hemicel -luloses, and lignin. The straw lignin (Biolignin) is an attractive product, for which new applications are sought. In the present work, straw lignin (L) was converted into liquid lignopolyols via a batch reaction with propylene oxide (PO). The effects of the lignin content (L%) in the initial reaction mixture (L/(L+PO) on the oxypropylation process and the properties of whole lignopolyols and L/PO copolymers were studied. Almost complete disappearance of L-OHphen and L-COOH groups in copolymers was accompanied by an increase in the L-OHaliph groups’ content therein. The polydispersity (Mw/Mn) of all copolymers obtained decreased essentially compared to the reference. The extent of PO grafting onto OH groups increased with decreasing lignin content in the initial reaction mixture. At a lignin content of 15–30% in the initial reaction mixture, the lignopolyols fulfil the requirements of polyol polyethers for rigid polyurethane foam production. The further increase in the lignin content leads to the appearance of the non-liquefied fraction and the undesirable increase in the viscosity of the liquefied part

Characterization of Bark Rich-In-Tannins Extracts from Deciduous Trees with Emphasis on Their Antioxidant Activity

The barks of deciduous trees spread over a wide area of Northern Europe, were sequentially extracted using solvents of increasing polarity. The highest yields of hydrophilic extractives were found for ash tree and goat willow (23.6% and 23.8%, respectively). The highe st total contents of polyphenols were found for black alder and goat willow bark (0.18 GAE  g -1 and 0.12 GAE  g -1 , respectively). Hydrophilic extract from the both grey and black alder barks contained high amount (up to 7 % on bark dry mass) of condensed tannins (CT) or oligomeric proanthocyanidins (OPC). In tests with free radicals (ABTS ●+ , DPPH ● ), the high radical scavenging capacities of the hydrophilic extracts enriched with OPC were demonstrated. The antioxidant efficiency of the hydrophilic extracts and purified OPC from alder barks was tested by their influence on thermo-oxidative destruction of model polyurethane (PU) films. The hydrophilic extracts enriched with tannins have good potential as a technical antioxidant for polyurethanes, with the most prominent activity for the hydrophilic extract from black alder and goat willow bark

Fractionation of technical lignins as a tool for improvement of their antioxidant properties

The modern biorefinery concept is aimed at the elaboration of sustainable processes with the most profitable utilization of all biomass products obtained at the technological cycle. Lignin separated as by-product in the lignocellulosic chemical processing is recognized as an important component of polymer systems. The presence of sterically hindered phenolic hydroxyl groups in the lignin macromolecule opens the possibility of its application as antioxidant for composites, e.g. polyurethanes (PU), which are considered as one of the most versatile polymeric materials. In the present work, the object of investigations was lignin obtained as a product, so-called BIOLIGNIN™, of wheat straw organosolv processing for pulp and fuel ethanol production (CIMV pilot plant, France). However, heterogeneity of the lignin obtained negatively influences its applicability that can be overcome by fractionation. Three soluble fractions were isolated from CIMV lignin by a sequential extraction with dichloromethane (A fraction), methanol (B fraction) and mixture of both the solvents (C fraction) and characterized in terms of their composition, functionality and structure using analytical pyrolysis (Py-GC/MS), 31P NMR and Size Exclusion Chromatography (SEC) methods. Antioxidant properties of BIOLIGNIN™ fractions were assessed in the tests with free radicals ABTS+ and DPPH. Application of Py-GC/MS for characterization of the fractions opened an opportunity to found some novel “structure–activity” correlations needed for understanding and tuning of antioxidant properties of lignins. The antioxidant activity of the fractions under investigation was tested by their influence on thermo-oxidative destruction of prepared model PU films. The data of TGA method (oxidative conditions) clearly testified the antioxidant effect of all three fractions with the most prominent activity for C fraction. The shifting of the exothermal maxima connected with oxidizing of volatile products of PU destruction to the higher temperature region by 20–30 K and 30–40 K was registered

Py-GC/MS for Characterisation of Non-Hydrolyzed Residues from Bioethanol Production from Softwood

Analytical pyrolysis combined with gas chromatography/mass spectrometry (Py-GC/MS) was used to analyze chemical composition of non-hydrolyzed residues (LHRs) obtained by three methods of bioethanol production: softwood acid hydrolysis (AH), separate enzymatic hydrolysis and fermentation (SHF), and simultaneous saccharification and fermentation (SSF). Complementary techniques, such as EPR- and FTIR-spectroscopy, and routine chemical analysis procedures were used for this study as well. The Py-GC/MS analysis of the LHRs has shown a higher efficiency of carbohydrates hydrolysis upon SSF process in comparison with SHF and AH processes. Comparison of chemical analysis results and data obtained by Py-GC/MS of LHRs brought the direct evidence of incorporation of carbohydrates-derived fragments into the lignin matrix and formation of so-called pseudo-lignin upon different stages of softwood processing. Modifications of lignin component of LHRs on various stages of the process of bioethanol production, such as oxidation and condensation reactions, cleavage of ether bonds and destruction of side propane chain, were revealed using Py-GC/MS

Can Lignin Wastes Originating From Cellulosic Ethanol Biorefineries Act as Radical Scavenging Agents?

Lignin is a co-product from the biorefinery and paper industry. Its non-energetic valorization remains a field of extensive R&D developments. In this perspective, this study is undertaken to evaluate the radical scavenging ability of some herbaceous lignins. These lignins, extracted from Miscanthus (Miscanthus x giganteus) or Switchgrass (Panicum Virgatum L.), are selected as benchmarks for this study as a function of their chemical structure and average molecular weight. These technical lignins, side-products in the bioethanol production process, are found to display a moderate antioxidant activity as evaluated by the DPPH (1,1-diphenyl-2-picrylhydrazil) free radical scavenging test system. A correlation between the radical scavenging properties and the molecular features is proposed and discussed. Infrared spectroscopy is evaluated as a straightforward qualitative prediction tool for the radical scavenging capacity