Enhancing the Antioxidant Activity of Technical Lignins by Combining Solvent Fractionation and Ionic‐Liquid Treatment

Abstract A grass soda technical lignin (PB1000) underwent a process combining solvent fractionation and treatment with an ionic liquid (IL), and a comprehensive investigation of the structural modifications was performed by using high‐performance size‐exclusion chromatography, 31P NMR spectroscopy, thioacidolysis, and GC–MS. Three fractions with distinct reactivity were recovered from successive ethyl acetate (EA), butanone, and methanol extractions. In parallel, a fraction deprived of EA extractives was obtained. The samples were treated with methyl imidazolium bromide ([HMIM]Br) by using either conventional heating or microwave irradiation. The treatment allowed us to solubilize 28 % of the EA‐insoluble fraction and yielded additional free phenols in all the fractions, as a consequence of depolymerization and demethylation. The gain of the combined process in terms of antioxidant properties was demonstrated through 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH.) radical‐scavenging tests. Integrating further IL safety‐related data and environmental considerations, this study paves the way for the sustainable production of phenolic oligomers competing with commercial antioxidants.

[1]  D. Evtuguin,et al.  Lignin Modification Supported by DFT-Based Theoretical Study as a Way to Produce Competitive Natural Antioxidants , 2019, Molecules.

[2]  A. Jaiswal,et al.  Moving towards the second generation of lignocellulosic biorefineries in the EU: Drivers, challenges, and opportunities , 2019, Renewable and Sustainable Energy Reviews.

[3]  M. Lindström,et al.  Solvent fractionation of softwood and hardwood kraft lignins for more efficient uses: Compositional, structural, thermal, antioxidant and adsorption properties , 2019, Industrial Crops and Products.

[4]  M. Mittelbach,et al.  Influence of Ethanol Organosolv Pulping Conditions on Physicochemical Lignin Properties of European Larch , 2019, International Journal of Chemical Engineering.

[5]  C. Si,et al.  Enhancing the solubility and antioxidant activity of high-molecular-weight lignin by moderate depolymerization via in situ ethanol/acid catalysis , 2019, Industrial Crops and Products.

[6]  A. Ragauskas,et al.  From lignin to valuable products-strategies, challenges, and prospects. , 2019, Bioresource technology.

[7]  C. Si,et al.  One-pot lignin depolymerization and activation by solid acid catalytic phenolation for lightweight phenolic foam preparation , 2018, Industrial Crops and Products.

[8]  F. Allais,et al.  Chemo-Enzymatic Synthesis of Renewable Sterically-Hindered Phenolic Antioxidants with Tunable Polarity from Lignocellulose and Vegetal Oil Components , 2018, International journal of molecular sciences.

[9]  R. Gosselink,et al.  Lignin Based Functional Additives for Natural Rubber , 2018, ACS Sustainable Chemistry & Engineering.

[10]  Roland Weber,et al.  An overview of chemical additives present in plastics: Migration, release, fate and environmental impact during their use, disposal and recycling. , 2018, Journal of hazardous materials.

[11]  S. V. D. Bosch,et al.  Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading. , 2018, Chemical Society reviews.

[12]  M. Lindström,et al.  Membrane filtration of kraft lignin : Structural charactristics and antioxidant activity of the low-molecular-weight fraction , 2018 .

[13]  C. Lapierre,et al.  Imidazolium-Based Ionic Liquids as Efficient Reagents for the C-O Bond Cleavage of Lignin. , 2018, ChemSusChem.

[14]  C. Si,et al.  A novel and efficient process for lignin fractionation in biomass-derived glycerol-ethanol solvent system , 2018 .

[15]  G. G. Eshetu,et al.  Comprehensive Insights into the Thermal Stability, Biodegradability, and Combustion Chemistry of Pyrrolidinium-Based Ionic Liquids. , 2017, ChemSusChem.

[16]  J. Beaugrand,et al.  Syringaresinol: A Renewable and Safer Alternative to Bisphenol A for Epoxy-Amine Resins. , 2017, ChemSusChem.

[17]  P. Ducrot,et al.  Chemo-enzymatic preparation and characterization of renewable oligomers with bisguaiacol moieties: promising sustainable antiradical/antioxidant additives , 2016 .

[18]  P. Ducrot,et al.  ADMET polymerization of biobased monomers deriving from syringaresinol , 2016 .

[19]  Xian Jun Loh,et al.  Towards lignin-based functional materials in a sustainable world , 2016 .

[20]  John D. Hayler,et al.  CHEM21 selection guide of classical- and less classical-solvents , 2016 .

[21]  B. Chabbert,et al.  Use of food and packaging model matrices to investigate the antioxidant properties of biorefinery grass lignins. , 2015, Journal of agricultural and food chemistry.

[22]  Thomas J. Farmer,et al.  Opportunities for Bio-Based Solvents Created as Petrochemical and Fuel Products Transition towards Renewable Resources , 2015, International journal of molecular sciences.

[23]  S. Maity.  Opportunities, recent trends and challenges of integrated biorefinery: Part II. , 2015 .

[24]  Guy Marlair,et al.  Coupling of OECD standardized test and immunomarkers to select the most environmentally benign ionic liquids option--towards an innovative "safety by design" approach. , 2015, Journal of hazardous materials.

[25]  P. Ducrot,et al.  Renewable alternating aliphatic-aromatic poly(ester-urethane)s prepared from ferulic acid and bio-based diols , 2015 .

[26]  C. Boeriu,et al.  Fractionation of five technical lignins by selective extraction in green solvents and characterisation of isolated fractions , 2014 .

[27]  John D. Hayler,et al.  A survey of solvent selection guides , 2014 .

[28]  C. Crestini,et al.  Tailoring the Molecular and Thermo-Mechanical Properties of Kraft Lignin by Ultrafiltration , 2014 .

[29]  L. Avérous,et al.  Chemical modification of lignins: Towards biobased polymers , 2014 .

[30]  Y. Barrière,et al.  Impact of the brown-midrib bm5 mutation on maize lignins. , 2014, Journal of agricultural and food chemistry.

[31]  R. Rogers,et al.  Review: Oxidation of Lignin Using Ionic Liquids—An Innovative Strategy To Produce Renewable Chemicals , 2014 .

[32]  P. Ducrot,et al.  Renewable Alternating Aliphatic–Aromatic Copolyesters Derived from Biobased Ferulic Acid, Diols, and Diacids: Sustainable Polymers with Tunable Thermal Properties , 2014 .

[33]  J. Sedbrook,et al.  p-Coumaroyl-CoA:monolignol transferase (PMT) acts specifically in the lignin biosynthetic pathway in Brachypodium distachyon , 2014, The Plant journal : for cell and molecular biology.

[34]  J. Marrot,et al.  Solvent free nucleophilic introduction of fluorine with [bmim][F] , 2014 .

[35]  Višnja Gaurina Srček,et al.  A brief overview of the potential environmental hazards of ionic liquids. , 2014, Ecotoxicology and environmental safety.

[36]  R. Gosselink,et al.  Fractionation of technical lignins as a tool for improvement of their antioxidant properties. , 2013 .

[37]  P. Ducrot,et al.  Chemo-enzymatic preparation of new bio-based bis- and trisphenols: new versatile building blocks for polymer chemistry , 2013 .

[38]  Konstantinos V Kotsanopoulos,et al.  Migration Phenomenon in Food Packaging. Food–Package Interactions, Mechanisms, Types of Migrants, Testing and Relative Legislation—A Review , 2013, Food and Bioprocess Technology.

[39]  G. Marlair,et al.  Revisiting physico-chemical hazards of ionic liquids , 2012 .

[40]  I. Mondragon,et al.  Lignin Separation and Fractionation by Ultrafiltration , 2010, Separation of Functional Molecules in Food by Membrane Technology.

[41]  G. Gellerstedt,et al.  Kraft lignin as feedstock for chemical products: The effects of membrane filtration , 2009 .

[42]  Tatiana Dizhbite,et al.  Characterization of the radical scavenging activity of lignins--natural antioxidants. , 2004, Bioresource technology.

[43]  Wolfgang G. Glasser,et al.  Recent Industrial Applications of Lignin: A Sustainable Alternative to Nonrenewable Materials , 2002 .

[44]  D. Argyropoulos,et al.  2 Chloro 4,4,5,5 tetramethyl 1,3,2 dioxaphospholane, a reagent for the accurate determination of the uncondensed and condensed phenolic moieties in lignins , 1995 .

[45]  C. Lapierre,et al.  New insights into the molecular architecture of hardwood lignins by chemical degradative methods , 1995 .

[46]  C. Berset,et al.  Use of a Free Radical Method to Evaluate Antioxidant Activity , 1995 .

[47]  E. Graf,et al.  Antioxidant potential of ferulic acid. , 1992, Free radical biology & medicine.

[48]  J. Czerkawski.  The determination of lignin , 1967, British Journal of Nutrition.