Antioxidant activity of various lignins and lignin-related phenylpropanoid units with high and low molecular weight

Jevgenija Ponomarenko, Maris Lauberts, Tatiana Dizhbite, Liga Lauberte, Vilhelmina Jurkjane and Galina Telysheva


The antioxidant activities (AoAs) of 50 different technical lignins have been determined. The lignins of various botanical origins (annual plants, coniferous trees, and deciduous trees) were isolated and fractionated by different techniques (delignification by alkali, kraft process, fast pyrolysis, and hydrolysis). The structure and the functionality of lignins were characterized by functional group analyses (phenolic OH, carboxyl, and methoxyl groups), analytical pyrolysis pyrolysis/gas chromatography/mass spectrometry/flame ionization detector (Py-GC/MS/FID), electron paramagnetic resonance, size exclusion chromatography, and titrimetric methods, and the AoAs were evaluated as the capacity to scavenge the DPPH· and ABTS·+ free radicals. The relationship between the lignin structure and the AoA was characterized by pair correlation, partial correlation, and multivariate regression analyses, including correlated components regression. The results were compared with those of lignin model compounds and low molecular weight phenylpropanoids. It has been shown that molecular weight does not influence essentially the AoA of lignins. There is a relationship between the activities of low and high molecular weight polyphenols; their mechanisms of action are also similar. The structure-related AoA of lignins has been quantified for the first time.

  • Alves, A., Schwanninger, M., Pereira, H., Rodrigues, J. (2006) Analytical pyrolysis as a direct method to determine the lignin content in wood. Part 1: comparison of pyrolysis lignin with Klason lignin. J. Anal. Appl. Pyrol. 76:209–213.

  • Arshanitsa, A., Ponomarenko, J., Dizhbite, T., Andersone, A., Gosselink, R.J.A., van der Putten, J., Lauberts, M., Telysheva, G. (2013) Fractionation of technical lignins as a tool for improvement of their antioxidant properties. J. Anal. Appl. Pyrol. 103:78–85.

  • Balasundram, N., Sundram, K., Samman, S. (2006) Phenolic compounds in plants and agri-industrial by-products: antioxidant activity, occurrence, and potential uses. Food Chem. 99:191–203.

  • Baltrusaityte, V., Venskutonis, P., Cheksteryte, V. (2007) Radical scavenging activity of different floral origin honey and beebread phenolic extracts. Food Chem. 101:502–514.

  • Barclay, L.R.C., Xi, F., Norris, J.Q. (1997) Antioxidant properties of phenolic lignin model compounds. J. Wood Chem. Technol. 17:73–90.

  • Björkman, A. (1956) Studies on finely divided wood. Part 1: extraction of lignin with neutral solvents. Svenk Papperstidn. 59:477–485.

  • Bracco, P., Brunella, V., Zanetti, M., Luda, M.P., Costa, L. (2007) Stabilisation of ultra-high molecular weight polyethylene with Vitamin E. Polym. Degrad. Stabil. 92:2155–2162.

  • Brand-Williams, W., Cuvelier, M.E., Reset, C. (1995) Use of a free radical method to evaluate antioxidant activity. Food Sci. Technol. 28:25–30.

  • Brunow, G., Lundquist, K., Gellerstedt, G. (1999) Lignin. In: Analytical Methods in Wood Chemistry Pulping and Papermaking. Eds. Sjöström, E., Alén, R. Springer-Verlag, Berlin. pp. 77–124.

  • Crestini, C., Melone, F., Sette, M., Saladino, R. (2011) Milled wood lignin: a linear oligomer. Biomacromolecules 12:3928–3935.

  • Davison, B.H., Parks, J., Davis, M.F., Donohoe, B.S. (2013) Plant cell walls: basics of structure, chemistry, accessibility and the influence on conversion. In: Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals. Ed. Wyman, C.E. John Wiley & Sons, Ltd. pp. 23–38.

  • Di Meo, F., Lemaur, V., Cornil, J., Lazzaroni, R., Duroux, J.L., Olivier, Y., Trouillas, P. (2013) Free radical scavenging by natural polyphenols: atom versus electron transfer. J. Phys. Chem. A 117:2082–2092.

  • Dizhbite, T., Telysheva, G., Jurkjane, V., Viesturs, U. (2004) Characterization of the radical scavenging activity of lignins – natural antioxidants. Bioresource Technol. 95:309–317.

  • Dizhbite, T., Telysheva, G., Dobele, G., Arshanitsa, A., Bikovens, O., Andersone, A., Kampars, V. (2011) Py-GC/MS for characterization of non-hydrolyzed residues from bioethanol production from softwood. J. Anal. Appl. Pyrol. 90:126–132.

  • Dizhbite, T., Ponomarenko, J., Andersone, A., Dobele, G., Lauberts, M., Krasilnikova, J., Mironova-Ulmane, N., Telysheva, G. (2012) Role of paramagnetic polyconjugated clusters in lignin antioxidant activity (in vitro). IOP Conf. Ser. Mater. Sci. Eng. 38:012033 (doi:10.1088/1757-899X/38/1/012033).

  • Dobele, G., Dizhbite, T., Urbanovich, I., Andersone, A., Ponomarenko, J., Telysheva, G. (2009) Pyrolytic oil on the basis of wood and the antioxidant properties of its water-soluble and -insoluble fraction. J. Anal. Appl. Pyrol. 85:81–85.

  • Domenek, S., Louaifi, A., Guinault, A., Baumberger, S. (2013) Potential of lignins as antioxidant additive in active biodegradable packaging materials. J. Polym. Environ. 21:692–701.

  • Gorinstein, S., Cvirkova, M., Machackova, I., Haruenkit, R., Park, Y.S., Jung, S.T., Yamamoto, K., Martinez, A.L., Katrich, E., Trakhtenberg, S. (2002) Characterization of antioxidant compounds in Jaffa sweeties and white grapefruits. Food Chem. 84:503–510.

  • Kozlowski, D., Trouillas, P., Calliste, C., Marsal, P., Lazzaroni, R., Duroux, J.L. (2007a) Density functional theory study of the conformational, electronic, and antioxidant properties of natural chalcones. J. Phys. Chem. A 111:1138–1145.

  • Kozlowski, D., Marsal, P., Steel, M., Mokrini, R., Duroux, J.L., Lazzaroni, R., Trouillas, P. (2007b) Theoretical investigation of the formation of a new series of antioxidant depsides from the radiolysis of flavonoid compounds. Radiat. Res. 168:243–252.

  • Lapierre, C., Mila, I., Begum, A.N., Fukushima, K., Heinonen, S.M., Adlercreutz, H., Remesy, C., Scalbert, A. (2004) New precusors of mammalian lignans in rats. In: Proceeding of the 8th European Workshop on Lignocellulisics and Pulp, Riga, Latvia, August 22–25. pp. 101–104.

  • Leopoldini, M., Pitarch, I.P., Russo, N., Toscano, M. (2004) Structure, conformation, and electronic properties of apigenin, luteolin, and taxifolin antioxidants. A first principle theoretical study. J. Phys. Chem. A 108:92–96.

  • Litwinienko, G., Ingold, K.U. (2007) Solvent effects on the rates and mechanisms of reaction of phenols with free radicals. Acc. Chem. Res. 40:222–230.

  • Louaifi, A., Guinault, A., Domenek, S., Ducruet, V., Baumberger, S. (2011) Valorisation of industrial lignon as additive with antioxidiant properties in PLA. Ital. J. Food Sci. 23:142–145.

  • Louli, V., Ragoussis, N., Magoulas, K. (2004) Recovery of phenolic antioxidants from wine industry by-products. Bioresource Technol. 92:201–208.

  • Morikawa, T. (2007) Search for bioactive constituents from several medicinal foods: hepatoprotective, antidiabetic, and antiallergic activities. J. Nat. Med. 61:112–126.

  • Moure, A., Cruz, J.M., Franco, D., Domõanguez, J.M., Sineiro, J., Domoanguez, H., Josea, M., Parajoa, C. (2001) Review: natural antioxidants from residual sources. Food Chem. 72:145–171.

  • Ohra-aho, T., Gomes, F.J.B., Colodette, J.L., Tamminen, T. (2013) S/G ratio and lignin structure among Eucalyptus hybrids determined by Py-GC/MS and nitrobenzene oxidation. J. Anal. Appl. Pyrol. 101:166–171.

  • Ozsoy, N., Can, A., Yanardag, R., Akev, N. (2008) Antioxidant activity of Smilax excelsa L. leaf extracts. Food Chem. 110: 571–583.

  • Pan, X., Kadla, J.F., Ehara, K., Gilkes, N., Saddler, J.N. (2006) Organosolv ethanol lignin from hybrid poplar as a radical scavenger: relationships between lignin structure, extraction conditions, and antioxidant activity. J. Agric. Food Chem. 54:5806–5813.

  • Ponomarenko, J., Dizhbite, T., Lauberts, M., Viksna, A., Dobele, G., Bikovens, O., Telysheva, G. (2014a) Characterization of softwood and hardwood LignoBoost kraft lignins with emphasis on their antioxidant activity. Bioresources 9:2051–2068.

  • Ponomarenko, J., Trouillas, P., Martin, N., Dizhbite, T., Krasilnikova, J., Telysheva, G. (2014b) Elucidation of antioxidant properties of wood bark derived saturated diarylheptanoids: a comprehensive (DFT-supported) understanding. Phytochemistry 103:178–187.

  • Pouteau, C., Cathala, B., Dole, P., Kurek, B., Monties, B. (2005) Structural modification of Kraft lignin after acid treatment: characterization of the apolar extracts and the influence on the antioxidant properties in polypropylene. Ind. Crop. Prod. 21:101–108.

  • Ringena, O., Lebioda, S., Lehnen, R., Saake, B. (2006) Size-exclusion chromatography of technical lignins in dimethyl sulfoxide/water and dimethylacetamide. J. Chromatogr. A 1102:154–163.

  • Setzer, W.N. (2011) Lignin-derived oak phenolics: a theoretical examination of additional potential health benefits of red wine. J. Mol. Model. 17:1841–1845.

  • Seyoum, A., Asres, K., El-Fiky, F.K. (2006) Structure-radical scavenging activity relationships of flavonoids. Phytochemistry 67:2058–2070.

  • Shen, D.K., Gu, S., Luo, K.H., Wang, S.R., Fang, M.X. (2010) The pyrolytic degradation of wood-derived lignin from pulping process. Bioresource Technol. 101:6136–6146.

  • Tao, J., Morikawa, T., Toguchida, I., Ando, S., Matsuda, H., Yoshikawa, M. (2002) Inhibitors of nitric oxide production from the bark of Myrica rubra: structures of new biphenyl type diarylheptanoid glycosides and taraxerane type triterpene. Bioorg. Med. Chem. 10:4005–4012.

  • Torres, R., Urbina, F., Morales, C., Modak, B., Monache F. (2003) Antioxidant properties of lignans and ferulic acid from the resinous exudate of Larrea nitida. J. Chil. Chem. Soc. 48:61–63.

  • Trouillas, P., Marsal, P., Siri, D., Lazzaroni, R., Duroux, J.L. (2006) A DFT study of the reactivity of OH groups in quercetin and taxifolin antioxidants: the specificity of the 3-OH site. Food Chem. 97:679–688.

  • Trouillas, P., Marsal, P., Svobodova, A., Vostalova, J., Gazak, R., Hrbac, J., Sedmera, P., Kren, V., Lazzaroni, R., Duroux, J.L., Walterova, D. (2008) Mechanism of the antioxidant action of silybin and 2,3-dehydrosillybin flavonolignans: a joint experimental and theoretical study. J. Phys. Chem. A 112:1054–1063.

  • Volf, I., Ignat, J., Neamtu, M., Popa, I. (2014) Thermal stability, antioxidant activity and photo-oxidation of natural polyphenols. Chem. Pap. 68:121–129.

  • Wang, S., Melnyk, J.P., Tsao, R., Marcone, M.F. (2011) How natural dietary antioxidants in fruits, vegetables and legumes promote vascular health. Food Res. Int. 44:14–22.

  • Wolf, C., Krivec, T., Blassnig, J., Lederer, K., Schneider, W. (2002) Examination of the suitability of alpha-tocopherol as a stabilizer for ultra-high molecular weight polyethylene used for articulating surfaces in joint endoprostheses. J. Mater. Sci. Mater. Med. 13:185–189.

  • Yang, Y., Kinoshita, K., Koyama, K., Takahashi, K., Kondo, S., Watanabe, K. (2002) Structure-antiemetic-activity of some diarylheptanoids and their analogues. Phytomedicine 9:146–152.

  • Zakis, G.F. Functional Analysis of Lignins and Their Derivatives. TAPPI Press, Atlanta, 1994.

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