TANNINS AS NATURAL ANTIOXIDANTS

Table of Contents:

Plant phenols have received increasing interest due to their free radicalscavenging ability and their effects on the prevention of various oxidative reaction-associated diseases and stress. Recently, the isolation, use, and evaluation of natural phenolic compounds as pure or crude extracts from different plant resources have become a major field for health- and medical- related researches (Jin and Russell, 2010). In their work, Hagerman et al. (1998) evaluated tannins as biological antioxidants, and the results suggest that the tannins, which are found in many plants, are potentially very important biological antioxidants as they have quenching ability for peroxyl radicals about 15-30 times more than that of simple phenolics. Riedl and Hagerman (2001) determined the antioxidant activity of tannin-protein complexes, which are founded to act as scavengers and sinks for free radicals.

As an alternative antioxidant property, some phenolic compounds with dihydroxy groups can conjugate transition metals, preventing metal- induced free radical fonnation. Phenolic compounds with catecholate and gallate groups can inhibit metal-induced oxygen radical fonnation either by coordination with Fe²⁺ (or Cu²⁺) or enhancing the autoxidation of this ion (Jin and Russell, 2010). Phenolic compounds in the bark of Acacia mangium were extracted, and their antioxidant activities were investigated using l,l-diphenyl-2-picrylhydrazyl free radical-scavenging and ferric-reducing antioxidant power assays in the work of Liangliang et al. (2010). A significant linear relationship among antioxidant potency, antiradical activity, and the content of phenolic compounds of bark extracts was observed.

Generally, the action of polymer additives against a thermo-oxidative process is a main tool to preserve the desired polymer properties for a long period and at different conditions. A study on the efficiency of natural antioxidants, bio-based tannins, and other phenol byproducts, as stabilizers for polypropylene, is reported by Ambrogi et al. (2011). Their stabilizing activity was compared with that of a commercial phenolic antioxidant. The experimental results provided evidence for the effectiveness of natural stabilizers. Finally, increasing interest in the lowering or replacement of synthetic antioxidants has led to focus the research studies on natural antioxidants, especially on plant-origin materials.

CONCLUSIONS

Polyphenolic materials and specifically tannins, as this review focused, isolated or extracted from a broad variety of plant materials (from forestry or viticulture byproducts) are available in high quantities. They are historically used in the leather tanning and adhesive industries. Increasingly, CTs are polyphenolic oligomers based on a flavanyl repeat units with the hydroxylation pattern providing potent antioxidant activity. These properties, their availability, and the relative ease to chemical modification make tannins attractive for many projects and investigations such as polymer additives or modifiers. They could be modified by acetylation, hydrolysis, condensation, polymerization, etc. They may also be copolymerized with formaldehyde and aminoplast or phenolic resins to elaborate thermosetting binders for particle panels as well. They could also be formulated as adhesives by direct hydrolysis followed by polymerization. Several new emerging applications are in adhesive industries for partially replacing hazardous phenol by phenolic resins. On the other hand, the antioxidant properties of tannins are not a surprise. The antioxidant activity of polyphenols and other properties make these compounds a veiy interesting potential raw material for the development of green materials.

KEYWORDS

• natural polyphenols
• tannins
• chemistry of tannins
• tannin applications
• hydrolyzable tannins
• condensed tannins

REFERENCES

Andersen OM, Markham KR. 2006. Flavonoids: chemistry, biochemistry and applications.

Chaps 3 and 6. Boca Raton, London: Taylor and Francis.

Alan C, Indu В Jaganath, Michael N Clifford. 2006. Phenols, polyphenols and tannins: an overview. Chap. 1. In: Alan C, Clifford MN, Hiroshi A (Editors). Plant secondary metabolites: occurrence, structure and role in the human diet. Oxford, UK: Blackwell Publishing Ltd. Ambrogi V, Cerruti P, Carfagna C, Malinconico M, Marturano V, Perrotti M, Persico P. 2011. Natural antioxidants for polypropylene stabilization. Polymer Degradation and Stability. 96:2152-2158.

Amine M, Ahmed A, Antonio P, Fatima C, Bertrand C. 2010. Preparation and mechanical characterization of particle board made from maritime pine and glued with bio-adhesives based on cornstarch and tannins. Maderas Ciencia у Tecnologia. 12:189-197.

Amine M, Antonio P, Aluned A, Fatima C, Bertrand C. 2013. Polenta corn starch-mimosa tannin-based urea formaldehyde adhesives for interior grade particleboard. Journal of Materials and Environment Science. 4:496-501.

Antwi-Boasiako C, Animapauh SO. 2012. Effect of solvent type on tannin extractability from three Tetrapleura tetraptera (Schum. and Thonn.) taubert positions for wood composite adhesive formulation. Journal of Emerging Trends in Engineering and Applied Sciences. 3:517-525.

Antwi-Boasiako C, Animapauh SO. 2012. Tannin extraction from the barks of three tropical hardwoods for the production of adhesives. Journal of Applied Sciences Research. 8: 2959-2965.

Ascacio-Valdes JA, Buenrostro-Figueroa JJ, Carbo AA, Barragan AP, Herrera RR, Aguilar CN. 2011. Ellagitannins: biosynthesis, biodegradation and biological properties. Journal of Medicinal Plants Research. 5:4696-4703.

Aouf C, Nouailhas H, Fache M, Caillol S, Boutevin B, and Fulcrand H. 2013. Multifunctionalization of gallic acid, synthesis of a novel bio-based epoxy resin. European Polymers Journal. 49:1185-1195.

Barbosa Jr V, Elaine Cristina R, lice Aiko TR, Elisabete F. 2010. Biobased composites from tannin-phenolic polymers reinforced with coir fibers. Industrial Crops and Products. 32:305-312.

Basso MC, Xinjun L, Vanessa F, Antonio P, Samuele G, Alain C. 2011. Green formaldehyde- free foams for thermal insulation. Advanced Material Letters. 2:378-382.

Benyahya S, Aouf C, Caillol S, Boutevin B, Pascault JP, Fulcrand H. 2014. Functionalized green tea tannins as phenolic prepolymers for bio-based epoxy resins. Industrial Crops and Products 53:296-307.

Bisanda ETN, Ogola WO, Tesha JV. 2003. Characterisation of tannin resin blends for particle board applications. Cement and Concrete Composites 25:593-598.

Bossu CM, Ferreira EC, Chaves FS, Menezes EA, Nogueira ARA. 2006. Flow injection system for hydrolysable tannin determination. Microchemical Journal. 84:88-92.

Chuan Wei OO. 2008. Preparation and evaluation of mangrove tannins-based adsorbent for the removal of heavy metal ions from aqueous solution. Ph.D. Thesis, School of Chemical Sciences, Universiti Sains Malaysia, Penang, Malaysia.

Dixon RA, De-Yu X, Shashi BS. 2005. Proanthocyanidins-a final frontier in flavonoid research. New Phytologist. 165:9-28.

Elaine CR, Elisabete F. 2012. Tannin-phenolic resins: synthesis, characterization, and application as matrix in bio based composites reinforced with sisal fibers. Composites: Part

B. 43:2851-2860.

Electra P, Zoi N. 2011. D 3.3: resins that can be produced by the European bio industry. In: Non-food crops-to-industry schemes in EU27. WP1. Non-food crops, Grant agreement no. 227299, avalaible at: www.crops2industry.eu

Graciela P, Juanita F, Jaime B. 2003. Removal of metal ions by modified pinus radiata bark and tannins from water solutions. Water Research. 37:4974-4980.

Grigsby WJ, Bridson JH, Cole L, Jaime-Anne E. 2013. Esterification of condensed tannins and their impact on the properties of poly (lactic acid). Polymers. 5:344-360.

Grigsby WJ, Bridson JH, Cole L, Helena F. 2014. Evaluating modified tannin esters as functional additives in polypropylene and biodegradable aliphatic polyester. Macromolecular Materials and Engineering. 299:1251-1258.

Hagerman EA, Ken M R, Alexander Jones G, Kara NS, Nicole TR, Pual WH, Thomas R. 1998. High molecular weight plant polyphenolics (tannins) as biological antioxidant. Journal of Agricultural and Food Chemistry. 46:1887-1892.

Haslam E. 1988. Plant polyphenols (Syn. vegetable tannins) and chemical defence-а reappraisal. Journal of Chemical Ecology. 14:1789-1805.

Hergert HL. 1989. Condensed tannins in adhesives: introduction and historical perspective. Chap. 12 In: Hemingway RW, Conner AH, Branham SJ (Editors). Adhesives from renewable resources ACS symposium, Series 385. Washington, DC: American Chemical Society.

Hillis WE. 1979. Natural polyphenols (tannins) as a basis for adhesives. In: Proc of phenolic resins: chemistry and application. June 6-8. Weyerhaeuser Co., Tacoma, WA.

Horvath PJ 1981. The nutritional and ecological significance of acer-tannins and related polyphenols. M.Sc. Thesis, Cornell University, Ithaca, NY, USA.

Frederique B, Sandra TL, Antonio P, Paola N, Michel PC. 2012. Development of green adhesives for fiberboard manufacturing using tannins and lignin from pulp mill residues. Cellulose Chemistry and Technology. 46:449-455.

Frollini E, Oliveira FB, Ramires EC, Barbosa Jr V. 2008. Composites based on tannins: production, process and uses (Portuguese). Brazil Patent, BRPI0801091.

Frutos P, Hervas G, Giraldez FJ, Mantecon AR. 2004. Tannins and ruminant nutrition. Spanish Journal of Agricultural Research. 2:191-202.

Jaganathi IB, Alan C. 2010. Dietary flavonoids and phenolic compounds. Chap. 1 In: Fraga CG (Editor). Plant phenolics and human health: biochemistry, nutrition and pharmacology. John Wiley and Sons, Inc.

Jin D, Russell JM. 2010. Plant phenolics: extraction, analysis and their antioxidant and anticancer properties. Molecules. 15:7313-7352.

Jinjie G, Xinghai S, Meiqin C, Rui W, Min W. 2003. A novel biodegradable antimicrobial PU foam from wattle tannin. Journal of Applied Polymer Science. 90:2756-2763.

Karamali K, Teunis VR. 2011. Tannins: classification and definition. Natural Product Reports. 18:641-649.

Lan P, Francois G, Anttnio P, Zhou Ding G, Nicolas В. 2012. Wood adhesives from agricultural by-products: lignins and tannins for the elaboration of particle boards. Cellulose Chemistry and Technology. 46:457-462.

Laurent R, Chahinez A, Eric D, Helene F. 2013. Depolymerisation of condensed tannins in ethanol as a gateway to bio sourced phenolic synthons. Green Chemistry. 15:3268-3275.

Liangliang Z, Jiahong C, Yongmei W, Dongmei W, Man Xu. 2010. Phenolic extracts from acacia mangium bark and their antioxidant activities. Molecules. 15:3567-3577.

Li J, Li C, Wang W, Zhang W, Li J. 2016. Reactivity of larch and valonia tannins in synthesis of tannin-formaldehyde resins. Bioresources. 11:2256-2268.

Mahmut OZ, Cengiz S, Ayhan SI. 2006. Studies on synthesis, characterization, and metal adsorption of mimosa and valonia tannin resins. Journal of Applied Polymer Science. 102: 786-797.

Maestri DM, Nepote V, Lamarque AL, Zygadlo JA. 2006. Natural products as antioxidants. Chap. 5 In: Filippo I (Editor). Phytochemistry: advances in Research. Kerala, India: Research Signpost.

Mamta S, Jyoti S, RajeevN, Dharmendra S, AbhishekG. 2013. Phytochemistry of medicinal plants. Journal of Pharmacognosy and Phytochemistry 1:168-182.

Mark D. 2010. Tannin management in the vineyard. Fact Sheet, available at: mvw.gwrdc.corn.au

Mehmet EA, Siikru D. 2006. Removal of heavy metal ions using chemically modified adsorbents. Journal of International Environmental Application and Science. 1:27-40.

Michel CV, Roberto CC, Bruno C da Silva, Gisely de L Oliveira. 2011. Tannin extraction from the bark of Pirns oocarpa var. Oocarpa with sodium carbonate and sodium bisulfite. Floresta e Ambiente. 18:1-8.

Mohamed NB, Alessandro G. 2008. Monomers, polymers, and composites from renewable resources. Chap. 8, Oxford, UK: Elsevier.

Ndazi B, Tesha JV, Karlsson S, Bisanda ET. 2006. Production of rice husks composites with acacia mimosa tannin-based resin. Journal of Material Science. 41:6978-6983.

Nonhlanhla MR. 2011. Multidimensional fractionation of wood based tannins. Master Thesis, Department of Chemistry and Polymer Science, University of Stellenbosch, South Africa.

Onifade KR. 2001. Production of tannin from the bark of eucalyptus camadulensis. A.U. Journal of Technology (Assumption University of Thailand). 5:66-72.

Pizzi A. 2006. Recent developments in eco-efficient bio-based adhesives for wood bonding: opportunities and issues. Journal of Adhesion Science and Technology. 20:829-846.

Pizzi A, Scharfetter HO. 2003. The chemistry and development of tannin-based adhesives for exterior plywood. Journal of Applied Polymer Science. 22:1745-1761.

Pizzi A, Tekely P. 1995. Mechanism of polyphenolic tannin resin hardening by hexamethylenetetramine: CP-MAS ^BC-NMR. Journal of Applied Polymer Science. 56:1645-1650.

Pizzi A. 2003. Natural phenolic adhesives I: tannin. Chap. 27. In: Pizzi A, Mittal KL (Editors). Handbook of adhesive technology, 2nd ed. revised and expanded. NY: Marcel and Dekker.

Raquez JM, Deleglise M, Lacrampe MF, Krawczak P. 2010. Thermosetting (bio) materials derived from renewable resources: a critical review. Progress in Polymer Science. 35: 487-509.

Ramakrishnan K, Krishnan MRV. 1994. Tannin—classification, analysis and applications. Ancient Science of Life Journal. 13:232-238.

Riedl KM, Hagerman AN. 2001. Tannin-protein complexes as radical scavengers and radical sinks. Journal of Agricultural and Food Chemistry. 49:4917-4923.

Stephane Q, Ken SF. 1996. Ellagitannin chemistry. Chemistry Review. 96:475-503.

Sumin K, Hyun-Joong K. 2003. Curing behavior and viscoelastic properties of pine and wattle tannin-based adhesives studied by dynamic mechanical thermal analysis and FT-IR-ATR spectroscopy. Journal of Adhesion Science and Technology. 17:1369-1383.

Takuo O, Hideyuki I. 2011. Tannins of constant structure in medicinal and food plants- hydrolysable tannins and polyphenols related to tannins. Molecules. 16:2191-2217.

Terry Sellers Jr, George D Miller Jr. 2004. Laboratory manufacture of high moisture southern pine strand board bonded with three tannin adhesive types. Forest Products Journal. 54: 296-301.

Tondi G, Pizzi A, Olives R. 2008. Natural tannin-based rigid foams as insulation for doors and wall panels. Maderas Ciencia у Tecnologla. 10:219-227.

Yoshitake S, Kentaro S, Kazuyuki C. 2004. Adsorption characteristics of tannin for heavy metal ions. Prepared for presentation at AIChE 2003 annual meeting, November 7-12, 2004, Austin Convention Center, TX. Avalaible at: www.nt.ntnu.no/users/skoge/prost/.../ aiche-2004/pdffiles/.../265j.pdf.

Vazquez G, Lopez-Suevos F, Gonzalez-Alvarez J, Antorrena G. 2005. Curing process of phenol-urea-frmaldehyde-tannin (PUFT) adhesives: kinetic studies by DSC and DMA. Journal of Thermal Analysis and Calorimetry. 82:143-149.

Versari A, Du Toit W, Parpineloo GP. 2013. Oenological tannins. Australian Journal of Grape and Wine Research. 19:1-10.

Warren JG, James HB, Cole L, Jaime-Anne E. 2013. Esterification of condensed tannins and their impact on the properties of poly(lactic acid). Polymers. 5:344-360.