Development of methodology for identification the nature of the polyphenolic extracts by FTIR associated with multivariate analysis.

Tannins are polyphenolic compounds of complex structures formed by secondary metabolism in several plants. These polyphenolic compounds have different applications, such as drugs, anti-corrosion agents, flocculants, and tanning agents. This study analyses six different type of polyphenolic extracts by Fourier transform infrared spectroscopy (FTIR) combined with multivariate analysis. Through both principal component analysis (PCA) and hierarchical cluster analysis (HCA), we observed well-defined separation between condensed (quebracho and black wattle) and hydrolysable (valonea, chestnut, myrobalan, and tara) tannins. For hydrolysable tannins, it was also possible to observe the formation of two different subgroups between samples of chestnut and valonea and between samples of tara and myrobalan. Among all samples analysed, the chestnut and valonea showed the greatest similarity, indicating that these extracts contain equivalent chemical compositions and structure and, therefore, similar properties.

[1]  J. Bayona,et al.  Part-per-trillion determination of pharmaceuticals, pesticides, and related organic contaminants in river water by solid-phase extraction followed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry. , 2010, Analytical chemistry.

[2]  Céline Douat-Casassus,et al.  Plant Polyphenols: Chemical Properties, Biological Activities, and Synthesis , 2011 .

[3]  N. Brosse,et al.  Condensed tannins from grape pomace: Characterization by FTIR and MALDI TOF and production of environment friendly wood adhesive , 2012 .

[4]  Jose Gonzalez-Rodriguez,et al.  A specific case in the classification of woods by FTIR and chemometric: discrimination of Fagales from Malpighiales , 2014, Cellulose.

[5]  C. Pasquini.  Near Infrared Spectroscopy: fundamentals, practical aspects and analytical applications , 2003 .

[6]  M. Redington,et al.  Fourier transform infrared analyses of bog and modern oak wood (Quercus petraea) extractives , 2004, Wood Science and Technology.

[7]  A. Pizzi,et al.  Natural tannin–furanic thermosetting moulding plastics , 2013 .

[8]  T. Rababah,et al.  Total phenolics and antioxidant activities of fenugreek, green tea, black tea, grape seed, ginger, rosemary, gotu kola, and ginkgo extracts, vitamin E, and tert-butylhydroquinone. , 2004, Journal of agricultural and food chemistry.

[9]  J. Araña,et al.  Highly concentrated phenolic wastewater treatment by the photo-Fenton reaction, mechanism study by FTIR-ATR. , 2001, Chemosphere.

[10]  S. S. Costa,et al.  Flavonoides: Potenciais agentes Terapêuticos para o Processo Inflamatório , 2009 .

[11]  J. Beltrán-Heredia,et al.  Surface water and wastewater treatment using a new tannin-based coagulant. Pilot plant trials. , 2010, Journal of environmental management.

[12]  L. Pieters,et al.  Condensed vegetable tannins: Biodiversity in structure and biological activities , 1999 .

[13]  M. J. van der Merwe,et al.  Analysis of commercial proanthocyanidins. Part 1: the chemical composition of quebracho (Schinopsis lorentzii and Schinopsis balansae) heartwood extract. , 2012, Phytochemistry.

[14]  G. Vázquez,et al.  MALDI-TOF, HPLC-ESI-TOF and 13C-NMR characterization of chestnut (Castanea sativa) shell tannins for wood adhesives , 2012, Wood Science and Technology.

[15]  O. Unsalan,et al.  FT‐Raman and FT‐IR spectral and quantum chemical studies on some flavonoid derivatives: Baicalein and Naringenin , 2009 .

[16]  Andrea Versari,et al.  Fingerprint of enological tannins by multiple techniques approach , 2010 .

[17]  Céline Douat-Casassus,et al.  Plant polyphenols: chemical properties, biological activities, and synthesis. , 2011, Angewandte Chemie.

[18]  Sumin Kim,et al.  Curing behavior and viscoelastic properties of pine and wattle tannin-based adhesives studied by dynamic mechanical thermal analysis and FT-IR-ATR spectroscopy , 2003 .

[19]  Wen‐Jau Lee,et al.  Properties of resorcinol-tannin-formaldehyde copolymer resins prepared from the bark extracts of Taiwan acacia and China fir. , 2006, Bioresource technology.

[20]  A. Pizzi,et al.  MALDI‐TOF‐CID for the microstructure elucidation of polymeric hydrolysable tannins , 2013 .

[21]  Rafael S. Peres,et al.  Black Wattle Tannin As Steel Corrosion Inhibitor , 2012 .

[22]  P. Tahir,et al.  Characterization of Acacia mangium polyflavonoid tannins by MALDI-TOF mass spectrometry and CP-MAS 13C NMR , 2010 .

[23]  M. Rodehutscord,et al.  Effects of long-term supplementation of chestnut and valonea extracts on methane release, digestibility and nitrogen excretion in sheep. , 2014, Animal : an international journal of animal bioscience.

[24]  A. Meyer,et al.  Identification of spectral regions for the quantification of red wine tannins with fourier transform mid-infrared spectroscopy. , 2008, Journal of agricultural and food chemistry.

[25]  A. Pizzi,et al.  Phenolic resin wood panel adhesives based on chestnut (Castanea sativa) hydrolysable tannins , 2013 .

[26]  A. Afşar,et al.  An investigation about the effect of oxazolidine on modified valonia extract tanning , 2008 .

[27]  Giovanna Piantanida,et al.  Non-destructive spectroscopic investigation on historic Yemenite scriptorial fragments: evidence of different degradation and recipes for iron tannic inks , 2013, Analytical and Bioanalytical Chemistry.

[28]  P. Diouf,et al.  Antioxidant properties of wood extracts and colour stability of woods , 2006 .

[29]  Bruce Slutsky,et al.  Chemometrics: A Practical Guide By Kenneth R. Beebe, Randy J. Pell, and Mary Beth Seasholtz. Wiley-Interscience Series on Laboratory Automation. John Wiley & Sons: New York, 1998, xi + 348 pp, ISBN 0-471-12451-6 , 1998, Journal of chemical information and computer sciences.

[30]  Marco Flôres Ferrão,et al.  Direct determination of tannins in Acacia mearnsii bark using near-infrared spectroscopy , 2014 .

[31]  C. Benchaar,et al.  Assessment of the effect of condensed (acacia and quebracho) and hydrolysable (chestnut and valonea) tannins on rumen fermentation and methane production in vitro. , 2013, Journal of the science of food and agriculture.

[32]  L. Falcao,et al.  Tannins characterisation in new and historic vegetable tanned leathers fibres by spot tests , 2011 .

[33]  N. Graham,et al.  Characterisation and coagulation performance of a tannin-based cationic polymer: A preliminary assessment , 2008 .

[34]  M. Özacar,et al.  Equilibrium and kinetic data, and adsorption mechanism for adsorption of lead onto valonia tannin resin , 2008 .

[35]  D. E. Akin.  Forage Cell Wall Degradation and ρ‐Coumaric, Ferulic, and Sinapic Acids1 , 1982 .

[36]  M. Joslyn,et al.  ASTRINGENCY OF FRUITS AND FRUIT PRODUCTS IN RELATION TO PHENOLIC CONTENT. , 1964, Advances in food research.

[37]  A. Celzard,et al.  Tannin/furanic foams without blowing agents and formaldehyde , 2013 .

[38]  A. Aslan.  Improving the Dyeing Properties of Vegetable Tanned Leathers Using Chitosan Formate , 2013 .

[39]  G. A. Gasmelseed,et al.  Characterization of Lawsonia inermis (Henna) as Vegetable Tanning Material , 2012 .

[40]  M. Florescu,et al.  FTIR SPECTROSCOPY FOR THE ANALYSIS OF VEGETABLE TANNED ANCIENT LEATHER , 2006 .

[41]  Bernhard Lendl,et al.  Toward the optical tongue: flow-through sensing of tannin-protein interactions based on FTIR spectroscopy. , 2002, Journal of the American Chemical Society.

[42]  M. Breese,et al.  Fourier Transform Infrared characterization of Pai wood (Afzelia africana Smith) extractives , 1998, Holz als Roh- und Werkstoff.

[43]  R. Cates,et al.  TOWARD A GENERAL THEORY OF PLANT. ANTIHERBIVORE CHEMISTRY , 1976 .

[44]  Aurelia Meghea,et al.  Spectral Technics for Identifying Tanning Agents in the Heritage Leather Items , 2007 .

[45]  G. Downey,et al.  Mid-infrared spectroscopy coupled with chemometrics: a tool for the analysis of intact food systems and the exploration of their molecular structure-quality relationships - a review. , 2010, Chemical reviews.

[46]  A. Pizzi,et al.  Characterization and performance of Rhizophora apiculata mangrove polyflavonoid tannins in the adsorption of copper (II) and lead (II) , 2009 .

[47]  Age K. Smilde,et al.  Principal Component Analysis , 2003, Encyclopedia of Machine Learning.

[48]  C. Absalon,et al.  Global fractionation of oak heartwood extractable polymers (lignins, polysaccharides and ellagitannins) by selective precipitations , 2005 .

[49]  R. Peralta,et al.  Inhibition of salivary and pancreatic α-amylases by a pinhão coat (Araucaria angustifolia) extract rich in condensed tannin , 2014 .

[50]  D. Reid,et al.  Analysis of commercial proanthocyanidins. Part 4: solid state (13)C NMR as a tool for in situ analysis of proanthocyanidin tannins, in heartwood and bark of quebracho and acacia, and related species. , 2013, Phytochemistry.

[51]  J. Beltrán-Heredia,et al.  Multiparameter Quantitative Optimization in the Synthesis of a Novel Coagulant Derived from Tannin Extracts for Water Treatment , 2012, Water, Air, & Soil Pollution.

[52]  M. Ferrão,et al.  Methods of multivariate analysis of NIR reflectance spectra for classification of yerba mate , 2014 .

[53]  A. Pizzi,et al.  Considerations on the macromolecular structure of chestnut ellagitannins by matrix‐assisted laser desorption/ionization‐time‐of‐flight mass spectrometry , 2002 .

[54]  R. J. Green,et al.  Interactions of tea tannins and condensed tannins with proteins. , 2010, Journal of pharmaceutical and biomedical analysis.

[55]  A. Pizzi,et al.  Structure and oligomers distribution of commercial Tara (Caesalpina spinosa) hydrolysable tannin. , 2013 .

[56]  L. Falcao,et al.  Tannins characterization in historic leathers by complementary analytical techniques ATR-FTIR, UV-Vis and chemical tests , 2013 .

[57]  M. L. Gimenes,et al.  Photodegradation of petrol station wastewater after coagulation/flocculation with tannin-based coagulant , 2013 .

[58]  Isao Kouno,et al.  α-Amylase and lipase inhibitory activity and structural characterization of acacia bark proanthocyanidins. , 2011, Journal of natural products.

[59]  Elba Lúcia Cavalcanti de Amorim,et al.  Taninos: uma abordagem da química à ecologia , 2005 .

[60]  Eduardo Agosin,et al.  Quantitative analysis of red wine tannins using Fourier-transform mid-infrared spectrometry. , 2007, Journal of agricultural and food chemistry.

[61]  M. Rodehutscord,et al.  Effects of different tannin-rich extracts and rapeseed tannin monomers on methane formation and microbial protein synthesis in vitro. , 2013, Animal : an international journal of animal bioscience.

[62]  A. Pizzi,et al.  MALDI-TOF mass spectrometry of polyflavonoid tannins , 2001 .

[63]  C. Birkinshaw,et al.  The effects of acetylation on the extractives of Sitka Spruce (Picea sitchensis) and Larch (Larix leptoleptis) wood , 2004, Holz als Roh- und Werkstoff.