Anthocyanin degradation of Hibiscus sabdariffa extracts during storage monitored by MCR-ALS on UV-VIS spectra

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(1)The Food Factor I Barcelona Conference Barcelona (Spain), 2-4 November 2016. Algerian food composition table D.E Mekhancha, Ly. Yagoubi-Benatallah, C.C. Dahel-Mekhancha, R. Karoune , I. Bouldjadj, H. Kadi, A. Benini, I. Mekaoussi, F. Mansour, L. Bechiri, M.T. Hamoud, H. Boucherba, M. Bencharif, I. Sersar, O. Allam and L. Nezzal Laboratoire Alimentation, Nutrition et Santé/Université de Constantine, Route de Aïn El Bey, 25000 Constantine, Algérie. The Food Factor I Barcelona Conference Barcelona (Spain), 2-4 November 2016. Anthocyanin degradation of Hibiscus sabdariffa extracts during storage monitored by MCR-ALS on UV-VIS spectra N. Achir1, C. Mertz2, A. Sinela3, K. Vidot2, H. Fulcrand4, M. Dornier1 1. Montpellier SupAgro, UMR95 QualiSud, 1101 av. Agropolis, B.P. 5098, F-34093 Montpellier cedex 5, France CIRAD, UMR95 QualiSud, 73 av. J.F Breton, TA B-95/16, F-34398 Montpellier cedex 5, France Instituto Superior de Tecnologia Agro-alimentar de Malanje (ISTAM), EN 230 km 2, Malanje, Angola 4 INRA-IPV, Unité de Recherche des Polymères et des Techniques Physicochimiques, 2 place Viala, 34060 Montpellier, France 2 3. Introduction Food composition tables are essential tools for assessing nutritional quality of diet. Many countries and organizations develop these tables on a national or regional level to standardize the nutritional quality analysis food tools and to carry out useful and relevant comparisons [1], [2], [3], [4]. Objective To develop an Algerian food composition table, standardized tool essential to the diet nutritional analysis. Methods All food marketed and consumed in Algeria (produced locally or imported) is considered as Algerian food. The data are essentially compiled according to procedures recommended by the INFOODS (FAO/UNU) [5] including identification of food, choice of tagnames and Langual descriptors [6]. Foods are classified according to their dominant nutritional potential. Results Algerian food composition table currently includes more than 300 foods divided into 5 groups (starch products, vegetables and fruits, animal’s products protidic, high energy density products and low nutrient densities and various products cannot be classified in the four first groups). Each food is presented by a card where appear : Energy (kJ/100g; kcal/100g), Water (g/100g), Protein (g/100g), Carbohydrate (g/100g), Fat (g/100g), fibres (g/100g), Calcium (mg/100g), Phosphorus (mg/100g), Iron (mg/100g), Retinol (μg/100g) and Retinol equivalent (ER/100g), Thiamin (mg/100g), Riboflavin (mg/100g), Niacin (mg/100g), and Niacin equivalent (EN/100g), vitamin C (mg/100g), and 4 main essential (mg/100g) amino acids (lysine, sulfur amino acids, threonin, tryptophan). These data are supplemented by 19 nutritional densities, edible part for 100g as purchased, 10 Langual descriptors, and a diagram illustrating the share of major nutrients in the energy density. Conclusion Algerian food composition table is an indispensable tool for nutritional assessment in Algerian diet. It can be adopted by users to translate amounts of food consumed nutrients. Keywords: Food Composition Table ; Nutriments ; Energy density ; Food ; Algeria. References: [1] http://www.eurofir.net/eurofir_knowledge/european_databases [2] https://pro.anses.fr/tableciqual/ [3] http://www.nubel.com/fra/banque_de_données_noms_de_marques.asp [4] http://www.sge-ssn.ch/fr/info-alimentaires/ouvrages-de-reference/ [5] http://www.fao.org/infoods/software_fr.stm [6] http://www.langual.org/. Calyces of Hibiscus sabdariffa are traditionally used to prepare a red beverage rich in anthocyanins (delphinidinand cyanidin-3-O-sambubioside) by decoction in water. These molecules are subjected to degradation during storage leading to a undesirable color intensity decay and change from red to brown in few months. The chemical origins of this quality loss have been already identified as scission and mainly condensation reactions leading to uncolored or brown polymers of anthocyanins (Sinela et al., 2016). Scission and condensed products are known to be instable and/or of various molecular weight. Their concentration is therefore very difficult to get unless numerous time- and money-consuming analysis. An alternative of getting mecanistic and kinetic insigth into anthocyanin degradation during processing or storage is the UV-VIS spectra analysis with chemometric tools. Indeed, UV-VIS spectra are easy to get, but may be complex to interpret as they result from the contribution of all molecules that absorb in this spectral region, which is the case of most of the polyphenols. The objective of this study is to use spectral deconvolution by mean of Multivariate Curve ResolutionAlternating Least Squares (MCR-ALS) on spectral evolution of Hibiscus sabdariffa extract obtained by soaking calyx powder in water at a ratio 1/9 (g/g) during one month of storage at 37°C. In this work, we propose a twosteps approach: a first deconvolution on two fractions of the extract, low molecular and high molecular weigth fractions obtained by size-exclusion chromatography and a MCR done on the spectrum of the whole extract. Absorbance from 250 to 700 nm (each 0.5 nm) was recorded on 10 samples at different storage times. MCRALS was carried out on the 10 spectra using a toolbox developped by Jaumot et al. (2005) on Matlab (The MathWorks, Inc., Natick, MA, USA) with a non negativity constraint algorithm. To improve the mathematical resolution and the chemical validity, the data set was augmented with pure spectra obtained with standards in solution. The results showed that the deconvolution made on the fractions obtained with size-exclusion chromatography was useful to extract qualitative information in the form of spectra of the low and high molecular weigth compounds. Three spectra were clearly identified as anthocyanin (with a spectral contribution equivalent to their relative concentration), chlorogenic acid, scission products (gallic and protocatechuic acids) and two spectra were attributed to condensed molecules (because of their absorbance in the brown region) and other colorless anthocyanin forms in equilibium (because of their peak in the UV region). The five spectra were used to improve the MCR-ALS applied to the whole extract. For this second step, the relative concentration of each specy was obtained. The anthocyanin evolution could be modeled by a first-order kinetic with a rate value consistent with litterature. Chlorogenic, gallic and protocatechiuc acids were found stable as expected. A significant evolution was evidenced for condensed molecules whose relative concentration increased by a 1.6-fold. To conclude, MCR results on Hibiscus sabdariffa extracts, fractionnated and not, were interesting since they could successfully represent the evolution trend of the different species in solution during storage: the anthocyanin but also their degradation products. Keywords: delphinidin; cyanidin; phenolics; MCR-ALS; UV-VIS spectra References A. Sinela, N. Rawat, C. Mertz, N. Achir, H. Fulcrand, M. Dornier, Anthocyanins degradation during storage of Hibiscus sabdariffa extract and evolution of its degradation products, Food Chemistry, In press. J. Jaumot, R. Gargallo, A. de Juan, R. Tauler, A graphical user-friendly interface for MCR-ALS: a new tool for multivariate curve resolution in MATLAB. Chemom. Intell. Lab. Syst. 2005, 76 (1), 101–110.. 173. 174.

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