Extraction, identification and antioxidant activity of the phenolic secondary metabolites isolated from the leaves, stems and fruits of two shrubs of the Ericaceae family Oana-Crina Bujor To cite this version: Oana-Crina Bujor. Extraction, identification and antioxidant activity of the phenolic secondary metabolites isolated from the leaves, stems and fruits of two shrubs of the Ericaceae family. Other. Université d’Avignon, 2016. English. NNT : 2016AVIG0261. tel-01722698 HAL Id: tel-01722698 https://tel.archives-ouvertes.fr/tel-01722698 Submitted on 5 Mar 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. ―Gheorghe Asachi‖ Technical University of Iasi Faculty of Chemical Engineering and Environmental Protection, Romania University of Avignon – National Institute for Agricultural Research (INRA) UMR 408 Safety and Quality of Plant Products, Avignon, France Extraction, identification and antioxidant activity of the phenolic secondary metabolites isolated from the leaves, stems and fruits of two shrubs of the Ericaceae family - PhD THESIS - Chemist Oana-Crina Bujor Supervisors: Professor emeritus Valentin I. POPA Dr. Claire DUFOUR IASI, April 19th 2016 The composition of the thesis jury: President: Professor Nicolae Hurduc Faculty of Chemical Engineering and Environmental Protection ―Gheorghe Asachi‖ Technical University of Iasi, Romania Supervisors: Professor emeritus Valentin I. Popa Faculty of Chemical Engineering and Environmental Protection ―Gheorghe Asachi‖ Technical University of Iasi, Romania Dr. Claire Dufour UMR408 SQPOV ―Sécurité et Qualité des Produits d‘Origine Végétale‖ National Institute for Agricultural Research, Avignon, France Reviewers: Dr. Hélène Fulcrand UMR1083 ―Sciences Pour l‘Oenologie‖ National Institute for Agricultural Research, Montpellier, France Professor Florin Dan Irimie Faculty of Chemistry and Chemical Enginerring Babes-Bolyai University of Cluj-Napoca, Romania Professor Teodor Măluţan Faculty of Chemical Engineering and Environmental Protection ―Gheorghe Asachi‖ Technical University of Iasi, Romania To Rares, for his love and patience To my niece and my nephew, Alesia and Denis: the chemistry is all around us! ACKNOWLEDGEMENTS This PhD thesis was elaborated in the joint supervision between the ―Gheorghe Asachi‖ Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection (FCEEP), Romania and the University of Avignon and Vaucluse, France. The present work was carried out at the Department of Natural and Synthetic Polymers at the FCEEP, and in ―Chemistry of antioxidants‖ team of UMR 408 ―Safety and Quality of Plant Products (SQPOV)‖ at the National Institute for Agricultural Research (INRA) from Avignon. The travel costs to INRA-SQPOV Unit were financed by the Erasmus Program, which I gratefully acknowledge for the student mobility grants and particularly to Mrs. Liliana Lazăr and Mrs. Claudia Haasis for their support. I am also grateful to Dr. Catherine Renard, Head of the INRA-SQPOV Unit, for providing the facilities for my work in her unit. I am most grateful to my supervisors, Professor emeritus Valentin I. Popa and Dr. Claire Dufour, for their guidance throughout the thesis and for always had the door open for all questions and discussions concerning all aspects of the work … and not only. I am very grateful to Professor Valentin I. Popa for his encouragement to start this work and for all support, kindly guidance, advices, and insightful comments. I express my special thanks to Dr. Claire Dufour for introducing me to the world of antioxidant polyphenols and lipid oxidation and more important for knowledge on mass spectrometry. I appreciated their never failing support and suggestions, and the constructive advice and criticism without the scientific results of this work would not attain this high level. Her kindness and friendship were and are also very precious to me. ―Merci, Merci!‖. I would like to extend my gratitude to the members of my examination committee, Professor Nicolae Hurduc, Dr. Hélène Fulcrand, Professor Florin Dan Irimie and Professor Teodor Măluţan, for their time and interest in evaluating the scientific quality of this thesis. I wish to express my sincere acknowledgment to Professor Olivier Dangles, Head of Doctoral School 536 "Agricultural Sciences & Sciences" of University of Avignon, who promptly responded to my interest in collaboration with its university and give me the chance to do my research at the SQPOV Unit. I would like to thank him for his time, friendly attitude, advice and help in my grant and thesis applications. Two persons at the Faculty of Chemical Engineering and Environmental Protection of Iasi are specially acknowledged for their contributions to this study. I am grateful to Associate Professor Irina Volf for the opportunity to work at her laboratory and use the facilities available there for my researches and her advice and support during my thesis. I also thank Associate Professor Camelia Mihăilescu for her proficiency and guidance in experimental extraction analysis. Many sincere thanks go to the members of the ―Chemistry of antioxidants‖ team of INRA-SQPOV Unit for kindness and warm welcome and pleasant working atmosphere in the laboratory. Special thanks go to: Mrs. Marie- José Vallier for her sympathy and providing me guidance and help on my lab work whenever needed; Mrs. Michèle Loonis for her help and guidance in UPLC/MS analyses and especially for her gentleness and good ideas; Mr. Christian Ginies for helping me through the hard laboratory work in the digestion: «Je saisμ c‘est pour la recherche!»; Dr. Michel Carail for his advice on lab «trucs» and for trying to learn romanian. I would like to thank all the staff of INRA-SQPOV Unit for welcoming me as another member of their unit. Especially, I thanks to Dr. Carine Le Bourvellec for teaching me about the procyanidin analyses and their fruitful and pleasant contribution to this study. An extra thank is also addressed to the unit informaticians, Dominique Loonis and Eric Pietri, for helping me to solve the ―everyday‖ IT problems. I thank the Forestry Direction of Neamt for the access to Borca Mountains (Neamt, Romania) for collecting bilberry and lingonberry samples for my research. I also want to thank to Dr. Gina Tiron from National Meteorological Administration - Moldova Meteorological Center of Iasi, for providing the meteorological data. I am grateful to all my colleagues and friends at the Faculty of Chemical Engineering and Environmental Protection of Iasi and the INRA-SQPOV Unit of Avignon for making my work easier during these years: Andrei and Cornel are thanked for their ―useful advice‖ at the beginning of the thesis and helpfulness; Roxana is thanked for her all support and beautiful friendship; Adina for her collaboration for review, confident spirit and help while I was in France; Dan is thanked for his help with the lyophilisation of samples and friendship; my colleagues at the INRA-SQPOV Unit, Katérina, Anna-Lena, Rachel, Béa, Joseana, Dimitra, Albert, Romain, Sara, Julien, Aurélie, Djidji deserve great thanks for all their help, friendly welcome, kindness, lunches, coffee breaks and all the good moments that we have shared together during my work in Avignon. Finally, I am heartily thankful to my family, and especial to my sister for his encouragement and unconditional support. In particular, my dearest thanks are addressed to Rares for understanding me and my work, and for his love, tireless support and patience. Contents Contents INTRODUCTION...........................................................................................................7 LITERATURE REVIEW ........................................................................................................ 9 I. Phenolic compounds as secondary metabolites found in plants and foods .............. 11 I.1. Structure and classification ................................................................................ 12 I.1.1. Non-flavonoid polyphenols ............................................................................... 12 I.1.2. Flavonoids ........................................................................................................15 I.2. Methods for extraction and characterisation of phenolic compounds ............. 18 I.3. Applications of phenolic compounds in different biological systems ............... 20 I.3.1. Applications of phenolic compounds in the plants development ...................... 20 I.3.1.1. As plants growth bioregulators ................................................................ 20 I.3.1.2. As amendments in bioremediation .......................................................... 22 I.3.2. Applications of phenolic compounds in microorganisms development ............ 23 II. The antioxidant activity of phenolic compounds .......................................................... 25 II.1. The antioxidant action of phenolic compounds and their mechanisms ......... 25 II.1.1. Through reducing effects: H-atom and/or electron transfer ..........................