Exploration of astatine chemistry in solution : focus on the Pourbaix diagram in noncomplexing medium and characterization of astatine-mediated halogen bonds Lu Liu To cite this version: Lu Liu. Exploration of astatine chemistry in solution : focus on the Pourbaix diagram in noncom- plexing medium and characterization of astatine-mediated halogen bonds. Radiochemistry. Ecole na- tionale supérieure Mines-Télécom Atlantique, 2020. English. NNT : 2020IMTA0205. tel-03123005 HAL Id: tel-03123005 https://tel.archives-ouvertes.fr/tel-03123005 Submitted on 27 Jan 2021 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. 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THESE DE DOCTORAT DE L’ÉCOLE NATIONALE SUPERIEURE MINES-TELECOM ATLANTIQUE BRETAGNE PAYS DE LA LOIRE - IMT ATLANTIQUE ECOLE DOCTORALE N° 596 Matière, Molécules, Matériaux Spécialité : Chimie Analytique et Radiochimie Par Lu LIU Exploration de la chimie de l'astate en solution : Focalisation sur le diagramme de Pourbaix en milieu non complexant et caractérisation de liaisons halogènes induites par l'astate Thèse présentée et soutenue à Nantes, le 28 octobre 2020 Unité de recherche : SUBATECH, UMR 6457 Thèse N° : 2020IMTA0205 Rapporteurs avant soutenance : Claire LE NAOUR Chargée de recherche, HDR, CNRS, IJCLab Jean AUPIAIS Directeur de recherche, CEA, DAM Composition du Jury : Président : Christophe DEN AUWER Professeur, Université de Nice, ICN Rapporteurs : Claire LE NAOUR Chargée de recherche, HDR, CNRS, IJCLab Jean AUPIAIS Directeur de recherche, CEA, DAM Examinateurs : Philippe MOISY Directeur de Recherche, CEA, Marcoule Bernd GRAMBOW Professeur, IMT Atlantique, SUBATECH Dir. de thèse : Gilles MONTAVON Directeur de recherche, CNRS, SUBATECH Encadrants : Julie CHAMPION Maître de conférences, IMT Atlantique, SUBATECH Rémi MAURICE Chargé de recherche, CNRS, SUBATECH Acknowledgements Acknowledgements My Ph.D. project was realized in the radiochemistry group at SUBATECH under the direction of Dr. Gilles Montavon, Dr. Julie Champion and Dr. Re mi Maurice. As arriving at the end of this Ph.D. project, I would like to express my gratitude to all those people who made this work possible and an unforgettable experience for me. I owe my deepest gratitude to my supervisors, Gilles, Julie and Re mi. During this three- year period of my doctoral stage, they have all been very enthusiastic, reactive and complementary to each other concerning my research activities. I would like to thank them for the very nice and close daily guidance for designing, executing, analyzing and enhancing the research works. Their help delivered me a strong scientific background and prepared me for the forthcoming scientific journey. My special words of thanks should also go to my colleagues in SUBATEH, especially to Sylvain Pardoue, Ve ronique Baty, Ce line Bailly, Guillaume Blain, Nicolas Bessaguet, Katy Perrigaud, Anne Piscitelli, Karine David and Vale rie Bosse , for their help on the use of experimental equipment and devices such as the HPLC, COT meter, glove boxes, etc. I also would like to thank Romain Berny, Ronald Jahke , Maxime Birot, for the radioprotection service. I would like to acknowledge my coauthors of articles, Ning Guo, Cecilia Gomez Pech, Nicolas Galland, Seyfeddine Rahali, Je ro me Graton and Jean-Yves Le Questel, for their efforts and expertise on astatine, halogen bonds and quantum mechanical calculations, which lead to the publication of ours articles. I wish to express my sincere gratitude to all the jury members of my defense, Dr. Claire Le Naour, Prof. Christophe Den Auwer, Prof. Philippe Moisy, Dr. Jean Aupiais and Prof. Bernd Grambow. I am very grateful that they took much time to review my thesis very carefully I Acknowledgements and gave me many suggestions to improve my dissertation. I would like to deliver my special thanks to my schoolmates in Subatech, Haohan, Fengqi, Yifeng, Yajing, Yuwei, Anne-Laure, Yahaya, Emeline, and my friends Ziling, Kan, Zijun, Zijie, Yajun. They helped me a lot to integrate into life in France and they make my life in this country more colorful. Last but not least, I would like to thank my whole family, who have supported me in carrying a Ph.D. study abroad. And special thanks to my boyfriend, Liangzhao, who has always accompanied me, encouraged me and supported me during my Ph.D. studentship. II Contents Contents Acknowledgements ........................................................................................................................... I List of abbreviations and symbols ........................................................................................... VII List of figures .................................................................................................................................... XI List of tables................................................................................................................................... XIX Introduction ....................................................................................................................................... 1 Chapter 1. Literature survey ....................................................................................................... 5 1.1 Generality of astatine ............................................................................................................ 5 1.1.1 Discovery of astatine ............................................................................................................. 5 1.1.2 General properties of the astatine atom ........................................................................ 6 1.1.3 Two representative isotopes: 210At and 211At .............................................................. 7 1.2 Medicinal perspective for 211At ......................................................................................... 8 1.2.1 Nuclear medicine.................................................................................................................... 9 1.2.1.1 Nuclear medical imaging ................................................................................. 10 1.2.1.2 Targeted radiation therapy.............................................................................. 11 1.2.2 Radiolabeling ........................................................................................................................ 12 1.2.3 Application of 211At in targeted alpha-particle therapy ....................................... 14 1.2.3.1 Characteristics of the 211At radionuclide .................................................. 14 1.2.3.2 Radiolabeling with 211At .................................................................................. 14 1.2.3.3 In vivo stability of 211At-labeled complexes ............................................. 17 1.3 The chemistry of astatine in solution .......................................................................... 17 1.3.1 Production of 211At .............................................................................................................. 18 1.3.2 Speciation studies ............................................................................................................... 20 1.3.2.1 Experimental methods .................................................................................... 20 III Contents 1.3.2.2 Quantum chemistry methods ........................................................................ 22 1.3.3 Speciation of astatine in aqueous solutions in the absence of a complexing agent...................................................................................................................................... 23 1.3.5 Complexation between astatine cations and inorganic ligands ........................ 34 1.3.6 Complexation between astatine cations and organic ligands ............................ 38 1.3.7 Halogen bonding with Lewis bases .............................................................................. 40 1.4 Scientific motivations ......................................................................................................... 41 Chapter 2. Methodologies and materials ............................................................................. 43 2.1 Experimental methodologies .......................................................................................... 44 2.1.1 Electromobility ..................................................................................................................... 44 2.1.2 HPIEC ....................................................................................................................................... 48 2.1.3 Liquid/liquid competition ............................................................................................... 50 2.2 Analytical tools ..................................................................................................................... 52 2.2.1 Liquid scintillation counter ............................................................................................. 52 2.2.2 COT measurements ...........................................................................................................