[en] Colloidal bismuth therapeutics have been used for hundreds of years, yet remain mysterious. Here we report an X-ray pair distribution function (PDF) study of the solvolysis of bismuth disalicylate, a model for the metallodrug bismuth subsalicylate (Pepto-Bismol). This reveals catalysis by traces of water, followed by multistep cluster growth. The ratio of the two major species, {Bi9O7} and {Bi38O44}, depends on exposure to air, time, and the solvent. The solution-phase cluster structures are of significantly higher symmetry in comparison to solid-state analogues, with reduced off-center Bi3+ displacements. This explains why such "magic-size" clusters can be both stable enough to crystallize and sufficiently labile for further growth.
Disciplines :
Chemistry
Author, co-author :
Szczerba, Daniel; Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université Bourgogne Franche-Comté, 9 avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France
Tan, Davin; Department of Chemistry, McGill University, Montréal, Québec H3A 0B8, Canada
Do, Jean-Louis; Department of Chemistry, McGill University, Montréal, Québec H3A 0B8, Canada
Titi, Hatem M ; Department of Chemistry, McGill University, Montréal, Québec H3A 0B8, Canada
Mouhtadi, Siham; Université Franche-Comté, Insitut UTINAM-Équipe MSF, and Université Bourgogne Franche-Comté, 25030 Besançon, France
Chaumont, Denis; Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université Bourgogne Franche-Comté, 9 avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France
Del Carmen Marco de Lucas, María; Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université Bourgogne Franche-Comté, 9 avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France
Geoffroy, Nicolas; Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université Bourgogne Franche-Comté, 9 avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France
Meyer, Michel ; Insitut de Chimie Moléculaire de l'Université de Bourgogne, UMR 6302, CNRS, Université Bourgogne Franche Comté, 9 Avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France
Rousselin, Yoann; Insitut de Chimie Moléculaire de l'Université de Bourgogne, UMR 6302, CNRS, Université Bourgogne Franche Comté, 9 Avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France
Hudspeth, Jessica M; European Synchrotron Radiation Facility, BP 156, 38042 Grenoble, France
Bazhenov, Vasilii; European XFEL GmbH, Holzkoppel 4, 22869 Schenefeld, Germany
Arhangelskis, Mihails; Faculty of Chemistry, University of Warsaw, 1 Pasteura Street, 02-093 Warsaw, Poland
Halasz, Ivan ; Ruđer Bošković Institute, Bijenička cesta 54, 10000 Zagreb, Croatia
Friščić, Tomislav ; Department of Chemistry, McGill University, Montréal, Québec H3A 0B8, Canada
Kimber, Simon A J ; Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université Bourgogne Franche-Comté, 9 avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France
ANR - Agence Nationale de la Recherche ESRF - European Synchrotron Radiation Facility
Funding text :
We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron beam time on ID15B. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at P21.1. We thank Sakura Pascarelli for her kind help in Hamburg and the staff of ID15 at the ESRF for assistance with consumables. Agnieszka Poulain is acknowledged for support on the beamline. V.S. and P.S.-E. were funded by the ESRF-ILL International Summer Student Program. This work was supported by the EIPHI Graduate School (contract ANR-17-EURE-0002). Ce travail a été soutenu par le programme ”Investissements d’Avenir”, ISITE-BFC project (contract ANR- 15-IDEX-0003). We thank Agnès Birot for administrative support.
Mjos, K. D.; Orvig, C. Metallodrugs in medicinal inorganic chemistry. Chem. Rev. 2014, 114, 4540-4563, 10.1021/cr400460s
Anthony, E. J. et al. Metallodrugs are unique: opportunities and challenges of discovery and development. Chemical Science 2020, 11, 12888-12917, 10.1039/D0SC04082G
Sun, H.; Li, H.; Sadler, P. J. The biological and medicinal chemistry of bismuth. Chem. Ber. 1997, 130, 669-681, 10.1002/cber.19971300602
Lambert, J.; Midolo, P. The actions of bismuth in the treatment of Helicobacter pylori infection. Aliment. Pharmacol. Ther. 1997, 11, 27-33, 10.1046/j.1365-2036.11.s1.13.x
Yuan, S. et al. Metallodrug ranitidine bismuth citrate suppresses SARS-CoV-2 replication and relieves virus-associated pneumonia in Syrian hamsters. Nature microbiology 2020, 5, 1439-1448, 10.1038/s41564-020-00802-x
Mehring, M.; Mansfeld, D.; Paalasmaa, S.; Schürmann, M. Polynuclear Bismuth-Oxo Clusters: Insight into the Formation Process of a Metal Oxide. Chem.-Eur. J. 2006, 12, 1767-1781, 10.1002/chem.200500857
Mansfeld, D. et al. From {Bi22O26} to Chiral Ligand-Protected {Bi38O45}-Based Bismuth Oxido Clusters. Chem.-Eur. J. 2011, 17, 14805, 10.1002/chem.201102437
Miersch, L. et al. Hydrolysis of a Basic Bismuth Nitrate-Formation and Stability of Novel Bismuth Oxido Clusters. Chem.-Eur. J. 2011, 17, 6985-6990, 10.1002/chem.201100673
Schlesinger, M.; Miersch, L.; Rüffer, T.; Lang, H.; Mehring, M. Two Novel Nanoscaled Bismuth Oxido Clusters, [Bi38O45(OMc)22(C8H7-SO3)2(DMSO)6(H2O)1.5] · 2.5 H2O and [Bi38O45(HSal)22(OMc)2-(DMSO)15(H2O)] · DMSO · 2 H2O. Main Group Met. Chem. 2013, 36, 11-19, 10.1515/mgmc-2012-0073
Andrews, P. C. et al. Towards a structural understanding of the anti-ulcer and anti-gastritis drug bismuth subsalicylate. Angew. Chem. 2006, 118, 5766-5770, 10.1002/ange.200600469
André, V. et al. Mechanosynthesis of the metallodrug bismuth subsalicylate from Bi2O3 and structure of bismuth salicylate without auxiliary organic ligands. Angew. Chem. 2011, 123, 8004-8007, 10.1002/ange.201103171
Anker, A. S. et al. Structural Changes during the Growth of Atomically Precise Metal Oxido Nanoclusters from Combined Pair Distribution Function and Small-Angle X-ray Scattering Analysis. Angew. Chem. 2021, 133, 20570-20579, 10.1002/ange.202103641
Gebauer, D.; Kellermeier, M.; Gale, J. D.; Bergström, L.; Cölfen, H. Pre-nucleation clusters as solute precursors in crystallisation. Chem. Soc. Rev. 2014, 43, 2348-2371, 10.1039/C3CS60451A
Lee, J.; Yang, J.; Kwon, S. G.; Hyeon, T. Nonclassical nucleation and growth of inorganic nanoparticles. Nature Reviews Materials 2016, 1, 1-16, 10.1038/natrevmats.2016.34
Gary, D. C.; Terban, M. W.; Billinge, S. J.; Cossairt, B. M. Two-step nucleation and growth of InP quantum dots via magic-sized cluster intermediates. Chem. Mater. 2015, 27, 1432-1441, 10.1021/acs.chemmater.5b00286
Luan, C. et al. Four Types of CdTe Magic-Size Clusters from One Prenucleation Stage Sample at Room Temperature. J. Phys. Chem. Lett. 2019, 10, 4345-4353, 10.1021/acs.jpclett.9b01601
Jensen, K. M. et al. Polymorphism in magic-sized Au 144 (SR) 60 clusters. Nat. Commun. 2016, 7, 1-8, 10.1038/ncomms11859
Williamson, C. B. et al. Chemically reversible isomerization of inorganic clusters. Science 2019, 363, 731-735, 10.1126/science.aau9464
Furrer, G.; Phillips, B. L.; Ulrich, K.-U.; Pöthig, R.; Casey, W. H. The origin of aluminum flocs in polluted streams. Science 2002, 297, 2245-2247, 10.1126/science.1076505
Soderholm, L.; Almond, P. M.; Skanthakumar, S.; Wilson, R. E.; Burns, P. C. The structure of the plutonium oxide nanocluster [Pu38O56Cl54 (H2O) 8] 14-. Angew. Chem., Int. Ed. 2008, 47, 298-302, 10.1002/anie.200704420
Beecher, A. N. et al. Atomic structures and gram scale synthesis of three tetrahedral quantum dots. J. Am. Chem. Soc. 2014, 136, 10645-10653, 10.1021/ja503590h
Chandrasekhar, V.; Metre, R. K.; Sahoo, D. Bi38 Oxocarboxylate Cages are Keplerates-Synthesis and Structural Characterization of Two Bi38 Oxocarboxylate Cages. Eur. J. Inorg. Chem. 2014, 2014, 164-171, 10.1002/ejic.201301021
Perversi, G. et al. Co-emergence of magnetic order and structural fluctuations in magnetite. Nat. Commun. 2019, 10, 1-6, 10.1038/s41467-019-10949-9
Steed, J. W. Should solid-state molecular packing have to obey the rules of crystallographic symmetry?. CrystEngComm 2003, 5, 169-179, 10.1039/B304631A
Öpik, U.; Pryce, M. H. L. Studies of the Jahn-Teller effect. I. A survey of the static problem. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences 1957, 238, 425-447, 10.1098/rspa.1957.0010
Maroni, V. A.; Spiro, T. G. The Vibrational Spectrum of the Hydrolytic Hexamer of Bismuth (III) 1a. J. Am. Chem. Soc. 1966, 88, 1410-1412, 10.1021/ja00959a015
Voznyy, O.; Mokkath, J. H.; Jain, A.; Sargent, E. H.; Schwingenschlögl, U. Computational study of magic-size CdSe clusters with complementary passivation by carboxylic and amine ligands. J. Phys. Chem. C 2016, 120, 10015-10019, 10.1021/acs.jpcc.5b10908
