[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.
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