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16,992 results on '"[CHIM.ORGA]Chemical Sciences/Organic chemistry"'

1. Self-Sensitized Photooxidation of Naphthols to Naphthoquinones and the Use of Naphthoquinones as Visible Light Photocatalysts in Batch and Continuous Flow Reactors

Author

Maxime Lancel, Pierre Zimberlin, Catherine Gomez, Marc Port, Lhoussain Khrouz, Cyrille Monnereau, Zacharias Amara, Laboratoire Génomique, bioinformatique et chimie moléculaire (GBCM), Conservatoire National des Arts et Métiers [CNAM] (CNAM), HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, [CHIM]Chemical Sciences
Abstract

Visible light photooxidation of naphthols to produce naphthoquinones, such as the natural product juglone, has been known for decades and has been widely utilized to benchmark the performances of a variety of photocatalytic systems. We discovered that these transformations can occur without the help of a photocatalyst and, even more intriguingly, that the photocatatyst-free process provides higher yields compared to control experiments utilizing state-of-the-art photocatalysts. In addition, we demonstrate that naphthoquinones and their corresponding naphthol precursors can act as alternatives to commonly used organic and organometallic photocatalysts with applications to challenging targets, such as the antimalarial drug artemisinin. This approach was finally transposed in continuous flow reactors where high photocatalyst stability and process efficiency are demonstrated with a 23× improvement in the space-time yield.

Published
2023

2. Conservation of natural dyes in Tay Nghe An Biosphere Reserve, Vietnam

Author

Lưu-Đàm, N.A., Cardon, Dominique, Vietnam Academy of Science and Technology (VAST), Histoire, Archéologie et Littératures des mondes chrétiens et musulmans médiévaux (CIHAM), École normale supérieure de Lyon (ENS de Lyon)-Université Lumière - Lyon 2 (UL2)-École des hautes études en sciences sociales (EHESS)-Université Jean Moulin - Lyon 3 (UJML), Université de Lyon-Université de Lyon-Avignon Université (AU)-Centre National de la Recherche Scientifique (CNRS), International Society for Horticultural Science, R. Räisänen, A. de la Sayette, and D. Cardon

Subjects
Thai people, Vietnam, [CHIM.ORGA]Chemical Sciences/Organic chemistry, conservation, Horticulture, [SHS.HIST]Humanities and Social Sciences/History, natural dyes
Abstract

International audience; Dye plants are present in the everyday life of many ethnic minority groups in Vietnam, ranging from meals, costumes to festivals. The study focuses on those within the Tay Nghe An Biosphere Reserve. This Biosphere Reserve covers an area of 1,303,285 ha of tropical rainforest, one of the 12 main types of ecosystem identified by UNESCO-MAB, in nine mountainous districts. Through our investigation, the use of 40 species of dye plants was recorded. They are mainly employed for dyeing food, textiles, and tools. Additional data about usage were also provided. In particular, one species (Dye Yam – Dioscorea cirrhosa) was recorded for the first time as a source of brown colorant for food. © 2023 International Society for Horticultural Science. All rights reserved.

Published
2023

3. Alkylation of N,N-Dibenzylaminoacetonitrile: From Five- to Seven-Membered Nitrogen-Containing Heterocyclic Systems

Author

Jacques Renault, Christelle Bouvry, Jean-François Cupif, Jean-Pierre Hurvois, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CRLCC Eugène Marquis (CRLCC), and C.B. thanks the Comprehensive Cancer Center Eugène Marquis for financial support.

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry
Abstract

International audience; The syntheses of several alkaloids and nitrogen-containing compounds including N-Boc-coniine (14b), pyrrolizidine (1), δ-coniceine (2), and pyrrolo[1,2a]azepine (3) are described. New C-C bonds in the α position relative to the nitrogen atom were formed by the alkylation of metalated α-aminonitriles 4 and 6a-c with alkyl iodides possessing the requisite size and functionality. In all of the reported cases, the pyrrolidine ring was formed in the aqueous medium through a favorable 5-exo-tet process involving a primary or a secondary amino group and a terminal δ-leaving group. Conversely, the azepane ring was efficiently formed in N,N-dimethylformamide (DMF), as the preferred aprotic solvent, through an unreported 7-exo-tet cyclization process involving a more nucleophilic sodium amide and a terminal mesylate borne by a saturated six carbon chain unit. In this way, we successfully synthesized pyrrolo[1,2a]azepane 3 and 2-propyl-azepane 14c in good yields from inexpensive and readily available materials without tedious separation methods.

Published
2023

4. Bismuth Nanoparticles Supported on Biobased Chitosan as Sustainable Catalysts for the Selective Hydrogenation of Nitroarenes

Author

Mustapha El kadiri, Taha El Assimi, Pascal Thébault, Abdellatif El Meziane, Sébastien Royer, Abdelkrim El Kadib, Géraldine Gouhier, Mohammed Lahcini, Université Cadi Ayyad [Marrakech] (UCA), Polymères Biopolymères Surfaces (PBS), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université Euro Méditerranéenne de Fès (UEMF), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M)

Subjects
heterogeneous catalysis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, bismuth, nanocomposites, General Materials Science, [CHIM.CATA]Chemical Sciences/Catalysis, chitosan, hydrogenation
Abstract

International audience; The use of chitosan as a support in the field of catalysis has gained tremendous interest because of its abundance and sustainability. We herein disclose a straightforward strategy to trap and stabilize bismuth nanoparticles (BiNPs) on chitosan biopolymer Bi@CS and their use for catalytic applications. Bi@CS was configured as micrometer-thick films, porous beads, and native powders analyzed and next used for the controlled and selective reduction of nitroaromatic compounds to their corresponding anilines and azoarenes, respectively, by varying the concentration medium in reducing NaBH 4. A regioselective mechanism has been suggested. Powder nanocomposites CSp-BiNPs exhibited high catalytic capacity, and 10 corresponding anilines and 15 azoarenes were obtained with very high yields. The reductions were achieved under mild and sustainable reaction conditions (water solvent and room temperature) with easy processing and 12 recovery cycles. Shaped catalysts were easily recovered by simple filtration. This catalyst, derived from nontoxic and affordable bismuth metal supported on chitosan ocean waste, presents significant improvements in the realm of sustainable chemistry and could open a new channel of possibilities for green catalysis.

Published
2023

5. Recent Developments in Enantioselective Domino Reactions. Part A: Noble Metal Catalysts

Author

Hélène Pellissier, Institut des Sciences Moléculaires de Marseille (ISM2), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
multicomponent reactions, [CHIM.ORGA]Chemical Sciences/Organic chemistry, domino reactions, asymmetric synthesis, noble metals, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, transition metals
Abstract

International audience; This review updates the field of enantioselective domino reactions promoted by chiral catalysts derived from noble metals, including palladium, silver, rhodium, ruthenium, iridium and gold, published since the beginning of 2019. It illustrates how much a diversity of these catalysts allow unprecedented asymmetric domino reactions of many types to be achieved with excellent enantioselectivity, giving a direct access to a wide variety of complex chiral molecules.

Published
2023

6. Methylenecyanamide (CH2═NCN) and (Z)- and (E)-Iminoacetonitriles (NC–CH═NH), Dimers of Hydrogen Cyanide

Author

Hajer Ayachi, Houda Gazzeh, Taoufik Boubaker, Jean-Claude Guillemin, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Monastir - University of Monastir (UM), and The authors thank the Centre National d’Etudes Spatiales (CNES) and the 'Programme National Physique et Chimie du Milieu Interstellaire' (PCMI) of CNRS/INSU with INC/INP co-funded by CEA and CNES for a grant. H.A. received a fellowship from the University of Monastir.

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry
Abstract

International audience; (Z)- and (E)-iminoacetonitriles (NCCH═NH), two hydrogen cyanide dimers, are described as key compounds in prebiotic chemistry. Among the many possible dimers of HCN with covalent bonds, even the second on the scale of thermodynamic stability, methylenecyanamide (CH(2)═NCN), has been investigated little. We show that this compound can be isolated, is stable enough to give an adduct with a nucleophile or a diene, and can be easily generated under prebiotic conditions, highlighting a possible role in this medium. Comparison between isomers shows significant differences in formation and chemical reactivity.

Published
2023

7. Nickel‐Catalyzed Cyanoalkylation of Ketone Derivatives

Author

Anaïs Coffinet, Vincent Levacher, Isabelle Gillaizeau, Jean‐François Brière, Sylvain Oudeyer, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and University of RouenNormandy, INSA Rouen Normandy, the Centre National de laRecherche Scientifique (CNRS), European Regional DevelopmentFund (ERDF), Labex SynOrg (ANR-11-LABX-0029), Carnot InstituteI2C, the graduate school for research XL-Chem (ANR-18-EURE-0020 XL CHEM) and by Region Normandie.

Subjects
Pincer ligand, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Cyanoalkylation, Organometallic catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Ketone, Nickel complexes
Abstract

International audience; Although the metal-based catalyzed cyanomethylation of aldehydes is well-developed, a similar approach to ketones with acetonitrile derivatives remains a challenge. Thanks to Tolman type complexes, NiIIcomplexes with a pyridine(dicarboxamide) pincer ligand, analternative metal-catalyzed (1-5 mol% catalyst) cyanomethylation of an array of isatins and activated ketones is reported at room temperature. High isolated yields (up to 99%) were obtained not only with the poorly acidic acetonitrile but also with more challenging substituted alkyl cyanide nucleophiles. The in situ generated putative ion paired catalysts [NiCR2CN]-Cat+ likely benefit from the cation part (Cs+ or n-Bu4N+) to facilitate their formation and catalytic activity

Published
2023

8. Precise control of the site selectivity in ruthenium-catalyzed C–H bond amidations using cyclic amides as powerful directing groups

Author

Yu-Chao Yuan, Qiu-Li Lu, Xiao-Tong Zhu, Sergio Posada-Pérez, Miquel Solà, Albert Poater, Thierry Roisnel, Rafael Gramage-Doria, Xuzhou Medical University, Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona (IQCC), Universitat de Girona (UdG), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Y.-C. Y. acknowledges the Science and Technology of XuZhou (KC19042) for financial support. We also thank the Public Experimental Research Center, Xuzhou Medical University, for NMR determination. R. G-D. acknowledges the ANR-JCJC scheme (ANR-19-CE07-0039), CNRS and the University of Rennes 1 for financial support. S. P. P. thanks the Marie Curie fellowship (H2020-MSCA-IF-2020-101020330). A. P. is a Serra Húnter Fellow and thanks ICREA Academia Prize 2019 and Spanish Mineco for project ref. PGC2018-097722-B-I00. A. P. and M. S. thank the Spanish Ministerio de Ciencia e Innovación for projects PID2021-127423NB-I00 and PID2020-13711GB-I00 and the Generalitat de Catalunya for project 2017SGR39., and ANR-19-CE07-0039,REMOTCAT,Fonctionalisation 'remote' des molecules par catalyse supramoleculaire(2019)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis
Abstract

International audience; Selective C-H functionalizations aiming at the formation of new C-N bonds is of paramount importance in the context of step-and atom-economy methodologies in organic synthesis. Although the implementation of noble metal catalysts is prevalent, more benign cobalt pre-catalysts have recently appeared promising. However, they sometimes feature selectivity issues that limits its applicability in late-stage functionalization. Herein, we report on a highly reactive ruthenium-based catalytic system displaying excellent levels of mono-, regio-and site-selectivity exploiting a series of biologically-relevant cyclic amides as weak directing groups. The use of dioxazolone derivatives as the amidating reagent overcomes the issues encountered in the use of unstable azide derivatives for such transformations and it enables to perform these reactions under very mild reaction conditions (air, 40 o C). Moreover, a combination of deuteration experiments and a comparative study with different types of directing groups highlight the relevance of weak amide directing groups for enabling formation of six-membered cycloruthenate intermediates in key elementary steps of the catalytic cycle. In addition, DFT computational calculations were carried out for the first time for studying ruthenium-catalyzed C-N bond-forming processes via C-H activation assisted by weak directing groups, thereby elucidating the origin of the regio-and site-selectivity.

Published
2023

9. A highly conducting mixed-valence nickel bis(dithiolene) salt [Et4N][Ni(Me-thiazSe-dt)2]2 with selone substitution

Author

Hadi Hachem, Olivier Jeannin, Hengbo Cui, Reizo Kato, Marc Fourmigué, Dominique Lorcy, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Seoul National University [Seoul] (SNU), RIKEN - Institute of Physical and Chemical Research [Japon] (RIKEN), and This work was supported in part by Universite de Rennes (PhD grant to H. H.). The stay of H. H. to RIKEN was supported in part by RIKEN International Program Associate and by Rennes Métropole.

Subjects
Inorganic Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry
Abstract

International audience; The prototypical [Ni(dmit)(2)] complex (dmit: 1,3-dithiole-2-thione-4,5-dithiolate) is modified here by combining the N-R substitution found in [Ni(R-thiazdt)(2)] complexes (R-thiazdt: N-alkyl-thiazoline-2-thione-4,5-dithiolate) and the selone substitution found in [Ni(dmiSe)(2)] complex (dmiSe: 1,3-dithiole-2-selone-4,5-dithiolate) to give a novel N-methyl substituted, radical anionic complex formulated as [Ni(Me-thiazSe-dt)(2)](1-) (Me-thiazSe-dt: N-methyl-thiazoline-2-selone-4,5-dithiolate). Both this anionic complex and its mixed-valence Et(4)N(+) salt crystallize with a rare cis arrangement of the two dithiolene ligands around the Ni atom. In the 1 : 2 [Et(4)N][Ni(Me-thiazSe-dt)(2)](2) salt, the complexes organize into dimerized chains well isolated from each other, giving the salt a strong one-dimensional character. It shows however a high RT conductivity of 4.6 S cm(-1) and small activation energy of 33 meV, indicating a possible Mott insulator behavior, which is not suppressed under pressures up to 10 GPa.

Published
2023

10. Pyridyl-benzimidazole derivatives decorated with phenylazo substituents and their low-spin iron(<scp>ii</scp>) complexes: a study of the synthesis, structure and photoisomerization

Author

Jakub Orvoš, Róbert Fischer, Barbora Brachňaková, Ján Pavlik, Ján Moncoľ, Alexandra Šagátová, Marek Fronc, Jozef Kožíšek, Lucie Routaboul, Azzedine Bousseksou, Ivan Šalitroš, Slovak University of Technology in Bratislava, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Palacky University Olomouc, and Brno University of Technology [Brno] (BUT)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, Catalysis
Abstract

International audience; A series of phenylazo-substituted derivatives of pyridyl-benzimidazoles L1–L5 has been synthesized via a modified Mills reaction and their structural, spectral and photoswitching properties were investigated. NMR spectroscopy and single-crystal X-ray diffraction analysis of the desired compounds confirmed their E conformation. The light-induced E ↔ Z (also called trans ↔ cis) isomerization was monitored using UV-VIS and 1H NMR spectroscopy that revealed a reversible photochromic behavior governed by first-order kinetics. State-of-the-art meta-dynamics simulations (iMTD-GC) and ab initio calculations (CASSCF-NEVPT2 and STEOM-DLPNO-CCSD) made the analysis of the electronic structures of ligands possible, which helped to explain the bland E-to-Z conversion of L1 and pronounced switching of L2–L5 ligands. Furthermore, the computational studies identified the active wavelengths of E-to-Z conversion and allowed assessing the mechanisms of photoisomerization. Additionally, ligands L1 and L2 were used for the preparation of four ferrous coordination compounds C1–C4 in which the structural and magnetic investigations confirmed the permanent low-spin state and diamagnetic behavior in the solid state. On the other hand, dissolved compounds C1 and C2 are high-spin at room temperature and their blue light irradiation causes the decomplexation instead of the desired E-to-Z isomerization.

Published
2023

11. Synthesis of Chiral Heterocycles from Asymmetric Cascade Palladium Catalysis

Author

Hélène Pellissier, Institut des Sciences Moléculaires de Marseille (ISM2), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
heterocycles, asymmetric metal catalysis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, domino reactions, Organic Chemistry, chirality, [CHIM.CATA]Chemical Sciences/Catalysis, cascade reactions, Palladium
Abstract

Abstract: This review updates the field of asymmetric cascade palladium catalysis applied to the synthesis of chiral heterocycles since 2019. It illustrates how much a diversity of chiral palladium catalysts promote unprecedented asymmetric domino reactions of many types, allowing direct access to a wide variety of complex and densely functionalized chiral heterocyclic molecules.

Published
2023

12. Highly dispersed Rh single atoms over graphitic carbon nitride as a robust catalyst for the hydroformylation reaction

Author

Lole Jurado, Jerome Esvan, Ligia A. Luque-Álvarez, Luis F. Bobadilla, José A. Odriozola, Sergio Posada-Pérez, Albert Poater, Aleix Comas-Vives, M. Rosa Axet, Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Instituto de Ciencia de Materiales de Sevilla (ICMSE), Universidad de Sevilla / University of Sevilla-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona (IQCC), Universitat de Girona (UdG), Vienna University of Technology (TU Wien), Universitat Autònoma de Barcelona (UAB), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Catalysis
Abstract

International audience; Rhodium-catalysed hydroformylation, effective tool in bulk and fine-chemical synthesis, predominantly uses soluble metal complexes. For that reason, the metal leaching and the catalyst recycling are still the major drawbacks of this process. Single-atom catalysts have emerged as a powerful tool to combine the advantages of both homogeneous and heterogeneous catalysts. Since using an appropriate support material is key to create stable, finely dispersed, single-atom catalysts, here we show that Rh atoms anchored on graphitic carbon nitride are robust catalysts for the hydroformylation reaction of styrene.

Published
2023

13. Tricyclic SpiroLactams Kill Mycobacteria In Vitro and In Vivo by Inhibiting Type II NADH Dehydrogenases

Author

Sushovan Dam, Salia Tangara, Claire Hamela, Theo Hattabi, Léo Faïon, Paul Carre, Rudy Antoine, Adrien Herledan, Florence Leroux, Catherine Piveteau, Maxime Eveque, Marion Flipo, Benoit Deprez, Laurent Kremer, Nicolas Willand, Baptiste Villemagne, Ruben C. Hartkoorn, Centre d’Infection et d’Immunité de Lille - INSERM U 1019 - UMR 9017 - UMR 8204 (CIIL), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Centre National de la Recherche Scientifique (CNRS), CHU Lille, Médicaments et molécules pour agir sur les Systèmes Vivants - U 1177 (M2SV), Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille, Institut de Recherche en Infectiologie de Montpellier (IRIM), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM), the CPER grants were funded by European Union under the European Regional Development Fund (ERDF) and by the Hauts de Franceregional Council (contract n°20002842 and contract n°18006176), ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-19-CE18-0034,NL4TB,Nouvelle génération de composés Lead pour combattre la tuberculose(2019), and Willand, Nicolas

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Antitubercular Agents, Mycobacterium tuberculosis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, NAD, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Drug Discovery, Animals, Molecular Medicine, NADH, NADPH Oxidoreductases, [SDV.MP.BAC] Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Zebrafish
Abstract

International audience; It is critical that novel classes of antituberculosis drugs are developed to combat the increasing burden of infections by multidrug-resistant strains. To identify such a novel class of antibiotics, a chemical library of unique 3-D bioinspired molecules was explored revealing a promising, mycobacterium specific Tricyclic SpiroLactam (TriSLa) hit. Chemical optimization of the TriSLa scaffold delivered potent analogues with nanomolar activity against replicating and nonreplicating Mycobacterium tuberculosis. Characterization of isolated TriSLa-resistant mutants, and biochemical studies, found TriSLas to act as allosteric inhibitors of type II NADH dehydrogenases (Ndh-2 of the electron transport chain), resulting in an increase in bacterial NADH/NAD+ ratios and decreased ATP levels. TriSLas are chemically distinct from other inhibitors of Ndh-2 but share a dependence for fatty acids for activity. Finally, in vivo proof-of-concept studies showed TriSLas to protect zebrafish larvae from Mycobacterium marinum infection, suggesting a vulnerability of Ndh-2 inhibition in mycobacterial infections.

Published
2022

14. From polyethyleneimine hydrogels to Pickering-like smart 'On/Off' emulgels switched by pH and temperature

Author

Grégory Douyère, Loïc Leclercq, Véronique Nardello-Rataj, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
Pickering emulgels, pH, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Temperature, Hydrogels, Colloidal tectonics, Hydrogen-Ion Concentration, Multi-responsive systems, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Biomaterials, Colloid and Surface Chemistry, Polyethyleneimine hydrogels, Polyethyleneimine, Emulsions, Amines, Oils
Abstract

International audience; Hypothesis: According to the so-called colloidal tectonic concept, we assumed that a single self-complementary polymer-based tecton could be used to design self-assembled emulsions. The polymer must be of high-molecular weight with balanced bipolar properties generating those of rigidity and flexibility. Linear polyethyleneimine (LPEI, 25 kDa) was used because it acts as a buffer by continuous protonation/deprotonation of the amine groups.Experiments: The relationships between the physicochemical properties of LPEI (protonation, charge, size, aggregation and gelation) and emulsions (type, droplet size, rheological behavior and stability) were investigated to highlight the self-assembly and stabilization mechanisms during the construction events as well as the inherent properties of emulsions (responsiveness to external stimuli).Findings: In aqueous solution, after a first heat and cool cycle, the adequate and spontaneous self-assembly of hydrophobic and hydrophilic sections leads to hydrogels by the formation of a 3D network where the crystallized hydrophobic domains act as knots. In the presence of various oils, the hydrogels provide long-term stable Pickering emulgels. The as-prepared emulsions are highly controllable due to their self-assembled nature (up to 10 consecutive runs). Consequently, this new approach provides a facile route to construct self-assembled, reversible and dynamics Pickering-like emulsions by simplifying the colloidal tectonics concept.

Published
2022

15. 2-Azahetaryl-2-(oxoindolin-2-ylidene)acetonitriles as Colorimetric Probes for Zn: Synthesis and Optical Properties

Author

Vladyslav V. Shcherban, Olena O. Kuleshova, Tetiana Ye. Keda, Olga V. Khilya, Emmanuel Gras, Yulian M. Volovenko, Taras Shevchenko National University of Kyiv, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)

Subjects
imidoylchloride, 2-azahetaryl-2-(oxoindolin-2- ylidenes)acetonitrile, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, spectrophotometry, dipyrrin-like skeleton, General Chemistry, zinc probe
Abstract

International audience; A new one-pot approach for the synthesis of the Zn2+-sensitive probes 2-azahetaryl-2-(oxoindolin-2-ylidene)acetonitriles 3a–c and 4 is described. The method includes the in situ formation of imidoylchloride and its further condensation with azahetarylacetonitrile 1. The structure of the obtained compounds is studied using 1H nuclear magnetic resonance (NMR), 13C NMR, infrared (IR), high-resolution mass spectrometry (HRMS), and UV–Vis spectroscopy techniques. Two model ligands both exhibiting the highest extinction coefficient and the best solubility in a Tris buffer pH 7.2/dimethyl sulfoxide (DMSO) solution, namely 5-methyl-benzothiazole derivative 3b and benzoxazole derivative 4, are thoroughly studied as colorimetric probes for Zn2+. The probe 3b has the highest sensitivity to Zn2+, showing a limit of ion detection (LOD) calculated by the 3S criterion of 0.43 μM and selectivity upon masking Cu2+ ions with Na2S2O3. The composition of the complexes in the solution was determined by the limited logarithm method. The stability constant (lg K) values of 3b-Zn of 10.27 ± 0.02 and 4-Zn of 12.5 ± 0.2 indicate the formation of complexes of average stability.

Published
2022

16. Chirality Induction at the Helically Twisted Surface of Nanoparticles Generating Circularly Polarized Luminescence

Author

Jumpei Kuno, Nicolas Ledos, Pierre-Antoine Bouit, Tsuyoshi Kawai, Muriel Hissler, Takuya Nakashima, Nara Institute of Science and Technology, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Osaka Metropolitan University, This work was supported by JSPS KAKENHI grant numbers JP16H06522 in Scientific Research on Innovative Areas 'Coordination Asymmetry', JP22H05134 for Transformative Research Areas (A) 'Revolution of Chiral Materials Science using Helical Light Fields', and the Ministère de la Recherche et de l’Enseignement Supérieur, the CNRS, the Région Bretagne, the French National Research Agency (ANR Fluohyb ANR-17-CE09-0020). J.K. acknowledges a JSPS Research Fellowship for Young Scientists., and ANR-17-CE09-0020,FluoHyb,Nouveaux matériaux hybrides fluorescents basés sur le concept de l'émission induite par agrégation de chromophores organiques greffés sur des nanoparticules inorganiques.(2017)

Subjects
hybrid nanoparticles, coordination, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, Materials Chemistry, chirality, circularly polarized luminescence, General Chemistry
Abstract

International audience; Circularly polarized luminescence (CPL) can be generated either from fluorescent dyes with chiral structures or from achiral luminophores in chiral environments such as chiral hosts or chiral self-assemblies. Herein, we demonstrate the CPL induction to an achiral fluorophore grafted on an inorganic nanoparticle (NP) with a chiral shape. NPs composed of a mercury sulfide (HgS) cinnabar phase with a chiral crystal structure are investigated as a platform on which the achiral molecules self-assemble into a chiral arrangement. Both the crystallographic and morphological chiralities of HgS NPs are independently considered for the induction of a chiral arrangement of achiral dyes. The HgS NPs with an ellipsoidal shape (nanoellipsoids) are modified with the achiral fluorescent dye, resulting in no CPL emission. The larger HgS NPs with a chiral twisted structure (nanotwists) are found to give rise to CPL. The sign of CPL signals could be regulated through the modification of the twist direction of the HgS NPs. Chirality is considered to be induced in the arrangement or assembly of achiral fluorescent molecules on the chirally twisted surface of NPs

Published
2022

17. On drug discovery against infectious diseases and academic medicinal chemistry contributions

Author

Yves L Janin, Structure et Instabilité des Génomes (STRING), Muséum national d'Histoire naturelle (MNHN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Janin, Yves

Subjects
frequent hitters, [CHIM.ORGA]Chemical Sciences/Organic chemistry, hit to lead chemical library, medicinal chemistry, Organic Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, virtual docking, antibacterials
Abstract

International audience; This perspective is an attempt to document the problems that medicinal chemists are facing in drug discovery. It is also trying to identify relevant/possible, research areas in which academics can have an impact and should thus be the subject of grant calls. Accordingly, it describes how hit discovery happens, how compounds to be screened are selected from available chemicals and the possible reasons for the recurrent paucity of useful/exploitable results reported. This is followed by the successful hit to lead stories leading to recent and original antibacterials which are, or about to be, used in human medicine. Then, illustrated considerations and suggestions are made on the possible inputs of academic medicinal chemists. This starts with the observation that discovering a “good” hit in the course of a screening campaign still rely on a lot of luck – which is within the reach of academics –, that the hit to lead process requires a lot of chemistry and that if public–private partnerships can be important throughout these stages, they are absolute requirements for clinical trials. Concerning suggestions to improve the current hit success rate, one academic input in organic chemistry would be to identify new and pertinent chemical space, design synthetic accesses to reach these and prepare the corresponding chemical libraries. Concerning hit to lead programs on a given target, if no new hits are available, previously reported leads along with new structural data can be pertinent starting points to design, prepare and assay original analogues. In conclusion, this text is an actual plea illustrating that, in many countries, academic research in medicinal chemistry should be more funded, especially in the therapeutic area neglected by the industry. At the least, such funds would provide the intensive to secure series of hopefully relevant chemical entities which appears to often lack when considering the results of academic as well as industrial screening campaigns.

Published
2022

18. H2O2-Responsive Nanocarriers Prepared by RAFT-Mediated Polymerization-Induced Self-Assembly of N-(2-(Methylthio)ethyl)acrylamide for Biomedical Applications

Author

Hien Phan, Robert Cavanagh, Damien Destouches, Francis Vacherot, Blandine Brissault, Vincenzo Taresco, Jacques Penelle, Benoit Couturaud, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), University of Nottingham, UK (UON), Résistances Thérapeutiques du Cancer de la Prostate (TRePCa), and Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)

Subjects
[CHIM.POLY]Chemical Sciences/Polymers, [SDV.SP.PG]Life Sciences [q-bio]/Pharmaceutical sciences/Galenic pharmacology, Polymers and Plastics, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, Organic Chemistry
Abstract

International audience; H2O2-sensitive block copolymer nanoparticles (NPs) composed of a hydrophilic macro-chain transfer agent (macro-CTA) and a hydrophobic thioether-bearing block were prepared by polymerization-induced self-assembly (PISA) approach. The PISA process first involved the chain extension of poly((poly(ethylene glycol) methyl ether methacrylate)-co-(poly(ethylene glycol) methacrylate)) macro-CTA with a H2O2-responsive N-(2-(methylthio)ethyl)acrylamide (MTEAM) monomer, which self-assembled into P((PEGMA-co-PEGMAOH)-b-PMTEAM) block copolymer NPs. The polymerization kinetics indicated the evolution of particle size and morphology from spherical micelles, fused micelles, to vesicles over time. Upon incubation with 0.1 to 10 mM H2O2, spheres were fragmented due to the oxidation of the PMTEAM cores, thus transforming the hydrophobic thioethers into hydrophilic sulfoxides and disassociating the nanocarriers. 43% of the hydrophobic Nile red dye was encapsulated into the spherical micelles and demonstrated a controlled release in H2O2 incubation. Spherical micelles and vesicles displayed no cytotoxicity in MCF-7, DU145, and 22Rv1 cells. Both spheres and vesicles were efficiently internalized into MCF-7 cells, with spheres showing a higher level of uptake than vesicles due to the smaller sizes. In summary, PISA of P((PEGMA-co-PEGMAOH)-b-PMTEAM) allowed the direct formation and loading of hydrophobic dye into spherical micelles, which showed a controlled drug release in H2O2.

Published
2022

19. Tuning the Charge Transfer in λ5-Phosphinines with Amino Substituents

Author

Nicolas Ledos, Thitiporn Sangchai, Iryna Knysh, Manon H. E. Bousquet, Payal Manzhi, Marie Cordier, Denis Tondelier, Bernard Geffroy, Denis Jacquemin, Pierre-Antoine Bouit, Muriel Hissler, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Laboratoire de physique des interfaces et des couches minces [Palaiseau] (LPICM), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE09-0020,FluoHyb,Nouveaux matériaux hybrides fluorescents basés sur le concept de l'émission induite par agrégation de chromophores organiques greffés sur des nanoparticules inorganiques.(2017), and ANR-20-CE29-0005,BSE-forces,Géométries dans l'état excité dans le formalisme de Bethe-Salpeter(2020)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Biochemistry
Abstract

International audience; We report the substitution of lambda 5-phosphinines (2,6-dicarbonitrile diphenyl-1-λ 5-phosphinine) with amino-group. The impact of these modifications on both the optical and redox properties is investigated using a joint experimental/theoretical approach. In particular, we show that the choice of the donor diphenyl-amino group dramatically impacts the nature of the charge transfer. The use of di(methoxyphenyl)amine redshifts the optical properties and allows thermally activated delayed fluorescent in the solid-state. Finally, we demonstrated that lambda 5-phosphinines with amino-group can be used as active emitter in an electroluminescent device.

Published
2022

20. Catalysis Driven Six-Step Synthesis of Apratoxin A Key Polyketide Fragment

Author

Na Shao, Jean Rodriguez, Adrien Quintard, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), and ANR-19-CE07-0033,H2-drive,L'hydrogène comme initiateur de cascades énantiosélectives(2019)

Subjects
Biological Products, catalysis, multicatalysis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Depsipeptides, Polyketides, Organic Chemistry, Stereoisomerism, Total synthesis: polyketide, Physical and Theoretical Chemistry, enantioselective, anticancer, Biochemistry
Abstract

International audience; Apratoxin A is a potent anticancer natural product whose key polyketide fragment constitutes a considerable challenge for organic synthesis, with five prior syntheses requiring 12 to 20 steps for its preparation. By combining di erent redoxeconomical catalytic stereoselective transformations, the key polyketide fragment could be rapidly prepared. Followed by a siteselective protection of the diol, this strategy enables the preparation of the apratoxin A fragment in only six steps, representing the shortest route to this polyketide.

Published
2022

21. Selective Photocatalytic Dehydrogenation of Formic Acid by an In Situ-Restructured Copper-Postmetalated Metal–Organic Framework under Visible Light

Author

Houeida Issa Hamoud, Patrick Damacet, Dong Fan, Nisrine Assaad, Oleg I. Lebedev, Anna Krystianiak, Abdelaziz Gouda, Olivier Heintz, Marco Daturi, Guillaume Maurin, Mohamad Hmadeh, Mohamad El-Roz, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), American University of Beirut [Beyrouth] (AUB), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB), Université de Technologie de Belfort-Montbeliard (UTBM)-Université de Bourgogne (UB)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS), and University of Toronto

Subjects
Colloid and Surface Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Operando FTIR, Formic acid, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Photocatalysis, Biochemistry, MOFs, Copper, Catalysis, Hydrogen
Abstract

International audience; Formic acid is considered as one of the most promising liquid organic hydrogen carriers (LOHC). Its catalytic dehydrogenation processes generally suffer from low activity, low reaction selectivity, low stability of the catalysts and/or the use of noble-metal based catalysts. Herein, we report a highly selective, efficient, and noble metal-free photocatalyst for the dehydrogenation of formic acid. This catalyst is built from a post-metalation of a carboxylic-functionalized Zr-MOF by copper, namely UiO-66(COOH)2-Cu. The visible light driven photocatalytic dehydrogenation process through the release of hydrogen and carbon dioxide is monitored in real-time via operando FTIR and reveals almost 100% of selectivity with high stability (over 3 days) and conversion yield exceeding 60% (around 5 mmol.g-1 cat.h-1) at ambient conditions. These performance indicators make UiO-66(COOH)2-Cu among the top photocatalysts for formic acid dehydrogenation. Interestingly, the as-prepared UiO-66(COOH)2-Cu hetero-nanostructure was found moderately active under solar irradiation during an induction phase, whereupon it undergoes an in-situ restructuring process through intra-framework cross-linking with the formation of the anhydride analogue structure, UiO-66(COO)2-Cu, and nano-clustering of highly active and stable copper sites as evidenced by the operando studies coupled with steady state isotopic transient kinetic (SSITKA) experiment, TEM, XPS analysis and DFT calculations. Beyond revealing outstanding catalytic performance for UiO-66(COO)2-Cu, this work delivers an in-depth understanding of the photocatalytic reaction mechanism implying an evolutive behavior of the post-metalated copper as well as the MOF framework over the reaction. These key findings pave the ways towards the engineering of new simple and efficient catalysts for photocatalytic dehydrogenation of formic acid.

Published
2022

22. Characterization through scanning electron microscopy and μFourier transform infrared spectroscopy of microcalcifications present in fine needle aspiration smears

Author

Henry, Lucas, Bazin, Dominique, Policar, Clotilde, Haymann, Jean-Philippe, Daudon, Michel, Frochot, Vincent, Mathonnet, Muriel, Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL), Sorbonne Université (SU), Université Paris-Saclay, Laboratoire de Physique des Solides (LPS), Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Service d'Explorations fonctionnelles multidisciplinaires [CHU Tenon], CHU Tenon [AP-HP], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU)-Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU), Des Maladies Rénales Rares aux Maladies Fréquentes, Remodelage et Réparation, Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Hôpital Dupuytren [CHU Limoges], ENS-PSL (LH's PhD fellowship)Fondation pour la Recherche Biomédicale (project DEI20151234413), and Policar, Clotilde

Subjects
Thyroid, [CHIM.INOR] Chemical Sciences/Inorganic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Microscopie électronique à balayage, Spectroscopie infrarouge, Nodule, Smears, Building and Construction, Ponctions, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Scanning electron microscopy. Mots-clés. Thyroïde, [CHIM.OTHE] Chemical Sciences/Other, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electrical and Electronic Engineering, [CHIM.OTHE]Chemical Sciences/Other, Infrared spectroscopy
Abstract

International audience; In this contribution, we have characterized for the first time (to the best of our knowledge), microcalcifications present in fine needle aspiration (FNA) smears of thyroid nodules. Abnormal deposits were analysed through Fourier Transform Infrared Spectroscopy (FTIR) and Field Emission Scanning Electron Microscopy (FE-SEM) in order to obtain their chemical composition as well as their morphology at the micrometer scale. Thirty-one samples coming from 13 patients were investigated comprising five cases of papillary carcinoma, two of Graves’ disease, and six of adenomatous goitre. The smears were also stained for analysis of the cellular characteristics of these lesions for classifying according to the Bethesda classification. Two mineral species, amorphous and nanocrystallised apatite calcium phosphate, have been identified with very different morphologies. Moreover, FE-SEM observations at the micrometer scale underline the presence of different kinds of abnormal deposits.

Published
2022

23. Amido bisphosphonic acid as anchoring agent and photopolymerization initiator onto zirconium oxide surface

Author

Ben-Hadj-Salem, Jihen, Dragoe, Diana, Marie, Philippe, Froissart, Sandrine, Fouchet, Arnaud, Rouden, Jacques, Lecourt, Jérôme, Harnois, Christelle, Touil, Soufiane, Baudoux, Jérôme, Lepoittevin, Bénédicte, Laboratoire de chimie moléculaire et thioorganique (LCMT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Le Havre Normandie (ULH), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), and Laboratoire des composés Hétéro-Organiques et Matériaux Nanostructurés (LR18ES11)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, hybrid materials, bisphosphonic acid, photopolymerization, [CHIM]Chemical Sciences, zirconia, grafting from
Abstract

International audience; The surface modification of metal oxides by grafting an organic molecule allows the development of new specific properties on demand. In this work, we demonstrate the modification of the Yttria Tetragonal Zirconia Polycrystal (Y-TZP), which is a ceramic widely used in dental implantology, by polymer grafting of the surface in a three-steps protocol for tuning the wetting properties. The first step involved the preparation of zirconia pellet by sintering followed by their surface activation. In the second step, the organic initiator bearing a tertiary amine such as the N,N-dimethylamino group capable of initiating a radical photopolymerization reaction, was grafted onto the surface through a bisphosphonic acid functionality. In the last step, two monomers, namely methyl methacrylate and styrene, were photopolymerized on the zirconia surface by blue light irradiation.The chemical steps were monitored and characterized by X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE) and Atomic Force Microscopy (AFM). Wetting properties to different polar and nonpolar liquids and surface energies calculated with the Van Oss theory were found to vary systematically depending on the type of functionalization and grafting. This methodology is very promising for surface tuning of the dental ceramic.

Published
2023

24. Stereoselective formation of boron-stereogenic organoboron derivatives

Author

Abdou-Mohamed, Amel, Aupic, Clara, Fournet, Corentin, Parrain, Jean-Luc, Chouraqui, Gaëlle, Chuzel, Olivier, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Novachim, Aix Marseille Université, CNRS, '‘Provence-Alpes-Cote d’Azur’’ Council, and ANR-16-CE07-0002,BORON-HAT-TRICK,L'élément bore : une pierre angulaire pour la catalyse avec les espèces borénium, boryles et diborènes(2016)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry
Abstract

International audience; Four-coordinate organoboron derivatives present interesting chemical, physical, biological, electronical, and optical properties. Given the increasing demand for the synthesis of smart functional materials based on chiral organoboron compounds, the exploration of stereoselective synthesis of boron-stereogenic organo-derivatives is highly desirable. However, the stereoselective construction of organoboron compounds stereogenic at boron has been far less studied than other elements of the main group due to configurational stability concerns. Nowadays, these species are no longer elusive and configurationally stable compounds have been highlighted. The idea is to show the potential of the stereoselective building of the four-coordinate boron centre and encourage future endeavors and developments in the field.

Published
2023

25. Strongly Emitting Folic Acid-Derived Carbon Nanodots for One- and Two-Photon Imaging of Lyotropic Myelin Figures

Author

Benkowska-Biernacka, Dominika, Mucha, Sebastian, Firlej, Lucyna, Formalik, Filip, Bantignies, Jean-Louis, Anglaret, Eric, Samoć, Marek, Matczyszyn, Katarzyna, Institute of Advanced Materials, Wroclaw University of Science and Technology, Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Department of Physics and Astronomy [Columbia] (Mizzou Physics), University of Missouri [Columbia] (Mizzou), University of Missouri System-University of Missouri System, Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemical and Biological Engineering, Northwestern University, and Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], [CHIM.ORGA]Chemical Sciences/Organic chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft]
Published
2023

26. Catalytic Hydrogenation of derived-vegetable oils using ion-exchange resin-supported ruthenium nanoparticles

Author

Madureira, Antonio, Noël, Sébastien, Léger, Bastien, Kania, Nicolas, Ferreira, Michel, Ponchel, Anne, Monflier, Éric, UCCS Équipe Catalyse Supramoléculaire, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry
Abstract

International audience

Published
2023

27. Catalytic Hydrogenation of derived-vegetable oils using ion-exchange resin-supported ruthenium nanoparticles : scope & limitations

Author

Madureira, Antonio, Noël, Sébastien, Léger, Bastien, Kania, Nicolas, Ferreira, Michel, Ponchel, Anne, Monflier, Eric, UCCS Équipe Catalyse Supramoléculaire, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis
Abstract

National audience

Published
2023

28. Curated dataset of association constants between a cyclodextrin and a guest for machine learning

Author

Gökhan Tahıl, Fabien Delorme, Daniel Le Berre, Éric Monflier, Adlane Sayede, Sébastien Tilloy, Centre de Recherche en Informatique de Lens (CRIL), Université d'Artois (UA)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-20-THIA-0004,VIVAH,Vers une intelligence artificielle à visage humain(2020), UCCS Équipe Catalyse Supramoléculaire, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and UCCS Équipe Couches Minces & Nanomatériaux

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM]Chemical Sciences, [INFO]Computer Science [cs], General Chemistry, [INFO.INFO-AI]Computer Science [cs]/Artificial Intelligence [cs.AI]
Abstract

International audience

Published
2023

29. Exploiting poly(ε-caprolactone) grafted from hydrohydroxymethylated sunflower oil as biodegradable coating material of water-soluble fertilizers

Author

Abdelghani El Mouat, Taha El Assimi, Mustapha Raihane, Jérémy Ternel, Hervé Bricout, Eric Monflier, Sébastien Tilloy, Mohammed Lahcini, UCCS Équipe Catalyse Supramoléculaire, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Matériaux Innovants, Energie et Développement Durable [Marrakech] (IMED-Lab ), Faculté des Sciences et Techniques Marrakech (FSTG), Université Cadi Ayyad [Marrakech] (UCA)-Université Cadi Ayyad [Marrakech] (UCA), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Mohammed VI Polytechnic University

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, Organic Chemistry, Materials Chemistry, Surfaces, Coatings and Films
Abstract

International audience; In the present study, hyperbranched poly(ε-caprolactones) were prepared and used as coating materials to prepare slow release diammonium phosphate (DAP) fertilizer. Firstly, the sunflower oil was hydrohydroxymethylated by one-pot two-step process using Rh(acac)(CO)2 as catalyst, and triethylamine as ligand. Next, the bio-based hyperbranched poly(ɛ-caprolactone) (PCL) were prepared in open air by in-situ ring-opening polymerization of ε-caprolactone using hydrohydroxymethylated sunflower oil as macro-initiator and tetra(phenylethynyl)tin (Sn(C ≡ CPh)4) as catalyst. The structures of the prepared polymers (SFO-O-g-PCL) were confirmed by nuclear magnetic resonance (1H NMR) and the infrared spectroscopy (FTIR). Furthermore, molecular weight values around 20.000 g.mol−1 of PCL grafted in SFO-O-g-PCL were obtained, the thermal stability and morphology of the coated film were also evaluated using thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) respectively. The hydrophobic character of the films prepared from SFO-O-g-PCL was confirmed by measuring the contact angle of water droplets. In the second part, the DAP granular fertilizers were uniformly coated by the prepared material (SFO-O-g-PCL) using a laboratory rotary drum. Then the slow release performance in water of the coated and uncoated DAP fertilizer granules was evaluated by tracking the cumulative concentration of P2O5 released. Thus, it was found that only 10 % of P2O5 was released after 2 h of essay from the coated DAP compared to a total release of P2O5 from uncoated DAP (conventional fertilizer) during the same period. This finding opens a wide perspective to combine the advantages of hydrophobic polyesters and bio-based oils to produce biodegradable coating agents.

Published
2023

30. Thiol Catalysis of Selenosulfide Bond Cleavage by a Triarylphosphine

Author

Olga Firstova, Oleg Melnyk, Vincent Diemer, Centre d’Infection et d’Immunité de Lille - INSERM U 1019 - UMR 9017 - UMR 8204 (CIIL), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Centre National de la Recherche Scientifique (CNRS), and Diemer, Vincent

Subjects
Phosphines, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Proteins, [CHIM.CATA] Chemical Sciences/Catalysis, Indicators and Reagents, Sulfhydryl Compounds, [CHIM.CATA]Chemical Sciences/Catalysis, Peptides, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Catalysis
Abstract

International audience; The arylthiol 4-mercaptophenylacetic acid (MPAA) is a powerful catalyst of selenosulfide bond reduction by the triarylphosphine 3,3′,3″-phosphanetriyltris(benzenesulfonic acid) trisodium salt (TPPTS). Both reagents are water-soluble at neutral pH and are particularly adapted for working with unprotected peptidic substrates. Contrary to trialkylphosphines such as tris(2-carboxyethyl)phosphine hydrochloride (TCEP), TPPTS has the advantage of not inducing deselenization reactions. We believe that the work reported here will be of value for those manipulating selenosulfide bonds in peptidic or protein molecules.

Published
2022

31. Catalytic Stereoconvergent Synthesis of Homochiral β-CF3, β-SCF3, and β-OCF3 Benzylic Alcohols

Author

Andrej Emanuel Cotman, Pavel A. Dub, Maša Sterle, Matic Lozinšek, Jaka Dernovšek, Živa Zajec, Anamarija Zega, Tihomir Tomašič, Dominique Cahard, University of Ljubljana, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Jozef Stefan Institute [Ljubljana] (IJS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), and Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Cultural Studies, History, udc:54, ketones, Literature and Literary Theory, [CHIM.ORGA]Chemical Sciences/Organic chemistry, drug design, asymmetric catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, stereoselectivity, catalysts, alcohols, fluorine, density functional calculations, crystals, kinetic resolution, hydrogenation, ruthenium, adaptive crystals
Abstract

International audience; We describe an efficient catalytic strategy for enantio- and diastereoselective synthesis of homochiral β-CF3, β-SCF3, and β-OCF3 benzylic alcohols. The approach is based on dynamic kinetic resolution (DKR) with Noyori–Ikariya asymmetric transfer hydrogenation leading to simultaneous construction of two contiguous stereogenic centers with up to 99.9% ee, up to 99.9:0.1 dr, and up to 99% isolated yield. The origin of the stereoselectivity and racemization mechanism of DKR is rationalized by density functional theory calculations. Applicability of the previously inaccessible chiral fluorinated alcohols obtained by this method in two directions is further demonstrated: As building blocks for pharmaceuticals, illustrated by the synthesis of heat shock protein 90 inhibitor with in vitro anticancer activity, and in particular, needle-shaped crystals of representative stereopure products that exhibit either elastic or plastic flexibility, which opens the door to functional materials based on mechanically responsive chiral molecular crystals.

Published
2022

32. A bimetallic benzene-1,2,4,5-tetrathiolate (btt) molybdenocene complex Cp2Mo(btt)MoCp2: radical and diradical states

Author

Khalil Youssef, Corentin Poidevin, Antoine Vacher, Yann Le Gal, Oscar Charpentier, Marc Fourmigué, Arnaud Fihey, Frédéric Barrière, Thierry Roisnel, Dominique Lorcy, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Molybdenum, S ligands, Metallocenes, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Radical ions, General Chemistry, Through-bond interactions, Catalysis
Abstract

International audience; Benzene-1,2,4,5-tetrathiolate (btt) has been used as a bridging ligand to prepare a redox active (molybdenocene dithiolene)-based bimetallic complex Cp2Mo(btt)MoCp2, which exhibits four successive electron transfers up to the tetracation. Spectro-electrochemical investigations together with DFT and TD-DFT calculations evidence that the two electroactive MoS2C2 metallacycles are electronically coupled in the monocationic as in the dicationic state. Two salts of the dication [Cp2Mo(btt)MoCp2]2+ have been structurally characterized with PF6- and HSO4- counterions, showing different chair or boat conformations associated with variable folding angles of the two MoS2C2 metallacycles along the S---S hinge. The bis-oxidized dicationic complex exhibits a diradical character, with both radicals essentially localized on the metallacycles and with antiferromagnetic coupling evidenced from magnetic susceptibility measurements.

Published
2023

33. Basicity‐Controlled [3+2] Cyclization of 3‐Hydroxyquinolin‐ones and β‐Chlorinated Nitrostyrenes

Author

Jiamin Wu, Fei Hu, Guishun Bai, Yang Yang, Damien Bonne, Jean Rodriguez, Congyong Yue, Hong Wang, Xiaoze Bao, Zhejiang University of Technology, Institut des Sciences Moléculaires de Marseille (ISM2), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
heterocycles, catalysis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Michael addition, enantioselectivity, Organic Chemistry, Physical and Theoretical Chemistry, (3+2) cyclization
Abstract

International audience; The construction of novel skeletons through the recombination of natural products ring systems is attractive. Herein, a basicitycontrolled synthesis of (dihydro)furo[2,3-c]quinolin-4(5H)-one derivatives through (3 + 2) cyclization between 3-hydroxyquino-lin-2-ones and β-chlorinated nitrostyrenes was developed. In addition, preliminary study gave the chiral dihydrofuro[2,3c]quinolin-4(5H)-one derivatives with up to 83 % ee.

Published
2023

34. Continuous production of amines directly from alkenes via cyclodextrin-mediated hydroaminomethylation using only water as the solvent

Author

Thomas Roth, Rebecca Evertz, Niklas Kopplin, Sébastien Tilloy, Eric Monflier, Dieter Vogt, Thomas Seidensticker, TU Dortmund University, UCCS Équipe Catalyse Supramoléculaire, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], and Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Environmental Chemistry, [CHIM]Chemical Sciences, Pollution
Abstract

Aqueous hydroaminomethylation (HAM) is an atom economical route for the efficient production of amines in one reaction step, starting from basic chemicals like alkenes. Herein we present the first successful establishment of a continuous process for HAM in an aqueous multiphase system. The green mass transfer agents randomly methylated-β-cyclodextrins (CD) enabled the catalytic system consisting of rhodium/sulfoXantphos to achieve high yields of up to 70% with selectivities of up to 80% in several continuous experiments with a total run time of more than 220 h. The key here is that water and products have large polarity differences, but the reaction still proceeds effectively due to the addition of cyclodextrin, which made the application of solvents obsolete. The main achievements in this way were the investigation of the influence of the randomly methylated-β-cyclodextrin concentration on the reaction rate and the selectivity in batch studies and finding promising operating points in the first continuous experiments. In a final experiment, the separation temperature was investigated. It was shown that the catalyst loss in the product phase is enormously small at 0.003% h−1 of the initial mass (0.24% in total), which is the lowest ever reported value for the HAM on this scale. Within a run time of 78 hours, 2.87 kg of tertiary amine were produced using only 0.2 g (>14 000 : 1) of transition metal, while the loss of rhodium per kg of product produced was mostly around 0.15 mg kg−1, suggesting possible economical applicability. 25;9

Published
2023

35. Towards the controlled enzymatic synthesis of LNA containing oligonucleotides

Author

Nazarii Sabat, Dace Katkevica, Karlis Pajuste, Marie Flamme, Andreas Stämpfli, Martins Katkevics, Steven Hanlon, Serena Bisagni, Kurt Püntener, Filippo Sladojevich, Marcel Hollenstein, Chimie bioorganique des acides nucléiques - Bioorganic chemistry of nucleic acids, Institut Pasteur [Paris] (IP)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Latvian Institute of Organic Synthesis [Riga, Lituania], F. Hoffmann-La Roche [Basel], and The authors thank Institut Pasteur (starting funds to MH) and F. Hoffmann-La Roche Ltd., for financial support

Subjects
Locked nucleic acids, [CHIM.ORGA]Chemical Sciences/Organic chemistry, XNA, modified nucleotides, controlled enzymatic synthesis, General Chemistry, polymerases
Abstract

Enzymatic, de novo XNA synthesis represents an alternative method for the production of long oligonucleotides containing chemical modifications at distinct locations. While such an approach is currently developed for DNA, controlled enzymatic synthesis of XNA remains at a relative state of infancy. In order to protect the masking groups of 3′-O-modified LNA and DNA nucleotides against removal caused by phosphatase and esterase activities of polymerases, we report the synthesis and biochemical characterization of nucleotides equipped with ether and robust ester moieties. While the resulting ester-modified nucleotides appear to be poor substrates for polymerases, ether-blocked LNA and DNA nucleotides are readily incorporated into DNA. However, removal of the protecting groups and modest incorporation yields represent obstacles for LNA synthesis via this route. On the other hand, we have also shown that the template-independent RNA polymerase PUP represents a valid alternative to the TdT and we have also explored the possibility of using engineered DNA polymerases to increase substrate tolerance for such heavily modified nucleotide analogs.

Published
2023

36. Ruthenium Nanoparticles Stabilized with Methoxy-Functionalized Ionic Liquids: Synthesis and Structure–Performance Relations in Styrene Hydrogenation

Author

Deepthy Krishnan, Leonhard Schill, M. Rosa Axet, Karine Philippot, Anders Riisager, Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Danmarks Tekniske Universitet = Technical University of Denmark (DTU), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), and European Project: 860322,H2020-EU.1.3.1.,H2020-MSCA-ITN-2019,CCIMC(2020)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, functionalized ionic liquid, metal nanoparticle, ruthenium, catalysis, hydrogenation, styrene, General Materials Science, [CHIM.CATA]Chemical Sciences/Catalysis, Hydrogenation, Functionalized ionic liquid, Catalysis, Metal nanoparticle, Ruthenium, Styrene
Abstract

International audience; A series of ruthenium nanoparticles (RuNPs) were synthesized by the organometallic approach in different functionalized imidazolium ionic liquids (FILs). Transmission electron microscopy (TEM) showed well-dispersed and narrow-sized RuNPs ranging from 1.3 to 2.2 nm, depending on the IL functionalization. Thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) allowed the interaction between the RuNPs and the ILs to be studied. The RuNPs stabilized by methoxy-based FILs (MEM and MME) displayed a good balance between catalytic activity and stability when evaluated in the hydrogenation of styrene (S) under mild reaction conditions. Moreover, the catalysts showed total selectivity towards ethylbenzene (EB) under milder reaction conditions (5 bar, 30 °C) than reported in the literature for other RuNP catalysts.

Published
2023
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37. Half‐Sandwich Manganese Complex Bearing Fused Oxazoline‐NHC Ligand: Conformational Analysis and Evaluation in Asymmetric Ketone Hydrosilylation

Author

Matthieu Cavailles, Oleg A. Filippov, Vincent César, Noël Lugan, Dmitry A. Valyaev, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences [Moscow] (RAS), Centre National de la Recherche Scientifique (CNRS), and Ministry of Science and Higher Education of the Russian Federation

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, Manganese, Density functional calculations, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Hydrosilylation, Interligand interactions, [CHIM.COOR]Chemical Sciences/Coordination chemistry, N-heterocyclic carbenes, [CHIM.CATA]Chemical Sciences/Catalysis
Abstract

International audience; The first manganese complex bearing a chiral N-heterocyclic carbene (NHC) ligand was prepared and studied by spectroscopic methods and X-ray diffraction. While IR spectroscopy revealed the existence of two isomers in solution with distinct νCO band patterns, DFT calculations indicated that these isomers correspond to rotamers around the Mn−NHC bond and their different spectroscopic properties were rationalized by the occurrence of attractive π(C=C)⋅⋅⋅π*(C≡O) or σ(C−H)⋅⋅⋅π*(C≡O) intramolecular interligand interactions. The evaluation of this complex in catalytic hydrosilylation of acetophenone using Ph2SiH2 under UV irradiation led to the formation of the corresponding (R)-alcohol with low enantioselectivity.

Published
2023

38. Novel Catalyst Composites of Ni- and Co-Based Nanoparticles Supported on Inorganic Oxides for Fatty Acid Hydrogenations

Author

Ekaterina Mamontova, Corine Trabbia, Isabelle Favier, Alejandro Serrano-Maldonado, Jean-Bernard Ledeuil, Lénaïc Madec, Montserrat Gómez, Daniel Pla, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), and Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
C=C bonds hydrogenation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, titanium dioxide anatase, nickel-based nanoparticles, magnesium aluminum oxide spinel, fatty acids, valorization, industrial waste, General Materials Science, [CHIM.CATA]Chemical Sciences/Catalysis
Abstract

International audience; In the quest to develop nanometrically defined catalytic systems for applications in the catalytic valorization of agri-food wastes, small Ni-based nanoparticles supported on inorganic solid supports have been prepared by decomposition of organometallic precursors in refluxing ethanol under H 2 atmosphere, in the presence of supports exhibiting insulating or semiconductor properties, such as MgAl 2 O 4 and TiO 2 , respectively. The efficiency of the as-prepared Ni-based nanocomposites has been evaluated towards the hydrogenation of unsaturated fatty acids under solvent-free conditions, with high selectivity regarding the hydrogenation of C=C bonds. The influence of the support on the catalytic performance of the prepared Ni-based nanocomposites is particularly highlighted.

Published
2023
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39. Chalcogen bonding and variable charge transfer degree in two polymorphs of 1 : 1 conducting salts with segregated stacks

Author

Maxime Beau, Olivier Jeannin, Marc Fourmigué, Pascale Auban-Senzier, Claude Pasquier, Pere Alemany, Enric Canadell, Ie-Rang Jeon, Agence Nationale de la Recherche (France), Ministerio de Ciencia, Innovación y Universidades (España), Ministerio de Ciencia e Innovación (España), Generalitat de Catalunya, Agencia Estatal de Investigación (España), Fourmigué, Marc, Alemany, Pere 0000-0002-3139-6189], Canadell, Enric, Jeon, Ie Rang, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique des Solides (LPS), Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), University of Barcelona, Institut de Ciència de Materials de Barcelona (ICMAB), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), French National Research Agency Grant ANR [17-ERC3-0003], Generalitat de Catalunya [CEX2019-000917-S, CEX2021-001202-M], Spanish MICIU through the Severo Ochoa FUNFUTURE Excellence Centre distinction [PGC2018-096955-B-C44], Maria de Maeztu Units of Excellence Program [PID2021-128217NB-I00], MICIU, 2021SGR01519, 2021SGR00286, and ANR-17-ERC3-0003,MolFerro,Approches moléculaires vers les matériaux ferroélectriques multifonctionnels(2017)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, General Materials Science, General Chemistry, Condensed Matter Physics
Abstract

Harnessing a bis(selenomethyl)tetrathiafulvalene (TTF) derivative as a donor, conducting charge transfer (CT) salts are realized thanks to original packing structures supported by chalcogen bonding (ChB) interactions. Specifically, reaction of EDT-TTF(SeMe)2 (EDT = ethylenedithio) with an acceptor, 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane (F2TCNQ), afforded two polymorphs of 1 : 1 CT salts, α- and β-[EDT-TTF(SeMe)2](F2TCNQ). The donor and the acceptor molecules in both polymorphs organize into segregated and uniform stacks. Based on the structure, the α-salt shows a quasi-complete CT while the β-salt shows a partial CT with ρ ∼±0.8. The oxidation of TTF activates the σ-hole on Se atoms to be engaged in highly linear ChB interactions with the N atoms on F2TCNQ. The formation of directional ChB interactions resulted in original packing structures of the donor and the acceptor stacks that are distinct between α- and β-salts. In particular, the ChB motif observed in the β-salt allows F2TCNQ molecules within the stack to be closer than those in the α-salt. Consequently, the α-salt is a semi-conductor, while the β-salt shows metallic behaviour with a two-step metal-to-insulator (MI) transition. Moreover, the observed MI transition temperature in the β-salt (180 K) is substantially higher than that in other known CT salts, likely owing to the 3D coupling of the modulation in different chains brought about by the -SeMe substituents., Work in France was supported by the French National Research Agency Grant ANR 17-ERC3-0003 and a PhD grant (to M. Beau) from Région Bretagne. We thank the CDIFX in Rennes for the use of the X-ray diffractometer. Work in Spain was supported by MICIU through Grants PGC2018-096955-B-C44 and PID2021-128217NB-I00, Generalitat de Catalunya (2021SGR01519 and 2021SGR00286). E. C. acknowledges the support of the Spanish MICIU through the Severo Ochoa FUNFUTURE (CEX2019-000917-S) Excellence Centre distinction and P. A. acknowledges the support from the Maria de Maeztu Units of Excellence Program (CEX2021-001202-M)., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Published
2023

40. Designing Donor‐Acceptor Cyclopropane for the ThermalSynthesis of Carbocyclic Eight‐Membered Rings

Author

Kévin Masson, Maxime Dousset, Bohdan Biletskyi, Sara Chentouf, Jean‐Valère Naubron, Jean‐Luc Parrain, Laurent Commeiras, Paola Nava, Gaëlle Chouraqui, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Spectropôle - Aix Marseille Université (AMU SPEC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), and French Ministère de l’Enseignement Supérieur et de la Recherche (MESR)

Subjects
Donor-Acceptor Cyclopropane, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Rearrangement, General Chemistry, Eight-membered ring, Mechanistic studies
Abstract

International audience; An access to functionalised eight-membered carbocyclic ring compounds was developed by simply stirring an unusual vinylogous Donor-Acceptor Cyclopropane (DAC) in boiling o-xylene. Both experimental and computational studies were performed to explain the diastereoselectivity/regioselectivity transfer observed and to provide an overall picture of the mechanism.

Published
2023

41. Development of electrochemical sensors for bloodstream infection diagnostic

Author

Babin, Thibaut, Département Microtechnologies pour la Biologie et la Santé (DTBS), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Grenoble Alpes [2020-....], and Pascal Mailley

Subjects
Machine Learning, Capteurs électrochimiques, Identification sans marquage, Label-Free identification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, In vitro diagnostic, Electrochemical sensors, Diagnostic in vitro, Apprentissage machine, Hémoculture, Blood culture
Abstract

Blood culture is the gold standard for detecting bloodstream infections, which are widespread and potentially fatal. The time between the appearance of symptoms and the administration of appropriate treatment is therefore crucial. To perform a blood culture, cumbersome and expensive equipment is required but only offers a binary answer (infected or sterile) on the condition of the collected blood. The transport time between the collection site and the laboratory is time lost for diagnosis, resulting in a delay in therapeutic choices.This thesis aimed at evaluating the interest of electrochemical monitoring of a blood culture. First, a prototype of blood culture bottle instrumented by an electrochemical sensor array was developed. Many bacterial and fungal species were tested.The potentiometric measurements provided a multiparametric response, ensuring the detection without having to use a centralized and complex automaton. Moreover, these signals could be exploited by machine learning in order to identify the detected pathogen, without manipulation or chemical reagent. This technology would thus allow to valorize the transport time and to automate the first steps of identification to generate a relevant diagnosis in the shortest time.The last works carried out during this thesis allowed to study the biological and chemical phenomena involved during the detection and identification. These results open the way to numerous applications and research themes, particularly in the field of bacterial biofilms.; L'hémoculture est le test de référence pour détecter les infections du sang, des pathologies très répandues et potentiellement fatales. Le délai entre l’apparition des symptômes et l’administration d’un traitement adapté est donc une donnée cruciale. Pour effectuer une hémoculture, un équipement lourd et coûteux est nécessaire mais n’offre qu'une réponse binaire (infecté ou stérile) sur l'état du sang prélevé. Le temps de transport entre le lieu de prélèvement et le laboratoire est un temps perdu pour le diagnostic, entraînant un retard dans les choix thérapeutiques.Cette thèse a cherché à évaluer l’intérêt du suivi électrochimique d'une d'hémoculture. Dans un premier temps, un prototype de flacon instrumenté par un réseau de capteurs électrochimiques a été développé. De nombreuses espèces bactériennes et fongiques ont pu ainsi être testées.Les mesures potentiométriques obtenues ont permis d’obtenir une réponse multiparamétrique, assurant la détection sans avoir recours à un automate centralisé et complexe. De plus, ces signaux ont pu être exploités par apprentissage machine afin d’identifier le pathogène détecté, sans manipulation ou réactif chimique. Cette technologie permettrait donc de valoriser le temps de transport et d’automatiser les premières étapes d’identification pour générer un diagnostic pertinent dans les meilleurs délais.Les derniers travaux effectués pendant ce doctorat ont permis d’étudier les phénomènes biologiques et chimiques mis en jeu lors de la détection et l’identification. Ces résultats ouvrent la voie à de nombreuses applications et thématiques de recherche, notamment dans le domaine des biofilms bactériens.

Published
2023

42. Structure-activity relationships of actively FhuE transported rifabutin derivatives with potent activity against Acinetobacter baumannii

Author

M. Maingot, M. Bourotte, A.C. Vetter, B. Schellhorn, K. Antraygues, H. Scherer, M. Gitzinger, C. Kemmer, G.E. Dale, O. Defert, S. Lociuro, M. Brönstrup, N. Willand, V. Trebosc, Médicaments et molécules pour agir sur les Systèmes Vivants - U 1177 (M2SV), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille, and This research was financially co-funded by European Union underthe European Regional Development Fund (ERDF), by the Hauts DeFrance Regional Council (Contract n◦NP0020070) and by I-Site ULNE(ANR-16-IDEX-0004 ULNE).

Subjects
Pharmacology, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDV]Life Sciences [q-bio], Organic Chemistry, Drug Discovery, General Medicine, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology
Abstract

International audience

Published
2023

43. New Biocompatible β‐Phosphorylated Linear Nitrones Targeting Mitochondria: Protective Effect in Apoptotic Cells

Author

Marcel Culcasi, Caroline Delehedde, Mathieu Esgulian, Mathieu Cassien, Mathieu Chocry, Antal Rockenbauer, Sylvia Pietri, Sophie Thétiot‐Laurent, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), YELEN, Institute of Materials and Environmental Chemistry [Budapest], Research Centre for Natural Sciences, Hungarian Academy of Sciences (MTA)-Hungarian Academy of Sciences (MTA), and ANR-17-CE34-0006,MITODIAPM,Sondes mitochondriales et dispositifs de génération d'aérosols pour l'étude du stress oxydant et des dysfonctionnements cardiométaboliques induits par l'inhalation de faibles niveaux de particules ultrafines de pesticides chez l'animal(2017)

Subjects
EPR spin-trapping, superoxide quenching, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, mitochondria-targeted nitrones, 31P NMR, Molecular Medicine, Molecular Biology, Biochemistry, cellular viability
Abstract

International audience; Mitochondria, an essential organelle involved in cellular respiration, energy production, and cell death, is the main cellular source of reactive oxygen species (ROS), including superoxide. Mitochondrial diseases resulting from uncontrolled/excess ROS generation are an emerging public health concern and there is current interest for specific mitochondriotropic probes to get information on in situ ROS production. As such, nitrones vectorized by the triphenylphosphonium (TPP) cation have recently drawn attention despite reported cytotoxicity. Herein, we describe the synthesis of 13 low-toxic derivatives of N-benzylidene-1-diethoxyphosphoryl-1-methylethylamine N-oxide (PPN) alkyl chain-grafted to a pyridinium, triethylammonium or berberinium lipophilic cation. These nitrones showed in vitro superoxide quenching activity and EPR/spin-trapping efficiency towards biologically relevant free radicals, including superoxide and hydroxyl radicals. Their mitochondrial penetration was confirmed by 31P NMR and anti-apoptotic properties assessed inhydrogen peroxide treated Schwann cells. Two pyridinium substituted PPNs were identified as potentially better alternatives to TPP nitrones conjugates for studies of mitochondrial oxidative damage.

Published
2023

44. Robust definition and prediction of dispersive Hansen solubility parameter ?D with COSMO-RS

Author

Théophile Gaudin, Adrien Benazzouz, Jean-Marie Aubry, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
History, Polymers and Plastics, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Regular solution theory, Business and International Management, Physical and Theoretical Chemistry, Condensed Matter Physics, Hansen solubility parameters, Biochemistry, Industrial and Manufacturing Engineering, COSMO-RS, COSMOmorph
Abstract

International audience; A simple approach to predict dispersive Hansen solubility parameter δD is proposed, taking advantage of the separation of energies in the COnductor-like Screening MOdel for Realistic Solvation (COSMO-RS). The “COSMOmorph”, that is, the COSMO file(s) with all surface charge densities and dielectric energy equal to zero, allows an unambiguous splitting of energies and choice of structures and removes the requirement for the experimental existence of a homomorph. Reasonable agreement between δD of COSMOmorph and published δD for 89 solvents is obtained, with a standard deviation of 1.0 MPa1/2. Note that perfect agreement is not expected due to the shortcomings of the historical method.

Published
2023

45. Simmons–Smith Cyclopropanation of Alkenyl 1,2-Bis(boronates): Stereoselective Access to Functionalized Cyclopropyl Derivatives

Author

Maruti Mali, Gangavaram V. M. Sharma, Subhash Ghosh, Thierry Roisnel, Bertrand Carboni, Fabienne Berrée, Council of Scientific and Industrial Research [India] (CSIR), Academy of Scientific and Innovative Research [Ghaziabad, India] (AcSIR), Partenaires INRAE, CSIR Indian Institute of Chemical Technology [Hyderabad] (IICT), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and This research has been performed as part of the Indo-French 'Joint Laboratory for Natural Products and Synthesis towards Affordable Health'. We thank CSIR, CNRS, and the University of Rennes 1 for support of this research. We thank Dr. B. Sridhar from CSIR-IICT for the X-ray structure of compound 4ie. The CSIR-IICT communication number of this manuscript is IICT/Pubs./2022/022.

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry
Abstract

International audience; A Simmons-Smith stereodefined procedure for thesynthesis of cyclopropyl-1,2-bis(boronates) has been developedstarting from the corresponding alkenes. The resulting compoundswere then subjected to regioselective Suzuki-Miyaura couplings toproduce diversely tri- or tetra-substituted arylcyclopropanes in goodyields. Further functionalization with 2-lithiothiophene provided 1,2-bis(aryl)cyclopropanes.

Published
2022

46. Light-Driven Molecular Whirligig

Author

Chuan Gao, Andreas Vargas Jentzsch, Emilie Moulin, Nicolas Giuseppone, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Moulin, Emilie

Subjects
[CHIM.POLY] Chemical Sciences/Polymers, Polymers, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Molecular Motor Proteins, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Biochemistry, Catalysis, [CHIM.POLY]Chemical Sciences/Polymers, Colloid and Surface Chemistry, Torque, Humans, Child, Mechanical Phenomena
Abstract

International audience; An unidirectional light-driven rotary motor was looped in a figure-of-eight molecule by linking two polymer chains between its stator and rotor parts. By properly tuning the size of these linkers, clockwise rotation of the motor under UV light was shown to create conformationally strained twists between the polymer chains and, in this tensed conformation, the energy stored in the molecular object was sufficient to trigger the reverse rotation of the motor back to its fully relaxed state. The functioning principle of this motorized molecular device appears very similar to the one of macroscopic whirligig crafts used by children for fun. In addition, we found that in its out-of-equilibrium tensed state, the fluorescence emission of the molecular motor increased by 500% due to the mechanical constraints imposed by the polymer chains on its conjugated core. Finally, by calculating the apparent thermal energies of activation for the backward rotations at different levels of twisting, we quantitatively determined a lower estimate of the work generated by this rotary motor, from which a torque and a force were extracted, thus answering a long-term open question in this field of research.

Published
2022

47. Synthesis of Axially Chiral Cationic Benzo[c]phenanthridinium Derivatives

Author

Yoann Coquerel, Jean Rodriguez, Florian Rigoulet, Brian Castro Agudelo, Michel Giorgi, Babak Sayah, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Fédération Sciences Chimiques Marseille (FSCM), Spectropôle - Aix Marseille Université (AMU SPEC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Provepharm Life Solutions, and ANR-19-CE07-0041,TWISTAR,Synthèse, aromaticité et réactivité d'hydrocarbures polycycliques aromatiques déformés(2019)

Subjects
arynes, azadienes, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, azonia compounds, fluorescence, rotamers, axial chirality, crystallography, DFT, Catalysis
Abstract

Cationic polycyclic aromatic compounds containing one or more nitrogen atom(s), also known as azonia polycyclic aromatic compounds, form a valuable class of molecules because of their fluorescent and/or medicinal properties. N-Arylated hydroisoquinoline derivatives were synthesized through an aryne aza-Diels–Alder cycloaddition/N-arylation sequence. A subsequent two-electron oxidation allowed the synthesis of some axially chiral cationic benzo[c]phenanthridinium derivatives. The structural and optical properties of some of these molecules were determined. Their chirality was evidenced experimentally by single-crystal X-ray diffraction and 1H NMR spectroscopy, and their conformational behavior was examined by computational DFT methods.

Published
2022

48. CYTOTOXIC EVALUATION OF ORIGINAL PYRAZOLO[3,4-d]THIAZOLES AND PYRAZOLO[3,4-c]PYRAZOLES

Author

Ostache, Nicu-Cosmin, Pâris, Arnaud, Hiebel, Marie-Aude, Fînaru, Adriana-Luminita, Daniellou, Richard, Suzenet, Franck, Guillaumet, Gérald, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Bacău Vasile Alecsandri, ERASMUS grants and CNFIS-FDI-0151/2017_0087/2019_0130/2020_ 0123/2021), Francophone University Agency in Central and Eastern Europe (CE_124_FF_2016), Campus France (N 857352 B, N 902192 B), the Eiffel Scholarship Program of Excellence (N 870738 C), projects CHemBio (FEDER-FSE 2014-2020-EX003677), Techsab (FEDER-FSE 2014-2020- EX011313), the RTR Motivhealth (2019-00131403), University of Orléans, CNRS, France, ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), and ANR-11-LABX-0018,IRON,Radiopharmaceutiques Innovants en Oncologie et Neurologie(2011)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Pharmacology, Toxicology and Pharmaceutics
Abstract

International audience; A concise and versatile synthetic strategy for the synthesis of original substituted heterobicycles was developed, relying on the use of aromatic hydrazines in one-pot condensations and Ullmann-type intramolecular cyclization sequences, as well as on chemoselective brominations and palladium-mediated cross-coupling reactions. In this study, the two series of novel heterobicycles were tested for their cytotoxic potential. The compounds were structurally characterized by nuclear magnetic resonance spectrometry (1H NMR and 13C NMR), infrared spectroscopy (IR) and high-resolution mass spectrometry (HRMS). The IC50 values of these compounds on five tumour cell lines (A-549, HS-683, MCF-7, SK-MEL-28 and B16-F1) were obtained by MTT colorimetric assay. Six of the compounds exhibited excellent activity compared to 5-fluorouracil against two of the five cell lines tested, with IC50 values ranging from 0.1 to 10 μM.

Published
2022

49. Imaging and Measuring Vesicular Acidification with a Plasma Membrane-Targeted Ratiometric pH Probe

Author

Sophie Michelis, Lydia Danglot, Romain Vauchelles, Andrey S. Klymchenko, Mayeul Collot, Laboratoire de Bioimagerie et Pathologies (LBP), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut de psychiatrie et neurosciences de Paris (IPNP - U1266 Inserm), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris Cité (UPCité), and Collot, Mayeul

Subjects
[SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, Cell Membrane, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, Hydrogen-Ion Concentration, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Lysosomes, [SDV.BC] Life Sciences [q-bio]/Cellular Biology, Endocytosis, Fluorescent Dyes, Analytical Chemistry
Abstract

International audience; Tracking the pH variation of intracellular vesicles throughout the endocytosis pathway is of prior importance to better assess the cell trafficking and metabolism of cells. Small molecular fluorescent pH probes are valuable tools in bioimaging but are generally not targeted to intracellular vesicles or are directly targeted to acidic lysosomes, thus not allowing the dynamic observation of the vesicular acidification. Herein, we designed Mem-pH, a fluorogenic ratiometric pH probe based on chromenoquinoline with appealing photophysical properties, which targets the plasma membrane (PM) of cells and further accumulates in the intracellular vesicles by endocytosis. The exposition of Mem-pH toward the vesicle's lumen allowed to monitor the acidification of the vesicles throughout the endocytic pathway and enabled the measurement of their pH via ratiometric imaging.

Published
2022

50. Blue-Emitting 2-(2′-Hydroxyphenyl)benzazole Fluorophores by Modulation of Excited-State Intramolecular Proton Transfer: Spectroscopic Studies and Theoretical Calculations

Author

Maxime Munch, Erika Colombain, Timothée Stoerkler, Pauline M. Vérité, Denis Jacquemin, Gilles Ulrich, Julien Massue, Massue, Julien, Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Ecole européenne de chimie, polymères et matériaux [Strasbourg], Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, and Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)

Subjects
Models, Molecular, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Spectrometry, Fluorescence, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Materials Chemistry, Hydrogen Bonding, Protons, Physical and Theoretical Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Fluorescent Dyes, Surfaces, Coatings and Films
Abstract

International audience; This article describes the synthesis, spectroscopic studies, and theoretical calculations of nine original fluorophores based on the 2-(2′-hydroxyphenyl)benzazole (HBX) scaffold, functionalized at the 4-position of the phenol ring by ethynyl-extended aniline moieties. HBX dyes are well-known to display an excited-state intramolecular proton transfer (ESIPT) process, owing to a strong six-membered hydrogen bond in their structure that allows for an enol/keto tautomerism after photoexcitation. Appropriate electronic substitution can perturb the ESIPT process, leading to dual fluorescence, both excited tautomers emitting at specific wavelengths. In the examples described herein, it is demonstrated that the proton transfer can be finely frustrated by a modification of the constitutive heteroring, leading to a single emission band from the excited enol or keto tautomer or a dual emission with relative intensities highly dependent on the environment. Moreover, the nature of the functionalization of the N-alkylated aniline moiety also has a significant importance on the relative excited-state stabilities of the two tautomers in solution. To shed more light on these features, quantum chemical calculations by the density functional theory are used to determine the excited-state energies and rationalize the experimental spectroscopic data.

Published
2022

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