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13 results on '"Arnaud Rives"'

1. Carbo‐mer of barrelene: a rigid 3D‐carbon‐expanded molecular barrel

Author

Brice Kauffmann, Valérie Maraval, Alix Saquet, Arnaud Rives, Albert Poater, Chongwei Zhu, Remi Chauvin, Carine Duhayon, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona (IQCC), Universitat de Girona (UdG), Institut Européen de Chimie et Biologie (IECB), Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM), Centre National de la Recherche Scientifique (CNRS), CNRS ЯÉCIPROCS network, and Spanish MINECO for project PGC2018-097722-B-I00

Subjects
Supramolecular chemistry, Carbo-mer, Ionic bonding, Ether, 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Barrelene, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Butatriene, Alkyne, 010405 organic chemistry, Chemistry, Organic Chemistry, Covalent cage, General Chemistry, Carbon, 0104 chemical sciences, Crystallography, Charcoal, Density functional theory
Abstract

International audience; After extensive studies of 1D and 2D skeletal carbo‐mers based on C8π‐conjugatingdialkynylbutatriene units(DABs: ~C≡C–(R)C=C=C=C(R)–C≡C~) bridging spor sp2centers in carbo‐butene, ‐xylylene or ‐benzene derivatives, 3D versions are envisaged through carbo‐barrelenes and partially reduced derivatives thereofwhere two or three DAB blades span a bridge between sp3carbinol vertices or ether thereof. For R = Ph, stable representatives were synthesized through a pivotal [6]pericyclynedione, and extensively characterized by spectroscopic, electrochemical and crystallographic methods. Density functional theory calculations allow detailed analysis of structural and electronic features of the 7 Å high barrel‐shaped molecules, and show that they can behave as cages for ionic species. Beyond aesthetical concerns, the results could open prospects of applications in host‐guest supramolecular chemistry and single molecule charge transport.

Published
2021
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2. Dendrogenin A Synergizes with Cytarabine to Kill Acute Myeloid Leukemia Cells In Vitro and In Vivo

Author

Nizar, Serhan, Pierre-Luc, Mouchel, Philippe de, Medina, Gregory, Segala, Aurélie, Mougel, Estelle, Saland, Arnaud, Rives, Antonin, Lamaziere, Gaëtan, Despres, Jean-Emmanuel, Sarry, Clément, Larrue, François, Vergez, Laetitia, Largeaud, Michel, Record, Christian, Récher, Sandrine, Silvente-Poirot, Marc, Poirot, Institut Universitaire du Cancer de Toulouse - Oncopole (IUCT Oncopole - UMR 1037), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-CHU Toulouse [Toulouse]-Institut National de la Santé et de la Recherche Médicale (INSERM), Centre de Recherches en Cancérologie de Toulouse (CRCT), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Service d'Hématologie [IUCT Toulouse], Université Fédérale Toulouse Midi-Pyrénées-Institut Universitaire du Cancer de Toulouse - Oncopole (IUCT Oncopole - UMR 1037), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-CHU Toulouse [Toulouse]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-CHU Toulouse [Toulouse]-Institut National de la Santé et de la Recherche Médicale (INSERM), Affichem, Dendrogenix [Liège, Belgium], Microorganismes et physiopathologie intestinale (ERL INSERM U1157 - CNRS UMR 7203), Laboratoire des biomolécules (LBM UMR 7203), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC), Poirot, Marc, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Institut National de la Santé et de la Recherche Médicale (INSERM), Service Hématologie - IUCT-Oncopole [CHU Toulouse], Pôle Biologie [CHU Toulouse], Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Pôle IUCT [CHU Toulouse], Centre Hospitalier Universitaire de Toulouse (CHU Toulouse), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-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 Pierre et Marie Curie - Paris 6 (UPMC)-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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and This work was supported by an internal grant from the 'Institut National de la Recherche Médicale',the university of Toulouse III, Onco San Tech (projet DEMODA RMN13001BBA).

Subjects
Acute myeloid leukemia, tumor suppressor, primary cancer cells, [SDV]Life Sciences [q-bio], synergy, lcsh:Neoplasms. Tumors. Oncology. Including cancer and carcinogens, lcsh:RC254-282, Article, [SDV] Life Sciences [q-bio], hemic and lymphatic diseases, Dendrogenin A, cholesterol metabolism, lipids (amino acids, peptides, and proteins)
Abstract

International audience; Dendrogenin A (DDA) is a mammalian cholesterol metabolite that displays potent antitumor properties on acute myeloid leukemia (AML). DDA triggers lethal autophagy in cancer cells through a biased activation of the oxysterol receptor LXRβ, and the inhibition of a sterol isomerase. We hypothesize that DDA could potentiate the activity of an anticancer drug acting through a different molecular mechanism, and conducted in vitro and in vivo combination tests on AML cell lines and patient primary tumors. We report here results from tests combining DDA with antimetabolite cytarabine (Ara-C), one of the main drugs used for AML treatment worldwide. We demonstrated that DDA potentiated and sensitized AML cells, including primary patient samples, to Ara-C in vitro and in vivo. Mechanistic studies revealed that this sensitization was LXRβ-dependent and was due to the activation of lethal autophagy. This study demonstrates a positive in vitro and in vivo interaction between DDA and Ara-C, and supports the clinical evaluation of DDA in combination with Ara-C for the treatment of AML.

Published
2020
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3. A fast UPLC–HILIC method for an accurate quantification of dendrogenin A in human tissues

Author

Regis Soules, Etienne Chatelut, Fabien Audouard-Combe, Marc Poirot, Ben Allal, Arnaud Rives, Sandrine Silvente-Poirot, Camille Franchet, Philippe de Medina, Emilie Huc-Claustre, Florence Dalenc, Centre de Recherches en Cancérologie de Toulouse (CRCT), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Equipe Labellisée par la Ligue Nationale contre le Cancer, LNCC, Waters S.A.S. [Saint-Quentin En Yvelines, France], Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Claudius-Regaud (IUCO Toulouse), Institut Universitaire du Cancer Toulouse - Oncopôle (IUCT), Institut Universitaire du Cancer de Toulouse - Oncopole (IUCT Oncopole - UMR 1037), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-CHU Toulouse [Toulouse]-Institut National de la Santé et de la Recherche Médicale (INSERM), M. Poirot and S. Silvente-Poirot's team was funded by the Institut National de la Santé et de la Recherche Médicale (INSERM), the Université de Toulouse III, the Institut National du Cancer (INCA, PRTKK15-118, PLBIO18-130), the Fondation Toulouse Cancer Santé (2017CS065), and the associations 'Céline' and 'Flo'., Equipe labellisée Ligue contre le Cancer, Affichem [Toulouse, France], Dendrogenix [Liège, Belgium], Institut Claudius Regaud, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Institut National de la Santé et de la Recherche Médicale (INSERM), Service Anatomie et cytologie pathologiques [CHU Toulouse], Pôle Biologie [CHU Toulouse], Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse), Poirot, Marc, CRLCC Institut Claudius Regaud, Pôle Institut Universitaire du Cancer - Oncopole [CHU Toulouse] (Pôle IUC - Oncopole), CHU Toulouse [Toulouse]-Oncopole de Toulouse, Service d'Anatomo-Pathologie [CHU Toulouse], Centre Hospitalier Régional Universitaire de Toulouse (CHRU Toulouse), CHU Toulouse [Toulouse]-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)

Subjects
0301 basic medicine, Endocrinology, Diabetes and Metabolism, Metabolite, [SDV]Life Sciences [q-bio], Clinical Biochemistry, Breast Neoplasms, UPLC-MS, Mass spectrometry, Biochemistry, High-performance liquid chromatography, 03 medical and health sciences, chemistry.chemical_compound, 0302 clinical medicine, Endocrinology, Oxysterol, In vivo, Quantification, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Protein precipitation, Humans, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Breast, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Molecular Biology, [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Chromatography, Hydrophilic interaction chromatography, Method development, Imidazoles, Cell Biology, In vitro, 3. Good health, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], [SDV] Life Sciences [q-bio], 030104 developmental biology, Cholesterol, chemistry, Steroidal alkaloid, Dendrogenin B, 030220 oncology & carcinogenesis, Cancer cell, Dendrogenin A, Molecular Medicine, Female, Cholestanols, Chromatography, Liquid
Abstract

International audience; Dendrogenin A (DDA) is a newly-discovered steroidal alkaloid, which remains to date the first ever found in mammals. DDA is a cholesterol metabolites that induces cancer cell differentiation and death in vitro and in vivo, and thus behave like a tumor suppressor metabolite. Preliminary studies performed on 10 patients with estrogen receptor positive breast cancers (ER(+)BC) showed a strong decrease in DDA levels between normal matched tissue and tumors. This suggests that a deregulation on DDA metabolism is associated with breast carcinogenesis. To further investigate DDA metabolism on large cohorts of patients we have developed an ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS) procedure for the quantification of DDA in liquid and in solid tissues. This method enabled the identification of DDA analogues such as its geometric isomer C17 and dendrogenin B (C26) in human samples showing that other 5,6α-epoxycholesterol conjugation products with biogenic amines exist as endogenous metabolites . We report here the first complete method of quantification of DDA in liquid and solid tissues using hydrophilic interaction liquid chromatography (HILIC). Two different methods of extraction using either a Bligh and Dyer organic extraction or protein precipitation were successfully applied to quantify DDA in solid and liquid tissues. The protein precipitation method was the fastest. The fact that this method is automatable opens up possibilities to study DDA metabolism in large cohorts of patients.

Published
2019
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4. The cholesterol-derived metabolite dendrogenin A functionally reprograms breast adenocarcinoma and undifferentiated thyroid cancer cells

Author

Lavinia Vija-Racaru, Arnaud Mallinger, Marc Poirot, Sandrine Silvente-Poirot, Frédéric Courbon, Arnaud Rives, Bruno Payré, Philippe de Medina, Mathilde Bauriaud-Mallet, Severine Brillouet, Centre de Recherches en Cancérologie de Toulouse (CRCT), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Service de Médecine Nucléaire [Toulouse], CHU Toulouse [Toulouse], Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Microscopie Électronique Appliquée à la Biologie (CMEAB), Hôpital de Rangueil, CHU Toulouse [Toulouse]-CHU Toulouse [Toulouse]-Toulouse Réseau Imagerie-Genotoul ( TRI-Genotoul), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), This work was supported by the Institut National de la Santé et de la Recherche Médicale (INSERM), France and the Université de Toulouse, France., Affichem, Plateforme GénotoulCMEAB, Université Fédérale Toulouse Midi-Pyrénées, Departement /u563 : Oncogenèse, Signalisation et Innovation thérapeutique, Centre de Physiopathologie Toulouse Purpan (CPTP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut Claudius Regaud, Sterol metabolism and therapeutic innovations in oncology, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut Claudius Regaud, Centre de Physiopathologie Toulouse Purpan ex IFR 30 et IFR 150 (CPTP), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut Claudius Regaud, Institut Claudius Regaud, CRLCC Institut Claudius Regaud-CRLCC Institut Claudius Regaud-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Service de Médecine Nucléaire - Pierre-Paul Riquet [CHU Toulouse], Pôle imagerie médicale [CHU Toulouse], Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse), 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), Toulouse Réseau Imagerie-Genotoul ( TRI-Genotoul), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Département de Médecine Nucléaire [CHU Toulouse], Centre Hospitalier Universitaire de Toulouse (CHU Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), and Poirot, Marc

Subjects
0301 basic medicine, Endocrinology, Diabetes and Metabolism, medicine.medical_treatment, Cellular differentiation, [SDV]Life Sciences [q-bio], Clinical Biochemistry, Apoptosis, [SDV.BC.BC]Life Sciences [q-bio]/Cellular Biology/Subcellular Processes [q-bio.SC], Autoantigens, Biochemistry, Iodine Radioisotopes, Mice, 0302 clinical medicine, Endocrinology, Breast cancer, Iron-Binding Proteins, Tumor Cells, Cultured, Receptor, Thyroid cancer, ComputingMilieux_MISCELLANEOUS, Symporters, biology, Chemistry, Cell Cycle, Thyroid, Imidazoles, Receptors, Thyrotropin, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, 3. Good health, [SDV] Life Sciences [q-bio], [SDV.SP] Life Sciences [q-bio]/Pharmaceutical sciences, medicine.anatomical_structure, [SDV.SP.PHARMA] Life Sciences [q-bio]/Pharmaceutical sciences/Pharmacology, 030220 oncology & carcinogenesis, Differentiation, Molecular Medicine, Female, Tumor-suppressor, Mice, Nude, Antineoplastic Agents, Breast Neoplasms, [SDV.CAN]Life Sciences [q-bio]/Cancer, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, Adenocarcinoma, Iodide Peroxidase, Thyroglobulin, 03 medical and health sciences, [SDV.CAN] Life Sciences [q-bio]/Cancer, Thyroid peroxidase, [SDV.BC.BC] Life Sciences [q-bio]/Cellular Biology/Subcellular Processes [q-bio.SC], medicine, Animals, Humans, Cholesterol metabolism, Thyroid Neoplasms, Iodide transport, [SDV.BC] Life Sciences [q-bio]/Cellular Biology, Molecular Biology, Cell Proliferation, Cell Biology, medicine.disease, Xenograft Model Antitumor Assays, 030104 developmental biology, Cancer research, biology.protein, Dendrogenin A, [SDV.SP.PHARMA]Life Sciences [q-bio]/Pharmaceutical sciences/Pharmacology, Cholestanols, Hormone
Abstract

International audience; Dendrogenin A (DDA) is a tumor suppressor mammalian cholesterol-derived metabolite and a new class of ligand of the Liver X receptor (LXR), which displays tumor cell differentiation. In human MCF7 breast adenocarcinoma cells, DDA-induced cell differentiation was associated with an increased accumulation of neutral lipids and proteins found in milk indicating that DDA re-activates some functions of lactating cells. Active iodide transport occurs in the normal lactating mammary cells through the sodium/iodide symporter (NIS) and iodide (I) is secreted into milk to be used by the nursing newborn for thyroid hormones biosynthesis. In the present study, we assessed whether DDA may induce other characteristic of lactating cells such as NIS expression and iodine uptake in MCF7 breast cancer cells and extended this study to the papillary B-CPAP and undifferentiated anaplastic 8505c thyroid cancer cells. Moreover, we evaluated DDA impact on the expression of thyroid specific proteins involved in thyroid hormone biogenesis. We report here that DDA induces NIS expression in MCF7 cells and significantly increases the uptake of 131-I by acting through the LXR. In addition, DDA induces phenotypic, molecular and functional characteristics of redifferentiation in the two human thyroid carcinoma cell lines and the uptake of 131-I in the undifferentiated 8505c cells was associated with a strong expression of all the specific proteins involved in thyroid hormone biosynthesis, TSH receptor, thyroperoxidase and thyroglobulin. 131-I incorporation in the 8505c cells was stimulated by DDA as well as by the synthetic LXR ligand, GW3965. Together these data show that the re-differentiation of breast and thyroid cancer cells by DDA, is associated with the recovery of functional NIS expression and involves an LXR-dependent mechanism. These results open new avenues of research for the diagnosis of thyroid cancers as well as the development of new therapeutic approaches for radioiodine refractory thyroid cancers.

Published
2019
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5. Natural and semisynthetic oxyprenylated aromatic compounds as stimulators or inhibitors of melanogenesis

Author

Philippe de Medina, Nicolas Caron, Francesco Epifano, Sandrine Silvente-Poirot, Serena Fiorito, Arnaud Rives, Salvatore Genovese, Marc Poirot, Dipartimento di Scienze del Farmaco, Università degli studi 'G. d'Annunzio' Chieti-Pescara [Chieti-Pescara] (Ud'A), Centre de Recherches en Cancérologie de Toulouse (CRCT), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Affichem S.A. [Toulouse, France], and Poirot, Marc

Subjects
Melanogenesis, Cell Survival, [SDV]Life Sciences [q-bio], Anthraquinones, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, Benzoates, 01 natural sciences, Biochemistry, Benzaldehyde, Mice, Structure-Activity Relationship, 03 medical and health sciences, chemistry.chemical_compound, Coumarins, Drug Discovery, Melanin biosynthesis, Animals, Organic chemistry, Skin tanning effect, Molecular Biology, [SDV.BC] Life Sciences [q-bio]/Cellular Biology, Cells, Cultured, 030304 developmental biology, Whitening Agents, Benzoic acid, Melanins, Oxyprenylated natural products, Aldehydes, Biological Products, 0303 health sciences, Molecular Structure, 010405 organic chemistry, Chemistry, Organic Chemistry, Skin whitening effect, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, Coumarin, 0104 chemical sciences, 3. Good health, [SDV] Life Sciences [q-bio], [SDV.SP] Life Sciences [q-bio]/Pharmaceutical sciences, Cinnamates, [SDV.SP.PHARMA] Life Sciences [q-bio]/Pharmaceutical sciences/Pharmacology, Polar effect, [SDV.SP.PHARMA]Life Sciences [q-bio]/Pharmaceutical sciences/Pharmacology, Anthraquinone Derivatives
Abstract

International audience; It has been very recently shown how naturally occurring oxyprenylated coumarins are effective modulators of melanogenesis. In this short communication we wish to generalize the potentialities as skin tanning or whitening agents of a wider panel of natural and semisynthetic aromatic compounds, including coumarins, cinnamic and benzoic acids, cinnamaldehydes, benzaldehyde, and anthraquinone derivatives. A total number of 43 compounds have been tested assaying their capacity to inhibit or stimulate melanin biosynthesis in cultured murine Melan A cells. The wider number of chemicals herein under investigation allowed to depict a detailed structure-activity relationship, as the following: (a) benzoic acid derivatives are slightly pigmenting agent, for which the effect is more pronounced in compounds with longer O-side chains; (b) independently from the type of substitution, cinnamic acids are able to increase melanin biosynthesis, while benzaldehydes are able to decrease it; (c) coumarins with a 3,3-dimethylallyl or shorter skeletons as substituents in position 7 are tanning agents, while coumarins with farnesyloxy groups are whitening ones; (d) double oxyprenylation in position 6 and 7 and 3,3-dimethylallyl or geranyl skeletons have slight depigmenting capacities, while farnesyl skeletons tend to marginally increase the tanning effect; (e) the presence of electron withdrawing groups (acetyl, COOH, and -Cl) and geranyl or farnesyl oxyprenylated chains respectively in positions 3 and 7 of the coumarin nucleus lead to a whitening effect, and finally (f) oxyprenylated anthraquinones have only a weak depigmenting capacity.

Published
2019
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6. Synthesis of Functional Carbo-benzenes with Functional Properties: The C2 Tether Key

Author

Kévin Cocq, Valérie Maraval, Arnaud Rives, Cécile Barthes, Remi Chauvin, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Charge separation, Aryl, Organic Chemistry, Alkyne, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Computational chemistry, Carbo-mer, Molecule, Chemical stability, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Molecular materials, Alkyl
Abstract

Beyond demonstration of conceptual relevance and synthetic feasibility of aryl/alkyl-substituted representatives, carbo-benzene molecules started to gain prospects of broader impact through the emergence of alkynyl derivatives. This is first illustrated by examples of di- and hexaalkynyl-carbo-benzenes, a carbo-naphthalene, a carbo-biphenyl, and two carbo-terphenyls. A focus is then given to dialkynyl derivatives by reference to the peripherally C2-extruded parents. In the centro­symmetric quadrupolar series, the C2 expansion or ethynylogation effect is more particularly considered for 9H-fluoren-2-yl, tris(O-n-­alkyl)pyrogallyl, indol-3-yl, 4-anilinyl, and tetraphenyl-carbo-phenyl substituents on the following respective properties: two-photon absorption, chemical stability, columnar mesogenicity, on-surface photo­induced charge separation vs single-molecule conductance, and reduction potential. Topical results and prospects of application are discussed on the basis of crystallographic, spectroscopic, and electrochemical analyses vs DFT-calculated nuclear and electronic structures. For the sake of the discussion consistency, complementary experimental and computational results are disclosed in the dianilinyl series. Overall, it is shown that combined advances in strategy, protocols, and substrate scope of acetylenic synthesis remain crucial for the development of yet poorly explored but promising types of molecular materials.1 Introduction2 Hexaalkynyl-carbo-benzene3 ortho-Dialkynyl-carbo-benzene4 para-Dialkynyl-carbo-benzenes4.1 Bistrimethylsilylethynyl-carbo-benzene4.2 Bisfluorenylethynyl-carbo-benzene4.3 Bistrialkoxyarylethynyl-carbo-benzenes4.4 Bisindolylethynyl-carbo-benzene4.5 Bisanilinylethynyl-carbo-benzene5 Carbo-oligo(phenyleneethynylene)s6 Conclusions

Published
2019
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7. Improvement of 5,6α-epoxycholesterol, 5,6β-epoxycholesterol, cholestane-3β,5α,6β-triol and 6-oxo-cholestan-3β,5α-diol recovery for quantification by GC/MS

Author

Julie Leignadier, Marc Poirot, Sandrine Silvente-Poirot, Luigi Iuliano, Chiara Zerbinati, Arnaud Rives, Regis Soules, Emmanuel Noguer, Philippe de Medina, Centre de Recherches en Cancérologie de Toulouse (CRCT), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Affichem S.A. [Toulouse, France] (Société de Biotechnologie médicale), Department of Medico-Surgical Sciences and Biotechnologies [Latina, Italy], Vascular Biology & Mass Spectrometry Laboratory [Latina, Italy], Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome]-Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], This work was funded by the Institut National de la Santé et de la Recherche Médicale, the université Toulouse III, the Fondation de France (R11166BB), the Association pour la Recherche sur le Cancer (PJA 2013 12 00 342), the INCA (PRTK-K15-118), the European Union (FP7-309400: AFHELO and FP7-612261: TARGEAR)., European Project: 304900,EC:FP7:HEALTH,FP7-HEALTH-2012-INNOVATION-2,AFHELO(2012), European Project: 612261,EC:FP7:PEOPLE,FP7-PEOPLE-2013-IAPP,TARGEAR(2014), Sapienza - Università di Roma [Italy]-Sapienza - Università di Roma [Italy], Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA)-Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Poirot, Marc, Preclinical proof of concept of AF243 potency to prevent and/or treat sensorineural hearing loss - AFHELO - - EC:FP7:HEALTH2012-09-01 - 2016-05-31 - 304900 - VALID, and Targeting challenges of active ageing: innovative integrated strategies for the healing of age-related hearing loss - TARGEAR - - EC:FP7:PEOPLE2014-01-01 - 2017-12-31 - 612261 - VALID

Subjects
0301 basic medicine, Oxysterol, trimethylsilylation, [SDV]Life Sciences [q-bio], Diol, Molecular Conformation, [SDV.CAN]Life Sciences [q-bio]/Cancer, Isotope dilution, Mass spectrometry, Ring B oxysterols, Biochemistry, Gas Chromatography-Mass Spectrometry, 03 medical and health sciences, chemistry.chemical_compound, [SDV.CAN] Life Sciences [q-bio]/Cancer, Hydrolase, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Humans, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Solid phase extraction, Gas chromatrography, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Molecular Biology, [SDV.MHEP.EM] Life Sciences [q-bio]/Human health and pathology/Endocrinology and metabolism, chemistry.chemical_classification, [SDV.MHEP] Life Sciences [q-bio]/Human health and pathology, Chromatography, Organic Chemistry, Cell Biology, [SDV.MHEP.EM]Life Sciences [q-bio]/Human health and pathology/Endocrinology and metabolism, 3. Good health, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], [SDV] Life Sciences [q-bio], Cholesterol, 030104 developmental biology, Enzyme, Metabolism, chemistry, Trimethylsilylation, ring B oxysterols, epoxycholesterol, gas chromatrography, metabolism, Gas chromatography–mass spectrometry, Epoxycholesterol, Cholestanols, [SDV.MHEP]Life Sciences [q-bio]/Human health and pathology
Abstract

International audience; 5,6α-epoxycholesterol (5,6α-EC) and 5,6β-epoxycholesterol (5,6β-EC) are oxysterols involved in the anticancer pharmacology of the widely used antitumor drug tamoxifen. They are both metabolized into cholestane-3β,5α,6β-triol (CT) by the cholesterol-5,6-epoxide hydrolase (ChEH) enzyme, and CT is metabolized by an as-yet uncharacterized enzyme into 6-oxo-cholestan-3β,5α-diol (OCDO). A recent feasibility study showed that the 5,6-ECs may represent surrogate markers of tamoxifen activity in breast cancer patients undergoing endocrine therapy, thus there is a growing interest in their accurate quantification. These oxysterols are usually quantified by gas-liquid chromatography coupled to mass spectrometry (GC/MS), using an isotope dilution methodology with the corresponding deuterated oxysterol. This method is considered to be relative quantitative since all of the standards used are deuterated oxysterols, however it is not known whether the preparation of each oxysterol is affected in the same way by the extraction, pre-purification by solid phase extraction (SPE) and trimethylsilylation steps, particularly when using biological samples that contain many other reactive compounds. Thus, in this study we investigated the yield of the 5,6-ECs, CT and OCDO recovery from patient serum samples at different stages of their work-up and trimethylsilylation prior to GC/MS analysis, using [14C]-labeled analogs to follow these oxysterols at each step. We measured a 40 to 60% loss of material for the 5,6-ECs and OCDO, however we also describe the conditions that improved their recovery. Our data also show that the use of deuterated 5,6α-EC, 5,6β-EC, CT and OCDO is an absolute requirement for their accurate quantification.

Published
2017
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8. Quantitative analysis of the tumor suppressor dendrogenin A using liquid chromatography tandem mass spectrometry

Author

Arnaud Rives, Philippe de Medina, Claude Netter, Julie Leignadier, Emmanuel Noguer, Emilie Huc-Claustre, Citra Nagarathinam, Nizar Serhan, Regis Soules, Marc Poirot, Sandrine Silvente-Poirot, Affichem S.A. [Toulouse, France] (Société de Biotechnologie médicale), Centre de Recherches en Cancérologie de Toulouse (CRCT), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées, Thermo Fisher Scientific [Villebon sur Yvette, France], This work was funded by the Institut National de la Santé et de la Recherche Médicale, the université Toulouse III, the Fondation de France (R11166BB), the Association pour la Recherche sur le Cancer (PJA 2013 12 00 342), the INCA (PRTK-K15-118), and the European Union (FP7-309400: AFHELO and FP7-612261: TARGEAR)., European Project: 304900,EC:FP7:HEALTH,FP7-HEALTH-2012-INNOVATION-2,AFHELO(2012), European Project: 612261,EC:FP7:PEOPLE,FP7-PEOPLE-2013-IAPP,TARGEAR(2014), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT), Poirot, Marc, Preclinical proof of concept of AF243 potency to prevent and/or treat sensorineural hearing loss - AFHELO - - EC:FP7:HEALTH2012-09-01 - 2016-05-31 - 304900 - VALID, and Targeting challenges of active ageing: innovative integrated strategies for the healing of age-related hearing loss - TARGEAR - - EC:FP7:PEOPLE2014-01-01 - 2017-12-31 - 612261 - VALID

Subjects
0301 basic medicine, Polyamine, Metabolite, [SDV]Life Sciences [q-bio], Normal tissue, Molecular Conformation, Tandem mass spectrometry, 01 natural sciences, Biochemistry, High-performance liquid chromatography, law.invention, chemistry.chemical_compound, law, Liquid chromatography–mass spectrometry, Tandem Mass Spectrometry, Phytosterol, [SDV.BBM.BC] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Chromatography, High Pressure Liquid, [SDV.MHEP.EM] Life Sciences [q-bio]/Human health and pathology/Endocrinology and metabolism, [SDV.MHEP] Life Sciences [q-bio]/Human health and pathology, Imidazoles, Steroidal alkaloid, Hydrogen-Ion Concentration, [SDV.MHEP.EM]Life Sciences [q-bio]/Human health and pathology/Endocrinology and metabolism, 3. Good health, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], [SDV] Life Sciences [q-bio], Cholesterol, Female, Histamine, Breast Neoplasms, [SDV.CAN]Life Sciences [q-bio]/Cancer, 03 medical and health sciences, [SDV.CAN] Life Sciences [q-bio]/Cancer, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Humans, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Fragmentation (cell biology), [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Molecular Biology, Chromatography, 010401 analytical chemistry, Organic Chemistry, Cell Biology, 0104 chemical sciences, Dendrogenin, 030104 developmental biology, chemistry, Suppressor, Quantitative analysis (chemistry), Cholestanols, [SDV.MHEP]Life Sciences [q-bio]/Human health and pathology
Abstract

International audience; Dendrogenin A (DDA) was recently identified as a mammalian cholesterol metabolite that displays tumor suppressor and neurostimulating properties at low doses. In breast tumors, DDA levels were found to be decreased compared to normal tissues, evidencing a metabolic deregulation of DDA production in cancers. DDA is an amino-oxysterol that contains three protonatable nitrogen atoms. This makes it physico-chemically different from other oxysterols and it therefore requires specific analytical methods We have previously used a two-step method for the quantification of DDA in biological samples: 1) DDA purification from a Bligh and Dyer extract by RP-HPLC using a 250×4.6mm column, followed by 2) nano-electrospray ionization mass spectrometry (MS) fragmentation to analyze the HPLC fraction of interest. We report here the development a liquid chromatography tandem mass spectrometry method for the analysis of DDA and its analogues. This new method is fast (10min), resolving (peak width

Published
2017
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9. 3D and 2D supramolecular assemblies and thermotropic behaviour of a carbo-benzenic mesogen

Author

Brice Kauffmann, Hsiu-Fu Hsu, Chien-Jhang Su, Carine Duhayon, Valérie Maraval, Arnaud Rives, Tsai-Hui Wang, Chongwei Zhu, Chun-hsien Chen, Remi Chauvin, Shern-Long Lee, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, Department of Chemistry, Tamkang University, Tamkang University [New Taipei] (TKU), Department of Chemistry and Center for Emerging Material and Advanced Devices, National Taiwan University (CEMAD), National Taiwan Normal University (NTNU), Institut Européen de Chimie et Biologie (IECB), and Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 010405 organic chemistry, Mesogen, Metals and Alloys, Supramolecular chemistry, Mesophase, General Chemistry, 010402 general chemistry, 01 natural sciences, Thermotropic crystal, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Lattice constant, Liquid crystal, Materials Chemistry, Ceramics and Composites, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Single crystal, Powder diffraction
Abstract

International audience; Hexaalkoxy-di( phenylethynyl)-tetraphenyl-carbo-benzenes bearing six CnH2n+1 aliphatic chains (n = 12, 18) have been synthesized and characterized, including by single crystal XRD analysis. For n = 12, a liquid crystal behaviour was observed in the range of 109-130 degrees C. DSC, POM and PXRD analyses evidenced a rectangular columnar mesophase at 115 degrees C. The determined 3D lattice constants are consistent with 2D STM images of the so-called "carbo-mesogen'' deposited on an HOPG surface.

Published
2017
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10. First example of ring carbo-mer of 1,4-cyclohexadiene

Author

Valérie Maraval, Evelyne Chelain, Arnaud Rives, Thierry Brigaud, Cécile Barthes, Remi Chauvin, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Biologique (LCB), Université de Cergy Pontoise (UCP), and Université Paris-Seine-Université Paris-Seine

Subjects
chemistry.chemical_compound, Nucleophilic trifluoromethylation, Computational chemistry, Chemistry, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Butatrienes, 1,4-Cyclohexadiene, Ring (chemistry), Carbo-mers, Carbo-cyclohexadienes
Abstract

International audience; While a series of carbo-mers of 1,3-cyclohexadienes was reported through the use of a specifically developed synthetic strategy, no example of their 1,4-regioisomers was known. Inspired by the methodology elaborated for the preparation of the 1,3-isomers, the synthesis of the first example of carbo-mer of 1,4-cyclohexadiene is presented. Comparison of physico-chemical properties of this first representative with those of the recently described 1,3-regioisomer, especially UV-vis absorption properties, is also addressed.

Published
2015
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11. Carbo-cyclohexadienes vs. carbo-benzenes: Structure and conjugative properties

Author

Yulian M. Volovenko, Zoia Voitenko, Arnaud Rives, Iaroslav Baglai, Valérie Maraval, Cécile Barthes, Remi Chauvin, Nathalie Saffon-Merceron, Alix Saquet, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), and National Taras Shevchenko University of Kiev

Subjects
Crystal, Crystallography, Stereochemistry, Chemistry, Cyclohexadienes, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, Conjugated system, Chromophore, Electrochemistry, Spectral line
Abstract

International audience; Ideally Cs-/C2v-symmetric chromophores, constituted by two electro-active groups conjugated through the carbo-mer of the cyclohexa-1,3-diene core, are selectively prepared by the SnCl2-mediated reduction of tailored hexaoxy-[6]pericyclynes: in the latter substrates, one of the 1,4-dioxybut-2-yne edges is "chemically locked" by two CF3 substituents preventing complete reduction to the corresponding aromatic carbo-benzenic core, which is expected to be more "[small pi]-insulating" between the electro-active ends. The bis-trifluoromethylated carbo-cyclohexadiene products are also shown to be significantly stabilized with respect to their bis-phenylated analogues. Their structural (crystal X-ray diffraction analyses), spectroscopical (NMR and UV-vis spectra), physio-optical (dichromism in solution) and electrochemical (cyclic voltammograms) properties are compared on the basis of the electron-donating/electron-withdrawing nature of the substituents. These properties are also compared with those of their aromatic carbo-benzene and flexible carbo-n-butadiene counterparts.

Published
2015
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12. Functional carbo-butadienes: Nonaromatic conjugation effects through a 14-carbon, 24-pi-electron backbone

Author

Arnaud Rives, Valérie Maraval, Remi Chauvin, Nathalie Saffon-Merceron, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT-FR 2599), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)

Subjects
molecular wires, Stereochemistry, chemistry.chemical_element, Electron, 010402 general chemistry, Ring (chemistry), alkynes, 01 natural sciences, Catalysis, chemistry.chemical_compound, chromophores, Voltammetry, carbo-mers, cumulenes, 010405 organic chemistry, Chemistry, Aryl, Organic Chemistry, ring carbomers, mers, General Chemistry, aromaticity, Chromophore, 0104 chemical sciences, switches, derivatives, fluorescence, benzenes, Absorption (chemistry), homoaromaticity, Carbon, conjugation
Abstract

0947-6539; A systematic study of carbo-butadiene motifs not embedded in an aromatic carbo-benzene ring is described. Dibutatrienylacetylene (DBA) targets R-1 C(R)=C=C=C(Ph) C equivalent to C-C(Ph)=C=C=C(R)-R-2 are devised, in which R is C equivalent to CSiiPr(3) and R-1 and R-2 are R, H, or 4-X-C6H4, with the latter including three known representatives (X: H, NMe2, or NH2). The synthesis method is based on the SnCl2-mediated reduction of pentaynediols prepared by early or late divergent strategies; the latter allows access to a OMe-NO2 push-pull diaryl-DBA. If R-1 and R-2 are H, an over-reduced dialkynylbutatriene (DAB) with two allenyl caps was isolated instead of the unsubstituted DBA. If R-1 = R-2 = R, the tetraalkynyl-DBA target was obtained, along with an over-reduced DBA product with a 12-membered 1,2-alkylidene-1H(2),2H(2)-carbo-cyclobutadiene ring. X-ray crystallography shows that all of the acyclic DBAs adopt a planar trans-transoid-trans configuration. The maximum UV/Vis absorption wavelength is found to vary consistently with the overall pi-conjugation extent and, more intriguingly, with the p-donor character of the aryl X substituents, which varies consistently with the first (reversible) reduction potential and first (irreversible) oxidation peak, as determined by voltammetry.

Published
2014
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13. From Hexaoxy-[6]Pericyclynes to Carbo -Cyclohexadienes, Carbo -Benzenes, and Dihydro- Carbo -Benzenes: Synthesis, Structure, and Chromophoric and Redox Properties

Author

David Kieffer, Remi Chauvin, Christine Lepetit, Dmytro Kandaskalov, Léo Leroyer, Valérie Maraval, Nathalie Saffon-Merceron, Arnaud Rives, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT-FR 2599), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)

Subjects
Double bond, Stereochemistry, reduction, 010402 general chemistry, alkynes, 01 natural sciences, Catalysis, chemistry.chemical_compound, Electron affinity, dichromism, Molecular orbital, [CHIM.COOR]Chemical Sciences/Coordination chemistry, carbo-mers, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Aryl, Organic Chemistry, Aromaticity, General Chemistry, aromaticity, Chromophore, 0104 chemical sciences, NMR spectra database, Crystallography, Cyclic voltammetry
Abstract

International audience; When targeting the quadrupolar p-dianisyltetraphenyl-carbo-benzene by reductive treatment of a hexaoxy-[ 6]pericyclyne precursor 3 with SnCl2/HCl, a strict control of the conditions allowed for the isolation of three C18-macrocyclic products: the targeted aromatic carbo-benzene 1, a sub-reduced non-aromatic carbo-cyclohexadiene 4A, and an over-reduced aromatic dihydro-carbo-benzene 5A. Each of them was fully characterized by its absorption and NMR spectra, which were interpreted by comparison with calculated spectra from static structures optimized at the DFT level. According to the nucleus-independent chemical shift (NICS) value (NICS ≈ -13 ppm), the macrocyclic aromaticity of 5A is indicated to be equivalent to that of 1. This is confirmed by the strong NMR spectroscopic deshielding of the ortho- CH protons of the aryl substituents, but also by the strong shielding of the internal proton of the endocyclic trans- CH=CH double bond that results from the hydrogenation of one of the C≡C bonds of 3. Both the aromatics 1 and 5A exhibit a high crystallinity, revealed by SEM and TEM images, which allowed for a structural determination by using an X-ray microsource. A good agreement with calculated molecular structures was found, and columnar assemblies of the C18 macrocycles were evidenced in the crystal packing. The non-aromatic carbo-cyclohexadiene 4A is shown to be an intermediate in the formation of 1 from 3. It exhibits a remarkable dichromism in solution, which is related to the occurrence of two intense bands in the visible region of its UV/Vis spectrum. These properties could be attributed to the dibutatrienylacetylene(DBA) unit that occurs in the three chromophores, but which is not involved in a macrocyclic p-delocalization in 4A only. A versatile redox behavior of the carbo chromophores is evidenced by cyclic voltammetry and was analyzed by calculation of the ionization potential, electron affinity, and frontier molecular orbitals.

Published
2012
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