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Auteur Anne-Marie Caminade |
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Faire une suggestion Affiner la rechercheAmphiphilic fluorescent phosphorus dendrons : Synthesis, Characterisation, Applications in oncology / Jieru Qiu
Titre : Amphiphilic fluorescent phosphorus dendrons : Synthesis, Characterisation, Applications in oncology Type de document : texte imprimé Auteurs : Jieru Qiu, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Jean-Pierre Majoral, Directeur de thèse Langues : Anglais (eng) Tags : DENDRIMERS PHOSPHORUS NANOMEDICINE Résumé : "Nanotechnologies have the high potential to revolutionize various other classical technologies in many fields, due to the development of numerous nanodevice types, and have been intensively studied over the last decade. Among these nanoparticles, dendrimers and dendrons pertain to the "nano-world" by virtue of their size. Their nanometric sizes can be tailored as well, for instance, their multivalency and charges. Within the dendrimer space, phosphorus dendrimers and dendrons appear to be among the most useful dendritic systems due to the extraordinary reactivity and versatility of the phosphorus chemistry. In this thesis, we designed several families of original amphiphilic fluorescent phosphorus dendrons with interesting potential in the fields of nanomaterials and nanomedicine. Hexachlorocyclotriphosphazene used as a core was linked with five 4-hydroxybenzaldehyde and one monomer (pyrene and maleimide derivatives as fluorescent monomers and azabisdimethylphosphonate derivatives as non-fluorescent monomer). The dendrons were prepared up to generation 2 by a divergent method. The last step is the grafting of amino pyrrolidine or amino piperidine following by protonation with HCl to get the expected cationic amphiphilic fluorescent phosphorus dendrons. Their physical characterization were evaluated through numerous technics: NMR, UV, critical micelle concentration (CMC), dynamic light scattering (DLS), zeta potential, transmission electron microscopy (TEM), fluorescent spectra, circular dichroism and thermogravimetry. In a next step, the biological properties of the dendrons have been examined. The cytotoxicity of dendrons was determined using MTT test and Alamar Blue assay performed on eleven cells lines including both cancer cells and healthy cells (HL-60, HCT-116, A549, MCF7, PC3, U87, K562, K562R, MCR5, MDA-MB231 and HT-29 cells line). Hemolysis assays were used to test the effect of dendrons on the cell membrane. Their ability to bind genetic material was studied by gel electrophoresis using fluorescein-labeled small interference RNA siBCL-xL. Flow cytometry method was used to study the internalization of dendriplexes into tumor cells. In order to modulate the anticancer properties of the fluorescent dendrons, carbon quantum dots (CQDs) were chosen to conjugate with the pyrene dendrons in the presence of a cytotoxic agent like doxorubicin (DOX), physically loaded into 'micelles'. [...]"
Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 24/10/2019 Ecole_doctorale : Sciences de la Matière (SdM) ( Toulouse) Domaine : Chimie Macromoléculaire et Supramoléculaire En ligne : http://thesesups.ups-tlse.fr/4657/ Amphiphilic fluorescent phosphorus dendrons : Synthesis, Characterisation, Applications in oncology [texte imprimé] / Jieru Qiu, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Jean-Pierre Majoral, Directeur de thèse . - [s.d.].
Langues : Anglais (eng)
Tags : DENDRIMERS PHOSPHORUS NANOMEDICINE Résumé : "Nanotechnologies have the high potential to revolutionize various other classical technologies in many fields, due to the development of numerous nanodevice types, and have been intensively studied over the last decade. Among these nanoparticles, dendrimers and dendrons pertain to the "nano-world" by virtue of their size. Their nanometric sizes can be tailored as well, for instance, their multivalency and charges. Within the dendrimer space, phosphorus dendrimers and dendrons appear to be among the most useful dendritic systems due to the extraordinary reactivity and versatility of the phosphorus chemistry. In this thesis, we designed several families of original amphiphilic fluorescent phosphorus dendrons with interesting potential in the fields of nanomaterials and nanomedicine. Hexachlorocyclotriphosphazene used as a core was linked with five 4-hydroxybenzaldehyde and one monomer (pyrene and maleimide derivatives as fluorescent monomers and azabisdimethylphosphonate derivatives as non-fluorescent monomer). The dendrons were prepared up to generation 2 by a divergent method. The last step is the grafting of amino pyrrolidine or amino piperidine following by protonation with HCl to get the expected cationic amphiphilic fluorescent phosphorus dendrons. Their physical characterization were evaluated through numerous technics: NMR, UV, critical micelle concentration (CMC), dynamic light scattering (DLS), zeta potential, transmission electron microscopy (TEM), fluorescent spectra, circular dichroism and thermogravimetry. In a next step, the biological properties of the dendrons have been examined. The cytotoxicity of dendrons was determined using MTT test and Alamar Blue assay performed on eleven cells lines including both cancer cells and healthy cells (HL-60, HCT-116, A549, MCF7, PC3, U87, K562, K562R, MCR5, MDA-MB231 and HT-29 cells line). Hemolysis assays were used to test the effect of dendrons on the cell membrane. Their ability to bind genetic material was studied by gel electrophoresis using fluorescein-labeled small interference RNA siBCL-xL. Flow cytometry method was used to study the internalization of dendriplexes into tumor cells. In order to modulate the anticancer properties of the fluorescent dendrons, carbon quantum dots (CQDs) were chosen to conjugate with the pyrene dendrons in the presence of a cytotoxic agent like doxorubicin (DOX), physically loaded into 'micelles'. [...]"
Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 24/10/2019 Ecole_doctorale : Sciences de la Matière (SdM) ( Toulouse) Domaine : Chimie Macromoléculaire et Supramoléculaire En ligne : http://thesesups.ups-tlse.fr/4657/
Titre : Syntheses and biological applications of phosphorus dendrimers and dendrons Type de document : texte imprimé Auteurs : Liang Chen, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Xiangyang Shi, Directeur de thèse Langues : Anglais (eng) Tags : DENDRIMMER AMPHIPHILIC PHOSPHORUS DENDRONS NANOQUARIES GENE THERAPY NANOMEDICINE Résumé : "The aim of this work was to design several families of cationic phosphorus dendrimers and of neutral and cationic dendrons, and to investigate their potential in the field of biology/nanomedicine. Firstly, we revisited the cationic phosphorus dendrimers as a non-viral vector for gene delivery towards cancer therapy. The expression efficiency of genes was detected by fluorescence microscopy, flow cytometry, quantitative real time polymerase chain reaction (rt-qPCR) and Western blot assays. The results reveal that under the optimized conditions, the transfection of pDNA induces the significant p53 protein expression as verified through the resulting cell cycle arrest (regulation of p21 and Cdk4/Cyclin-D1 expression) and Western blotting. Moreover, the cancer gene therapy potential of the polyplexes was finally validated through therapy of a xenografted tumor model after intra-tumoral injection without systemic toxicity. In view of all the results already obtained, undoubtedly the use of cationic phosphorus dendrimers for biology holds great promises for the future. Secondly, the first-in-class Cu(II) and Au(III) metaled phosphorus dendrons (generation 1) bearing 10 Cu(II)Cl2 or [Au(III)Cl2]+ on their surface, and with C11 and C17 linear alkyl chains were synthesized. These dendrons showed significant antiproliferative activity against cancer cell lines such as 4T1 and MCF-7 (breast cancer). The best results concerning the antiproliferative activity to kill cancer cells were obtained with the Au(III) dendron complexes bearing short alkyl chain length. Cell death pathway analysis reveals that the metaled dendrons could alter the cell cycle- and apoptosis-related protein status of cells, resulting in cell cycle S-phase arrest and apoptosis. In particular, Au(III)-complexes induced the caspase-dependent cellular lethality by promoting the translocation of Bax to the mitochondria and the release of Cyto C, whereas the Cu(II)-complexes are weak activators of caspase-3, in line with their moderate antiproliferative activity in cancer cells. Taken together, these studies showed that these first-in-class metaled phosphorus dendrons represent a novel class of anticancer nanodrugs, and their development will open new avenues to tackle cancers. Lastly, we prepared the amphiphilic phosphorus dendron 1-C12G1 bearing a long linear alkyl chain (C12H25), and bearing ten protonated pyrrolidine groups in the surface. 1-C12G1 forms nanomicelles which allow to encapsulate anticancer drug DOX and complex the miR-21 inhibitor. Especially, the encapsulation efficiency of DOX can reach up to 83.60%. Meanwhile, gel retardation assay showed that the miR-21i complexed by 1-C12G1DOX were protected from degradation for up to 12 h and 24 h compared to the naked miR-21i.[...]" Document : Thèse de Doctorat Etablissement_delivrance : Toulouse 3 en cotutelle avec Donghua University (Shanghai, Chine) Date_soutenance : 31/08/2020 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie Macromoléculaire et Supramoléculaire En ligne : http://thesesups.ups-tlse.fr/4944/ Syntheses and biological applications of phosphorus dendrimers and dendrons [texte imprimé] / Liang Chen, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Xiangyang Shi, Directeur de thèse . - [s.d.].
Langues : Anglais (eng)
Tags : DENDRIMMER AMPHIPHILIC PHOSPHORUS DENDRONS NANOQUARIES GENE THERAPY NANOMEDICINE Résumé : "The aim of this work was to design several families of cationic phosphorus dendrimers and of neutral and cationic dendrons, and to investigate their potential in the field of biology/nanomedicine. Firstly, we revisited the cationic phosphorus dendrimers as a non-viral vector for gene delivery towards cancer therapy. The expression efficiency of genes was detected by fluorescence microscopy, flow cytometry, quantitative real time polymerase chain reaction (rt-qPCR) and Western blot assays. The results reveal that under the optimized conditions, the transfection of pDNA induces the significant p53 protein expression as verified through the resulting cell cycle arrest (regulation of p21 and Cdk4/Cyclin-D1 expression) and Western blotting. Moreover, the cancer gene therapy potential of the polyplexes was finally validated through therapy of a xenografted tumor model after intra-tumoral injection without systemic toxicity. In view of all the results already obtained, undoubtedly the use of cationic phosphorus dendrimers for biology holds great promises for the future. Secondly, the first-in-class Cu(II) and Au(III) metaled phosphorus dendrons (generation 1) bearing 10 Cu(II)Cl2 or [Au(III)Cl2]+ on their surface, and with C11 and C17 linear alkyl chains were synthesized. These dendrons showed significant antiproliferative activity against cancer cell lines such as 4T1 and MCF-7 (breast cancer). The best results concerning the antiproliferative activity to kill cancer cells were obtained with the Au(III) dendron complexes bearing short alkyl chain length. Cell death pathway analysis reveals that the metaled dendrons could alter the cell cycle- and apoptosis-related protein status of cells, resulting in cell cycle S-phase arrest and apoptosis. In particular, Au(III)-complexes induced the caspase-dependent cellular lethality by promoting the translocation of Bax to the mitochondria and the release of Cyto C, whereas the Cu(II)-complexes are weak activators of caspase-3, in line with their moderate antiproliferative activity in cancer cells. Taken together, these studies showed that these first-in-class metaled phosphorus dendrons represent a novel class of anticancer nanodrugs, and their development will open new avenues to tackle cancers. Lastly, we prepared the amphiphilic phosphorus dendron 1-C12G1 bearing a long linear alkyl chain (C12H25), and bearing ten protonated pyrrolidine groups in the surface. 1-C12G1 forms nanomicelles which allow to encapsulate anticancer drug DOX and complex the miR-21 inhibitor. Especially, the encapsulation efficiency of DOX can reach up to 83.60%. Meanwhile, gel retardation assay showed that the miR-21i complexed by 1-C12G1DOX were protected from degradation for up to 12 h and 24 h compared to the naked miR-21i.[...]" Document : Thèse de Doctorat Etablissement_delivrance : Toulouse 3 en cotutelle avec Donghua University (Shanghai, Chine) Date_soutenance : 31/08/2020 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie Macromoléculaire et Supramoléculaire En ligne : http://thesesups.ups-tlse.fr/4944/
Titre : Synthèse de mannodendrimères, analogues de la structure supramoléculaire du lipoarabinomannane mannosylé (ManLAM) et étude de leurs propriétés anti-inflammatoires Type de document : texte imprimé Auteurs : Emilyne Blattes, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Germain Puzo, Directeur de thèse Langues : Français (fre) Tags : MANLAM MANNODENDRIMERS DC-SIGN ANTI-INFLAMMATORY Résumé : "Le lipoarabinomannane mannosylé (ManLAM) est un lipoglycanne de l'enveloppe cellulaire de M. tuberculosis. Depuis une décennie, nous savons que ce lipoglycanne isolé possède in vitro et in vivo des propriétés anti-inflammatoires. Ce composé est capable d'inhiber la production d'L-12 et de TNF-alpha, par des cellules dendritiques humaines (DCs) stimulées au LPS. In vitro, l'activité de ce lipoglycanne est corrélée au récepteur DC-SIGN (dendritic cell-specific ICAM-3 grabbing non-integrin, une lectine de type C retrouvée à la membrane des DCs. Il prévient également, in vivo, le désordre respiratoire causé par l'asthme allergique chez la souris. Structuralement, le ManLAM est une macromolécule amphiphile (17kDa) composée d'une ancre mannosyl-phosphatidyl-myo-inositol (MPI) sur laquelle est greffé un squelette polysaccharidique. Ce dernier porte à ses extrémités des coiffes oligomannosylées de type mono-, di- et trimannosides d'enchainement alpha(1 dans 2). L'ancre MPI et les coiffes mannosylées sont les déterminants structuraux indispensables à l'activité du ManLAM, in vitro et in vivo. L'ancre MPI permet l'agrégation en solution des molécules de ManLAM, en micelle de 30 nm de diamètre où à leur surface, serait présenté les coiffes oligomannosylées. Il apparaît donc que la forme supramoléculaire du ManLAM en solution soit la forme bioactive immunomodulatrice. Le travail de thèse concerne la synthèse de dendrimères mannosylés mimes de l'organisation supramoléculaire du ManLAM en solution, présentant des propriétés anti-inflammatoires similaires. Les dendrimères sont des macromolécules synthétiques hyperbranchées et monodisperses, issus d'une synthèse organique extrêmement contrôlée. Nous avons utilisés dans ce projet des dendrimères phosphorés comme un équivalent du cœur de la micelle de ManLAM, à la surface desquels sont greffés différents oligomannosides de synthèse, identiques aux coiffes du ManLAM. Nous avons synthétisé 8 dendrimères mannosylés, de quatre tailles différentes (de la 1er (Gc1) à la 4ème (Gc4) génération) avec des Mono-, des Di- ou des Trimannosides à la surface. Cette synthèse multi-étapes est maitrisée et générale, et permet d'obtenir des quantités de molécules hydrosolubles compatibles avec des essais biologiques. De plus, ces mannodendrimères sont tous des ligands du récepteur DC-SIGN soit sous forme soluble soit sous forme membranaire. Cette étude fait émerger les composés Gc3Di, Gc4Di et Gc3Tri comme des ligands de haute affinité pour DC-SIGN, affinité comparable à celle de la forme supramoléculaire du ManLAM. Ces mannodendrimères semblent être spécifiques de DC-SIGN, du fait de la faible liaison de Gc4DiF, homologue fluorescent de Gc4Di, aux récepteurs SIGNR3 et MR. Gc3Tri et Gc4Di présentent également un caractère anti-inflammatoire ex vivo. Lors d'une co-incubation de DCs avec le LPS et Gc3Tri ou Gc4Di nous avons observé une inhibition de la production de TNF-alpha par ces cellules. Comme le ManLAM, cette inhibition est dose-dépendante et annihilée, pour Gc3Tri, par un anticorps bloquant DC-SIGN. Enfin, le mannodendrimère Gc3Tri prévient l'inflammation des poumons murins induite par inhalation de LPS, comme le ManLAM. Ces résultats prometteurs nous permettent de penser que Gc3Tri correspond à un mime synthétique de la forme bioactive du ManLAM, à la fois in vitro mais aussi in vivo." Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 Date_soutenance : 30/11/2010 Ecole_doctorale : Biologie, santé, biotechnologies (BSB) Domaine : Biochimie structurale et fonctionnelle En ligne : http://thesesups.ups-tlse.fr/1275/ Synthèse de mannodendrimères, analogues de la structure supramoléculaire du lipoarabinomannane mannosylé (ManLAM) et étude de leurs propriétés anti-inflammatoires [texte imprimé] / Emilyne Blattes, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Germain Puzo, Directeur de thèse . - [s.d.].
Langues : Français (fre)
Tags : MANLAM MANNODENDRIMERS DC-SIGN ANTI-INFLAMMATORY Résumé : "Le lipoarabinomannane mannosylé (ManLAM) est un lipoglycanne de l'enveloppe cellulaire de M. tuberculosis. Depuis une décennie, nous savons que ce lipoglycanne isolé possède in vitro et in vivo des propriétés anti-inflammatoires. Ce composé est capable d'inhiber la production d'L-12 et de TNF-alpha, par des cellules dendritiques humaines (DCs) stimulées au LPS. In vitro, l'activité de ce lipoglycanne est corrélée au récepteur DC-SIGN (dendritic cell-specific ICAM-3 grabbing non-integrin, une lectine de type C retrouvée à la membrane des DCs. Il prévient également, in vivo, le désordre respiratoire causé par l'asthme allergique chez la souris. Structuralement, le ManLAM est une macromolécule amphiphile (17kDa) composée d'une ancre mannosyl-phosphatidyl-myo-inositol (MPI) sur laquelle est greffé un squelette polysaccharidique. Ce dernier porte à ses extrémités des coiffes oligomannosylées de type mono-, di- et trimannosides d'enchainement alpha(1 dans 2). L'ancre MPI et les coiffes mannosylées sont les déterminants structuraux indispensables à l'activité du ManLAM, in vitro et in vivo. L'ancre MPI permet l'agrégation en solution des molécules de ManLAM, en micelle de 30 nm de diamètre où à leur surface, serait présenté les coiffes oligomannosylées. Il apparaît donc que la forme supramoléculaire du ManLAM en solution soit la forme bioactive immunomodulatrice. Le travail de thèse concerne la synthèse de dendrimères mannosylés mimes de l'organisation supramoléculaire du ManLAM en solution, présentant des propriétés anti-inflammatoires similaires. Les dendrimères sont des macromolécules synthétiques hyperbranchées et monodisperses, issus d'une synthèse organique extrêmement contrôlée. Nous avons utilisés dans ce projet des dendrimères phosphorés comme un équivalent du cœur de la micelle de ManLAM, à la surface desquels sont greffés différents oligomannosides de synthèse, identiques aux coiffes du ManLAM. Nous avons synthétisé 8 dendrimères mannosylés, de quatre tailles différentes (de la 1er (Gc1) à la 4ème (Gc4) génération) avec des Mono-, des Di- ou des Trimannosides à la surface. Cette synthèse multi-étapes est maitrisée et générale, et permet d'obtenir des quantités de molécules hydrosolubles compatibles avec des essais biologiques. De plus, ces mannodendrimères sont tous des ligands du récepteur DC-SIGN soit sous forme soluble soit sous forme membranaire. Cette étude fait émerger les composés Gc3Di, Gc4Di et Gc3Tri comme des ligands de haute affinité pour DC-SIGN, affinité comparable à celle de la forme supramoléculaire du ManLAM. Ces mannodendrimères semblent être spécifiques de DC-SIGN, du fait de la faible liaison de Gc4DiF, homologue fluorescent de Gc4Di, aux récepteurs SIGNR3 et MR. Gc3Tri et Gc4Di présentent également un caractère anti-inflammatoire ex vivo. Lors d'une co-incubation de DCs avec le LPS et Gc3Tri ou Gc4Di nous avons observé une inhibition de la production de TNF-alpha par ces cellules. Comme le ManLAM, cette inhibition est dose-dépendante et annihilée, pour Gc3Tri, par un anticorps bloquant DC-SIGN. Enfin, le mannodendrimère Gc3Tri prévient l'inflammation des poumons murins induite par inhalation de LPS, comme le ManLAM. Ces résultats prometteurs nous permettent de penser que Gc3Tri correspond à un mime synthétique de la forme bioactive du ManLAM, à la fois in vitro mais aussi in vivo." Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 Date_soutenance : 30/11/2010 Ecole_doctorale : Biologie, santé, biotechnologies (BSB) Domaine : Biochimie structurale et fonctionnelle En ligne : http://thesesups.ups-tlse.fr/1275/
Titre : Multifunctional water-soluble phosphorus dendrimers Type de document : texte imprimé Auteurs : Edwin, Ronald De Jonge, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Jean-Pierre Majoral, Directeur de thèse ; W. Knoll, Directeur de thèse Langues : Allemand (ger) Résumé : "Dendrimers are polymeric macromolecules with a regularly branched structure and are synthesised in an iterative fashion. Due to their monodispersity, well-defined shape and extremely high functionality, dendrimers are ideal nano-sized objects for functional and biocompatible surface coatings, biosensing and biomedicine. This dissertation describes the
synthesis of ten novel water-soluble phosphorus containing dendrimers and their application in different biological and biomimetic systems. The dendrimers can be divided into two classes; the first type contains either a ferrocene at the core or 24 ferrocenes in the branches. They showed reversible reduction-oxidation behaviour and might be applied in electronic multilayered architectures. Dendrimers of the second class carry a dithiolane functionalised core that can strongly bind to noble metals, like gold substrates. Although such dendrimer coated substrates were unable to tether defect-free lipid bilayer membranes, the coatings were successfully applied for culturing Human Osteoblast cells. The cell adhesion to a coating of polycationic dendrimers was so strong that cell division could not take place, specifically evoking apoptosis. The polyanionic dendrimers, however, promoted excellent cell adhesion and proliferation. Therefore, the practical application of such macromolecular architectures can be envisioned, such as in dendrimer coatings for tissue engineering and or medical implants."
"Dendrimere sind polymere Makromoleküle mit einer wohl definiertenStruktur. Dank ihrer Monodispersität, hohen Verästelung und sehr hohen Funktionalität sind Dendrimere ideale nanoskopische Objekte für die Beschichtung von hochfunktionellen, biokompatibelen Oberflächen zur Anwendung in Biosensorik und Biomedizin. Im Rahmen dieser Dissertation wurden zehn neue wasserlösliche phosphorhaltige Dendrimere synthetisiert. Mögliche Anwendungen in biologischen und biomimetischen Systemen wurden untersucht und diskutiert. Die synthetisierten Dendrimere können in zwei Klassen unterteilt werden. Dendrimere der ersten Klasse tragen entweder zentral ein Ferrocen oder insgesamt 24 Ferrocen-Moleküle in den Ästen. Diese Denrimere zeigen ein reversibles Reduktions- und Oxidationsverhalten und könnten damit in elektronische Multischichtsysteme inkorporiert werden. Dendrimere der zweiten Klasse tragen ein Dithiolan im Zentrum. Somit
konnten Edelmetalle, wie zum Beispiel Goldoberflächen, mit einer Dendrimerschicht funktionalisiert werden. Die erhaltenen Strukturen konnten leider nicht die Bildung einer defektfreien Lipidmembrane
unterstützen. Sie förderten allerdings die Adhäsion humaner Osteoblastzellen. Die Zelladhäsion auf Schichten aus polykationischen Dendrimeren war so stark, dass Zellteilung nicht länger möglich war und sogar spezifisch Apoptose hervorrief. Polyanionische Dendrimere dagegen führten zu exzellenter
Zelladhesion und -proliferation. Die erhaltenen makromolekularen Architekturen können somit als mögliche Oberflächenbeschichtungen, zum Beispiel für Humanimplantate, Anwendung finden."
Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 et Die vorliegende Arbeit wurde in der Zeit von April 2007 bis März 2010 am Laboratoire de Chimie de Coordination (CNRS, Toulouse, et Université de Mainz (Allemagne) Date_soutenance : 30/03/2010 Ecole_doctorale : L’Université Johannes Gutenberg à Mayence, Département de Biologie Domaine : Sciences naturelles, Biologie En ligne : https://openscience.ub.uni-mainz.de/handle/20.500.12030/2255 Multifunctional water-soluble phosphorus dendrimers [texte imprimé] / Edwin, Ronald De Jonge, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Jean-Pierre Majoral, Directeur de thèse ; W. Knoll, Directeur de thèse . - [s.d.].
Langues : Allemand (ger)
Résumé : "Dendrimers are polymeric macromolecules with a regularly branched structure and are synthesised in an iterative fashion. Due to their monodispersity, well-defined shape and extremely high functionality, dendrimers are ideal nano-sized objects for functional and biocompatible surface coatings, biosensing and biomedicine. This dissertation describes the
synthesis of ten novel water-soluble phosphorus containing dendrimers and their application in different biological and biomimetic systems. The dendrimers can be divided into two classes; the first type contains either a ferrocene at the core or 24 ferrocenes in the branches. They showed reversible reduction-oxidation behaviour and might be applied in electronic multilayered architectures. Dendrimers of the second class carry a dithiolane functionalised core that can strongly bind to noble metals, like gold substrates. Although such dendrimer coated substrates were unable to tether defect-free lipid bilayer membranes, the coatings were successfully applied for culturing Human Osteoblast cells. The cell adhesion to a coating of polycationic dendrimers was so strong that cell division could not take place, specifically evoking apoptosis. The polyanionic dendrimers, however, promoted excellent cell adhesion and proliferation. Therefore, the practical application of such macromolecular architectures can be envisioned, such as in dendrimer coatings for tissue engineering and or medical implants."
"Dendrimere sind polymere Makromoleküle mit einer wohl definiertenStruktur. Dank ihrer Monodispersität, hohen Verästelung und sehr hohen Funktionalität sind Dendrimere ideale nanoskopische Objekte für die Beschichtung von hochfunktionellen, biokompatibelen Oberflächen zur Anwendung in Biosensorik und Biomedizin. Im Rahmen dieser Dissertation wurden zehn neue wasserlösliche phosphorhaltige Dendrimere synthetisiert. Mögliche Anwendungen in biologischen und biomimetischen Systemen wurden untersucht und diskutiert. Die synthetisierten Dendrimere können in zwei Klassen unterteilt werden. Dendrimere der ersten Klasse tragen entweder zentral ein Ferrocen oder insgesamt 24 Ferrocen-Moleküle in den Ästen. Diese Denrimere zeigen ein reversibles Reduktions- und Oxidationsverhalten und könnten damit in elektronische Multischichtsysteme inkorporiert werden. Dendrimere der zweiten Klasse tragen ein Dithiolan im Zentrum. Somit
konnten Edelmetalle, wie zum Beispiel Goldoberflächen, mit einer Dendrimerschicht funktionalisiert werden. Die erhaltenen Strukturen konnten leider nicht die Bildung einer defektfreien Lipidmembrane
unterstützen. Sie förderten allerdings die Adhäsion humaner Osteoblastzellen. Die Zelladhäsion auf Schichten aus polykationischen Dendrimeren war so stark, dass Zellteilung nicht länger möglich war und sogar spezifisch Apoptose hervorrief. Polyanionische Dendrimere dagegen führten zu exzellenter
Zelladhesion und -proliferation. Die erhaltenen makromolekularen Architekturen können somit als mögliche Oberflächenbeschichtungen, zum Beispiel für Humanimplantate, Anwendung finden."
Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 et Die vorliegende Arbeit wurde in der Zeit von April 2007 bis März 2010 am Laboratoire de Chimie de Coordination (CNRS, Toulouse, et Université de Mainz (Allemagne) Date_soutenance : 30/03/2010 Ecole_doctorale : L’Université Johannes Gutenberg à Mayence, Département de Biologie Domaine : Sciences naturelles, Biologie En ligne : https://openscience.ub.uni-mainz.de/handle/20.500.12030/2255
Titre : Specifically functionalized dendrimers for catalysis in special media Type de document : texte imprimé Auteurs : Massimo Petriccone, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Rosa Maria Sebastian Perez, Directeur de thèse Langues : Anglais (eng) Tags : DENDRIMERS CATALYSIS PERFLUORINATED SUPERCRITICAL CO2 Résumé : "The presented research represents a comprehensive exploration of phosphorhydrazone (PPH) dendrimers, delving into their synthesis, functionalization, and catalytic applications, with a specific focus on para-substituted phenols for surface functionalization. The synthesis process entails a meticulous two-step reaction sequence, initiating from chlorinated phosphorus atoms in the core and progressing through substitution with 4-hydroxybenzaldehyde, ultimately culminating in dendrimer generation through condensation with MMHP(S)Cl2. To enable subsequent metal introduction were synthesized different phenolic derivates, alongside a model molecule designed to emulate iminophosphine reactivity while addressing phosphine oxidation concerns. The synthesis of bidentate phenols was described in detail, emphasizing the challenges faced and optimizations made, with a particular focus on the scalability of the procedures. The research also explores the modification of dendrimer surfaces to enhance solubility, with a specific emphasis on integrating perfluorinated ligands. Despite challenges in overall yield, alternative synthetic pathways were considered, resulting in the successful synthesis of phenols functionalized in the para position with alkylpolyfluorinated chains of varying lengths. Moving on to the characterization of PPH dendrimers, the study begins with the preparation of (1-methylhydrazineyl)phosphonothioic dichloride (MMHP(S)Cl2). Model molecules were synthesized to simulate PPH dendrimer surfaces, progressing to higher dendrimer generations. Distinctive features of PPH dendrimers, including their identification through 31P-NMR, were highlighted. A significant challenge in this phase involved ensuring the scalability of PPH dendrimer synthesis, which was successfully overcome. The research then shifts its focus to the precise functionalization of PPH dendrimers with previously synthesized phenolic substituents. The objective was to minimize di-symmetric substitution during the precise di-functionalization of the P(S)Cl2 function. Catalyst synthesis involved ligands with metal complexation for stability. Both precisely and stochastically substituted PPH dendrimers were successfully scaled up to the gram scale. In the final segment, the research delves into the catalytic activity of dendrimeric catalysts in various coupling reactions, both in organic and non-conventional solvents. Stille cross-coupling, Heck cross-coupling, and Suzuki coupling reactions were explored. The dendrimeric catalyst exhibited heightened activity in the Stille cross-coupling, showcasing a positive multivalence and generation dendritic effect. Despite insolubility in scCO2, the catalyst demonstrated activity for the Stille cross-coupling in heterogeneous conditions, emphasizing a positive generation dendritic effect. Additionally, the dendrimeric catalyst showed activity for the Heck cross-coupling in a biphasic fluorous/organic system. The study also addresses challenges associated with catalyst recovery in both organic and non-conventional solvents. Comparisons between precisely and stochastically difunctionalized dendrimers underscore positive multivalence and generation dendritic effects in specific reactions. Notably, higher activity of precisely substituted dendrimers from generation 1 to 3 compared to stochastically substituted homologues was demonstrated in the Stille cross-coupling. In summary, this research provides a thorough examination of dendrimer synthesis, functionalization, and catalytic applications, offering valuable insights and suggesting avenues for future refinement in sustainable catalytic processes."
Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 en cotutelle avec Universitat autònoma de Barcelona Date_soutenance : 01/03/2024 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie Macromoléculaire et Supramoléculaire En ligne : https://theses.fr/2024TLSES048 Specifically functionalized dendrimers for catalysis in special media [texte imprimé] / Massimo Petriccone, Auteur ; Anne-Marie Caminade, Directeur de thèse ; Rosa Maria Sebastian Perez, Directeur de thèse . - [s.d.].
Langues : Anglais (eng)
Tags : DENDRIMERS CATALYSIS PERFLUORINATED SUPERCRITICAL CO2 Résumé : "The presented research represents a comprehensive exploration of phosphorhydrazone (PPH) dendrimers, delving into their synthesis, functionalization, and catalytic applications, with a specific focus on para-substituted phenols for surface functionalization. The synthesis process entails a meticulous two-step reaction sequence, initiating from chlorinated phosphorus atoms in the core and progressing through substitution with 4-hydroxybenzaldehyde, ultimately culminating in dendrimer generation through condensation with MMHP(S)Cl2. To enable subsequent metal introduction were synthesized different phenolic derivates, alongside a model molecule designed to emulate iminophosphine reactivity while addressing phosphine oxidation concerns. The synthesis of bidentate phenols was described in detail, emphasizing the challenges faced and optimizations made, with a particular focus on the scalability of the procedures. The research also explores the modification of dendrimer surfaces to enhance solubility, with a specific emphasis on integrating perfluorinated ligands. Despite challenges in overall yield, alternative synthetic pathways were considered, resulting in the successful synthesis of phenols functionalized in the para position with alkylpolyfluorinated chains of varying lengths. Moving on to the characterization of PPH dendrimers, the study begins with the preparation of (1-methylhydrazineyl)phosphonothioic dichloride (MMHP(S)Cl2). Model molecules were synthesized to simulate PPH dendrimer surfaces, progressing to higher dendrimer generations. Distinctive features of PPH dendrimers, including their identification through 31P-NMR, were highlighted. A significant challenge in this phase involved ensuring the scalability of PPH dendrimer synthesis, which was successfully overcome. The research then shifts its focus to the precise functionalization of PPH dendrimers with previously synthesized phenolic substituents. The objective was to minimize di-symmetric substitution during the precise di-functionalization of the P(S)Cl2 function. Catalyst synthesis involved ligands with metal complexation for stability. Both precisely and stochastically substituted PPH dendrimers were successfully scaled up to the gram scale. In the final segment, the research delves into the catalytic activity of dendrimeric catalysts in various coupling reactions, both in organic and non-conventional solvents. Stille cross-coupling, Heck cross-coupling, and Suzuki coupling reactions were explored. The dendrimeric catalyst exhibited heightened activity in the Stille cross-coupling, showcasing a positive multivalence and generation dendritic effect. Despite insolubility in scCO2, the catalyst demonstrated activity for the Stille cross-coupling in heterogeneous conditions, emphasizing a positive generation dendritic effect. Additionally, the dendrimeric catalyst showed activity for the Heck cross-coupling in a biphasic fluorous/organic system. The study also addresses challenges associated with catalyst recovery in both organic and non-conventional solvents. Comparisons between precisely and stochastically difunctionalized dendrimers underscore positive multivalence and generation dendritic effects in specific reactions. Notably, higher activity of precisely substituted dendrimers from generation 1 to 3 compared to stochastically substituted homologues was demonstrated in the Stille cross-coupling. In summary, this research provides a thorough examination of dendrimer synthesis, functionalization, and catalytic applications, offering valuable insights and suggesting avenues for future refinement in sustainable catalytic processes."
Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 en cotutelle avec Universitat autònoma de Barcelona Date_soutenance : 01/03/2024 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie Macromoléculaire et Supramoléculaire En ligne : https://theses.fr/2024TLSES048
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