Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica
ROS (Reactive Oxygen Species), such as H2O2, HO● and O2-●, are naturally produced by the metabolism of living beings. However, they can appear in large quantities in the case of certain diseases (Alzheimer's, Parkinson's, sclerosis, cancer). Overproduction of ROS leads to higher cell morta...
| Autor: | |
|---|---|
| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2018 |
| País: | España |
| Institución: | CBUC, CESCA |
| Repositorio: | TDR. Tesis Doctorales en Red |
| OAI Identifier: | oai:www.tdx.cat:10803/666907 |
| Acceso en línea: | http://hdl.handle.net/10803/666907 |
| Access Level: | acceso abierto |
| Palabra clave: | Nanociència Nanociencia Nanoscience Nanopartícules Nanopartículas Nanoparticles Compostos de coordinació Compuestos de coordinación Coordination compounds Manganès Manganeso Manganese Sílice Silica Ciències Experimentals i Matemàtiques 54 |
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Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica |
| title |
Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica |
| spellingShingle |
Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica Turquet, François-Xavier Nanociència Nanociencia Nanoscience Nanopartícules Nanopartículas Nanoparticles Compostos de coordinació Compuestos de coordinación Coordination compounds Manganès Manganeso Manganese Sílice Silica Ciències Experimentals i Matemàtiques 54 |
| title_short |
Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica |
| title_full |
Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica |
| title_fullStr |
Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica |
| title_full_unstemmed |
Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica |
| title_sort |
Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silica |
| dc.creator.none.fl_str_mv |
Turquet, François-Xavier |
| author |
Turquet, François-Xavier |
| author_facet |
Turquet, François-Xavier |
| author_role |
author |
| dc.contributor.none.fl_str_mv |
Corbella i Cordomí, Montserrat Albela Castrillo, Mª Belén Corbella i Cordomí, Montserrat Universitat de Barcelona. Facultat de Física |
| dc.subject.none.fl_str_mv |
Nanociència Nanociencia Nanoscience Nanopartícules Nanopartículas Nanoparticles Compostos de coordinació Compuestos de coordinación Coordination compounds Manganès Manganeso Manganese Sílice Silica Ciències Experimentals i Matemàtiques 54 |
| topic |
Nanociència Nanociencia Nanoscience Nanopartícules Nanopartículas Nanoparticles Compostos de coordinació Compuestos de coordinación Coordination compounds Manganès Manganeso Manganese Sílice Silica Ciències Experimentals i Matemàtiques 54 |
| description |
ROS (Reactive Oxygen Species), such as H2O2, HO● and O2-●, are naturally produced by the metabolism of living beings. However, they can appear in large quantities in the case of certain diseases (Alzheimer's, Parkinson's, sclerosis, cancer). Overproduction of ROS leads to higher cell mortality. Some microorganisms have an Mn-based enzyme capable of catalyzing the disproportionation reaction of H2O2 into O2 and H2O. Several molecules have been synthesized to reproduce this process, however very few of them are active in aqueous environment. Recently, polynuclear synthetic Mn species have been introduced into mesoporous silica to protect them from the environment. Thus, these complexes of Mn are stable and even see their catalytic activity increase. In order to persevere in this way, this thesis presents new compounds of formula [Mn(bpy)(AntCO2)2]n and [{Mn(bpy)(AntCO2)}2(µ-AntCO2)2(µ-OH2)] for MnII (chain and dinuclear respectively) and [Mn4O2(AntCO2)6(bpy)2(ClO4)2] for MnIII (tetranuclear) based on this concept. These compounds have two types of ligands, 2,2'-bipyridine, commonly found for similar compounds and 9-anthracene carboxylate, a fluorescent ligand added for theragnostic purposes. The resolution of the crystal structure of the MnII dinuclear compound shows a compression along the axis on the direction of the monodentate anthracene carboxylate. Moreover, by hydrolysis the one- dimensional system can be converted to the dinuclear compound. In the synthesis of the Mn(III) compound some oxidation of the anthracene is observed and two organic compounds are obtained, an anthraquinone and an ester formed by reaction between the quinone and the carboxylate. The manganese compounds were inserted into silica nanoparticles (NPs), resol (a polyphenol resin) -silica and carbon-silica hybrids in order to allow their vectorization and to study the compatibility of hybrid NPs with this type of system. This work explores the magnetic properties of the complexes and the luminescent properties of the coordination compounds and materials. The Mn(II) compounds show weak antiferromagnetic interaction, and the best way to differentiate these compounds is by EPR spectroscopy: the chain shows a unique band at g~2 while for the dinculear compound the spectrum is more complex, with several features at low fields. Magnetic properties of the Mn(III) compound confirms that it is a tetranuclear with butterfly type geometry with stronger antiferromagnetic interaction between the central ions than between central-terminal ions. The study of the porosity of the materials and the quantification of the presence of manganese inside the materials shows a good incorporation rate of the compounds. However it seems that the compounds are not present homogenously inside the support and that they are broken into smaller units. This is confirmed with the study of the magnetic properties of the hybrid [Mn]@NPs materials. In addition, fluoresecence measurement show that both the support and the compounds are luminescent but that both emission are strongly quenched when the compounds are inside the nanoparticles. The study of the optic properties of the materials show that a large amount of the compounds is released when the loaded silica and carbon-silica nanoparticles are redispersed in ethanol. However, resol-silica nanoparticles seem a lot more efficient to retain the complexes inside and apparently do not need further functionalization to achieve this goal. Finally, some preliminary test of disproportionation of H2O2 catalyzed by the manganese systems show low to moderate activity of Mn compounds in acetonitrile and paves the way for optimizing hybrid systems in aqueous media. |
| publishDate |
2018 |
| dc.date.none.fl_str_mv |
2018 2019 2020 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/doctoralThesis info:eu-repo/semantics/publishedVersion |
| format |
doctoralThesis |
| status_str |
publishedVersion |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10803/666907 |
| url |
http://hdl.handle.net/10803/666907 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess |
| eu_rights_str_mv |
openAccess |
| dc.format.none.fl_str_mv |
216 p. application/pdf application/pdf |
| dc.publisher.none.fl_str_mv |
Universitat de Barcelona |
| publisher.none.fl_str_mv |
Universitat de Barcelona |
| dc.source.none.fl_str_mv |
TDX (Tesis Doctorals en Xarxa) reponame:TDR. Tesis Doctorales en Red instname:CBUC, CESCA |
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CBUC, CESCA |
| reponame_str |
TDR. Tesis Doctorales en Red |
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TDR. Tesis Doctorales en Red |
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|
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1869405416916516864 |
| spelling |
Insertion of fluorescent manganese compounds - models of catalase - into mesoporous nanoparticles of silica, resol-silica and carbon-silicaTurquet, François-XavierNanociènciaNanocienciaNanoscienceNanopartículesNanopartículasNanoparticlesCompostos de coordinacióCompuestos de coordinaciónCoordination compoundsManganèsManganesoManganeseSíliceSilicaCiències Experimentals i Matemàtiques54ROS (Reactive Oxygen Species), such as H2O2, HO● and O2-●, are naturally produced by the metabolism of living beings. However, they can appear in large quantities in the case of certain diseases (Alzheimer's, Parkinson's, sclerosis, cancer). Overproduction of ROS leads to higher cell mortality. Some microorganisms have an Mn-based enzyme capable of catalyzing the disproportionation reaction of H2O2 into O2 and H2O. Several molecules have been synthesized to reproduce this process, however very few of them are active in aqueous environment. Recently, polynuclear synthetic Mn species have been introduced into mesoporous silica to protect them from the environment. Thus, these complexes of Mn are stable and even see their catalytic activity increase. In order to persevere in this way, this thesis presents new compounds of formula [Mn(bpy)(AntCO2)2]n and [{Mn(bpy)(AntCO2)}2(µ-AntCO2)2(µ-OH2)] for MnII (chain and dinuclear respectively) and [Mn4O2(AntCO2)6(bpy)2(ClO4)2] for MnIII (tetranuclear) based on this concept. These compounds have two types of ligands, 2,2'-bipyridine, commonly found for similar compounds and 9-anthracene carboxylate, a fluorescent ligand added for theragnostic purposes. The resolution of the crystal structure of the MnII dinuclear compound shows a compression along the axis on the direction of the monodentate anthracene carboxylate. Moreover, by hydrolysis the one- dimensional system can be converted to the dinuclear compound. In the synthesis of the Mn(III) compound some oxidation of the anthracene is observed and two organic compounds are obtained, an anthraquinone and an ester formed by reaction between the quinone and the carboxylate. The manganese compounds were inserted into silica nanoparticles (NPs), resol (a polyphenol resin) -silica and carbon-silica hybrids in order to allow their vectorization and to study the compatibility of hybrid NPs with this type of system. This work explores the magnetic properties of the complexes and the luminescent properties of the coordination compounds and materials. The Mn(II) compounds show weak antiferromagnetic interaction, and the best way to differentiate these compounds is by EPR spectroscopy: the chain shows a unique band at g~2 while for the dinculear compound the spectrum is more complex, with several features at low fields. Magnetic properties of the Mn(III) compound confirms that it is a tetranuclear with butterfly type geometry with stronger antiferromagnetic interaction between the central ions than between central-terminal ions. The study of the porosity of the materials and the quantification of the presence of manganese inside the materials shows a good incorporation rate of the compounds. However it seems that the compounds are not present homogenously inside the support and that they are broken into smaller units. This is confirmed with the study of the magnetic properties of the hybrid [Mn]@NPs materials. In addition, fluoresecence measurement show that both the support and the compounds are luminescent but that both emission are strongly quenched when the compounds are inside the nanoparticles. The study of the optic properties of the materials show that a large amount of the compounds is released when the loaded silica and carbon-silica nanoparticles are redispersed in ethanol. However, resol-silica nanoparticles seem a lot more efficient to retain the complexes inside and apparently do not need further functionalization to achieve this goal. Finally, some preliminary test of disproportionation of H2O2 catalyzed by the manganese systems show low to moderate activity of Mn compounds in acetonitrile and paves the way for optimizing hybrid systems in aqueous media.Universitat de BarcelonaCorbella i Cordomí, MontserratAlbela Castrillo, Mª BelénCorbella i Cordomí, MontserratUniversitat de Barcelona. Facultat de Física201920202018info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersion216 p.application/pdfapplication/pdfhttp://hdl.handle.net/10803/666907TDX (Tesis Doctorals en Xarxa)reponame:TDR. Tesis Doctorales en Redinstname:CBUC, CESCAInglésADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs.info:eu-repo/semantics/openAccessoai:www.tdx.cat:10803/6669072026-06-14T12:46:07Z |
| score |
15.300724 |