Made available in DSpace on 2014-10-09T12:55:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:00Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Orientador: Maria Isabel Felisberti / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-05T05:18:11Z (GMT). No. of bitstreams: 1 Hanamoto_LilianSatomi_D.pdf: 13319819 bytes, checksum: 0e6b63b39a199cc970951da7436dd7f6 (MD5) Previous issue date: 2005 / Doutorado / Físico-Química / Doutor em Ciências

Made available in DSpace on 2014-10-09T12:55:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:00Z (GMT). No. of bitstreams: 0 / Neste trabalho foi estudada a estrutura cristalina do composto supercondutor cerâmico de alta temperatura crítica de fórmula nominal Hg0,82Re0,18Ba2Ca2Cu3O8 + e fórmula geral Hg,Re-1223, com diferentes teores de oxigênio, pela técnica de difração de raios X, empregando o método de Rietveld. As amostras estudadas apresentam diferentes teores de oxigênio pois, durante o processo de síntese, foram tratadas com misturas gasosas oxigênio/argônio nas proporções: 5:95, 10:90 e 15:85. Os resultados do refinamento estrutural das amostras demonstram que diferentes graus de oxigenação implicam em diferentes parâmetros de rede, posições e distâncias atômicas das fases presentes em cada amostra. Confirmou-se, nas amostras estudadas, a segregação de duas fases supercondutoras com a mesma estrutura cristalina, porém com parâmetros de rede ligeiramente diferentes, sendo que uma das fases não incorpora o cátion Re na sua composição. A fase principal, contendo Re, foi denominada Hg,Re-1223 e a fase segregada, que não contém Re foi denominada Hg-1223. Constatou-se que as fases supercondutoras Hg,Re-1223 e Hg-1223 apresentam diferentes tamanhos de cristalito e que, dentre as amostras estudadas, a que foi tratada sob fluxo de gás composto de 10% oxigênio e 90% argônio possui a maior porcentagem de fases supercondutoras e também a maior proporção da fase Hg,Re-1223. Através do uso da técnica de espalhamento anômalo de raios X, usando radiação síncrotron, confirmou-se a segregação de duas fases supercondutoras com teores diferentes de rênio. A partir dos resultados obtidos foi possível concluir que o tratamento da fase precursora sob fluxo de O2/Ar na proporção 10/90 é o que apresenta melhores resultados de síntese deste composto supercondutor. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Les travaux rapportés dans cette thèse consistent à synthétiser et à caractériser de nouveaux composés à clusters d'éléments de transition par assemblages de briques moléculaires à clusters octaédriques de molybdène. Ils s'inscrivent dans le cadre des activités du Laboratoire International Associé (LIA} CLUSPOM et ont conduit à de nombreuses collaborations notamment avec le Nikolaev Institute of Inorganic Chemistry de Novossibirsk en Russie. Les composés obtenus ont été caractérisés par diffraction des rayons X par la poudre et le monocristal, par spectroscopie infrarouge et de luminescence et par magnétométrie à SQUID. Le premier volet de cette recherche consiste à faire réagir des briques moléculaires hexacyanées [ Moc.B~s(CN}'•Jl" et [Mo.Br'.Q;,(CN}'•]'• (Q = S, Se) avec des métaux de transition pour obtenir des composés dont la stnrcture dérive de celle du Bleu de Prusse. Cette stratégie a permis de synthétiser douze nouveaux composés dont neuf polymères de coordination à structure 1-, 2- et 3-D. Une série de composés basés sur les motifs (MOoBr'8(CN)'6]'- et (Mo6Br;6Q;2(CN)'6f'"• (Q = S, Se} a mis en évidence l'existence de types architecturaux stables et une modulation possible des propriétés optiques et magnétiques par contrôle de la charge du motif. Les complexes de coordination ((Ni(NHJ)o},(Ni,(NHJ}s})IMOoBr6Q2( CN}6).1 2H20 présentent une structure cristalline basée sur des dimères de nickel stabilisés par des liaisons hydrogène. Les mesures d'aimantation magnétique en fonction de la température montrent q 'entre 270 et 13 K, l'ensemble des ions Ni" présente un comportement paramagnétique. Entre 13 et 2 K, seule la contribution paramagnétique des complexes octaédriques de nickel [Ni(NH3)6]" est mesurée. Il y a donc couplage magnétique, à faible température, entre les complexes de nickel des dimères. Des calculs théoriques sur ces phases ont mis en évidence que ce couplage est de type antiferromagnétique. Le second volet de recherche consiste à synthétiser, par hydrolyse contrôlée et auto-assemblage des motifs à clusters, des composés basés sur un réseau de liaisons hydrogène fortes et présentant des propriétés de luminescence et de conductivité protonique. Le composé (H)2[MOoCis(OH}G)l2H20 (X = Cl, Br} présente une conductivité de 1,4. 10"" S.cm••. / Results reported in this PhD thesis consist in synthesizing and characterizing new transition element clusters based compounds by assembling molybdenum octahedral clusters building blocks. They are part of the activities of the CLUSPOM International Associated Laboratory and have led to numerous collaborations especially with the Nikolaev Institute of Inorganic Chemistry of Novosibirsk in Russia. Compounds were characterized by X-ray powder and single crystal diffraction, infrared and luminescence spectroscopies and by SQU ID magnetometry. The first part of this research consists in reacting hexacyano molecular building blocks (Mo.Br's(CN)'6Jl" and (M o. B~6Q'2(CN)'6] '• (Q = S, Se) with transition metals to obtain compounds of which the structure derives from that of the Prussian Blue. This strategy made it possible to synthesize twelve new compounds including nine coordination polymers with structure 1-, 2- and 3-D. A series of compounds based on (Mo.Br's(CN )'6f and (Mo6Br'6Q'2(CN)'6]J.I4• (Q = S, Se) cluster units demonstrated the existence of stable architectural types and possible modulation of optical and magnetic properties by charge switching. The coordination complexes ({ Ni(NHJ}6 )4{Ni2(NHJ)s }]-[Mo.Br6Q2(CN)6].12H20 have a crystal structure which is based on nickel dimers stabilized by hydrogen bonds. Magnetic magnetization measurements as a function of temperature show that between 270 and 13 K, all Ni2+ cations exhibit a paramagnetic behavior. Between 13 and 2 K, only the paramagnetic contribution of nickel octahedral complexes (Ni(NHJ}t;]H is measured. There is therefore magnetic coupling, at low temperature, between the nickel complexes of the dimers. Theoretical calculations on these phases have shown that this coupling is of the antiferromagnetic type. The second part of the research consists in synthesizing, by controlled hydrolysis and self-assembly of cluster units, compounds based on a strong hydrogen bonding network and exhibiting luminescence and proton conductivity properties. The compounds (H)l[Mo.X8(0H)6]-12H20 (X= Cl, Br) and (H),[Mo6Br6Sl(OH)6] have conductivities of up to 1.4 x 10-o S.cm-1

½ž ËÙÑÑ ÖÝ Ó ×× ÖØ Ø ÓÒ ½ž½ž Ñ Ó ×× ÖØ Ø ÓÒ The aim of this thesis was to solve and describe the crystal struc- ture of selected inorganic phosphates. Nine different compounds have been studied, including the NASICON type phosphates Co0.5Ti2(PO4)3, Mn0.5Ti2(PO4)3, Na3.215Fe2(PO4)3, the iron(II) diphosphate Fe2P2O7 and hydrates of rare-earth hydrogen diphosphates LnHP2O7·3H2O (Ln = Y, Tb, Dy, Yb) and TbHP2O7·4H2O. While NASICON type phos- phates and rare-earth hydrogen diphosphates have a conventional three- dimensional crystal structure, the structure of α-Fe2P2O7 is incommen- surately modulated and has been described in (3+1)-dimensional super- space. ½ž¾ž ÇÚ ÖÚ Û Ó Ø ÓÒØ ÒØ Ó ×× ÖØ Ø ÓÒ Dissertation is divided in six parts. Part 1 introduce the crystal struc- ture analysis, the concept of aperiodic crystals and the superspace ap- proach. Part 2 describes course of X-ray diffraction experiment and used experimental equipment. The next three parts, Part 3, Part 4 and Part 5, in which the structures of NASICON-type phospates, iron(II) diphos- phate, and rare-earth hydrogen diphosphates are discussed, are the main parts of this work. Part 1. Introduction and Initiation Chapter 2, "Basic principles of crystal structure analysis" con- cerns by fundamentals of crystal structure analysis, i.e. behaviour of X-...

Glucocorticoids (Gc) are vital for development, maintenance of glucose homeostasis and the resolution of inflammation. As potent modulators of the immune response Gc are routinely prescribed in the management of a variety of inflammatory diseases including asthma and rheumatoid arthritis. However clinical use of Gc is limited by variation in patient sensitivity to Gc treatment and development of a wide range of side effects. In this thesis I present two studies that have advanced our understanding of Gc action in vivo. The first defines and characterises the cause of familial glucocorticoid resistance, and the second describes the action of two potent non-steroidal Gc in a cell line model. Familial Gc Resistance: Cases of primary generalised Gc resistance are very rare and typically present as mineralocorticoid and androgen excess leading to hypertension, hypokalemia and hirsutism. Gc resistance is attributed to loss of function mutations within the glucocorticoid receptor (GR). Here I identify a family with a novel mutation in GR exon 6 that gives rise to a very mild phenotype. Analysis of transformed patient peripheral blood lymphocytes revealed a 50% reduction in full length GR but no expression of a mutant form. As this did not rule out expression in vivo, the mutant receptor (Δ612GR) was characterised in a cell line. Investigation using reporter genes revealed that Δ612GR lacked any activity, but had dominant negative action when co expressed with full length GR. In response to Gc Δ612GR was not phosphorylated or targeted for degradation. Fluorophore tagged Δ612GR was unable to translocate to the nucleus in response to Gc, but delayed the translocation of full length GR when co-expressed. Together this indicates that Δ612GR is unable to bind ligand but has dominant negative action upon full length GR most likely due to heterodimerisation. Therefore I describe a novel GR mutation that results in Gc resistance but presents with a mild very phenotype. Novel Non-steroidal Gc: Non-steroidal Gc can be used as tools to determine how ligand structure directs GR function. Here I describe two highly potent non steroidal Gc ligands, GSK47867A and GSK47869A which alter the kinetics of receptor activity. Treatment with either ligand induces slow GR nuclear translocation, promotes GR nuclear retention and prolongs transcriptional activity following ligand withdrawal. Crystal structure analysis revealed that GSK47867A and GSK47869A specifically alter the surface charge of the GR at a site important for Hsp90 binding. GR bound to GSK47867A and GSK47869A shows prolonged activity in the presence of Hsp90 inhibitor geldanamycin. Therefore this work identifies a new chemical series that could prolong GR activity due to altered pharmacodynamics rather than altered pharmacokinetics.In summary this work uses a combination of genetic and chemical biology approaches to broaden our understanding of GR function. Characterisation of naturally occurring GR mutations gives insight into the complex function of the GR, and non-steroidal Gc act as useful tools that will aid in the design of improved therapeutics.

Les matériaux multiferroïques magnétoélectriques (ME) présentant simultanément des propriétés couplées de ferromagnétisme et de ferroélectricité suscitent beaucoup d’attention, non seulement pour leurs applications (comme la RAM magnétique de nouvelle génération), mais aussi pour la compréhension de la physique relative à ce couplage. Le but de cette thèse était de découvrir et de caractériser de nouveaux composés potentiellement multiferroïques, d’où le choix des trirutiles inverses. Ce manuscrit présente l'étude détaillée du trirutile inverse Mn2TeO6 et quelques résultats sur la série substituée au chrome Mn2-xCrxTeO6. Les composés Mn2TeO6 et substitués sont préparés par réaction à l'état solide à relativement basse température (<700°C). De nombreuses expériences de diffraction de neutrons et de rayons-X ont été réalisées pour étudier les structures cristallines et magnétiques en fonction de la température (de 700°C à 1.5K), ces données ont été analysées en lien avec les caractérisations des propriétés magnétiques et électriques. Mn2TeO6 s’est révélé un matériau complexe et riche en transitions en fonction de la température. En température décroissante, Mn2TeO6 présente d’abord une transition d’une structure tétragonale (P42/mnm) à une double maille monoclinique (P21/c) vers 400°C due à l'effet Jahn-Teller. Une seconde transition très hystérétique apparait à plus basse température, avec la coexistence de deux phases monocliniques entre 45 et 100K. Des transitions magnétiques sont également observées par des mesures de susceptibilité magnétique et de diffraction neutronique. La structure cristalline à température ambiante met en évidence un ordre orbitalaire, dû au manganèse trivalent, complexe et inédit avec une alternance d’octaèdres MnO6 allongés et aplatis décrivant des chevrons. L’impact de l’effet Jahn-Teller induit par le manganèse trivalent est confirmé dans les composés substitués au Cr (avec x ≥ 0,15) qui conservent la structure quadratique sur toute la gamme de température. / Magnetoelectric (ME) multiferroic materials, which present simultaneously two coupled properties between ferromagnetism and ferroelectricity, have attracted much attention recently, not only owing to their application perspectives, e.g., next-generation magnetic RAM, but also for the rich physics associated with the understanding of this coupling. Inverse trirutiles are of particular interest here since ME properties have been reported in this family of compounds. This manuscript presents the study of inverse trirutile Mn2TeO6 and its Cr-substitution series Mn2-xCrxTeO6. Mn2TeO6 and Cr-substituted series were prepared by solid state reaction at relatively low-temperature (< 700°C). Thanks to an extensive use of different techniques performed in a large temperature range (1.5K to 700°C), encompassing synchrotron, neutron and electron diffraction experiments combined with physical properties measurements, the very complex behaviour of Mn2TeO6 was revealed. A structural transition at 400°C from tetragonal (P42/mnm) to monoclinic (P21/c) is observed first, and related to a cooperative Jahn-Teller effect. Further cooling the sample, a hysteretic structural transition is observed spanning more than 50K, which leads to the coexistence of two monoclinic phases. A series of magnetic transitions are also observed between 48K and 22K, with magnetization, heat capacity measurement and neutron diffraction. Cr-substituted (x ≥ 0.15) samples crystallize in the tetragonal phase, implying the suppression of the cooperative Jahn-Teller effect, and involving a simpler, though short–range, magnetic order.

The complex molecule of the title compound, [Rh2{N(C6H5)COCH3}4(C8H7N)2], exhibits inversion symmetry. The four acetamidate ligands bridging the dirhodium core are arranged in a 2,2-trans manner with two N atoms and two O atoms coordinating to each RhIIatom trans to one another. The Neq - Rh - Rh - Oeq torsion angles on the acetamidate bridge vary between -4.07 (5) and -6.78 (7)°. The axial nitrile ligands complete the distorted octahedral coordination sphere of each RhIIatom and show a nonlinear coordination with Rh - N - C bond angles of 151.6 (3) and 152.5 (3)°. The bond lengths of the two nitrile triple bonds are 1.133 (5) and 1.137 (5) Å.

The tetraphosphine DPPEPM reacts with [PtMe2(cod)] to produce [PtMe2(DPPEPM-PP)] (1) in near quantitative yield. On standing in solution, the free P atoms become oxidized to give [PtMe2(DPPEPM(O) 2-PP)] (1a), which has been characterized by X-ray crystallography. In contrast, reactions of DPPEPM with [MCl2(cod)] (M = Pd, Pt) yield ionic products of the form [M(DPPEPM-PP)2]MCl4 (3, 4). When a solution of the platinum complex was allowed to stand, crystals of [Pt(μ-Cl)(μ-DPPEPM)2]Cl3 (5) were obtained. In a third set of reactions, treatment of [PtClR(cod)] (R = Me, Ph) or [PdClMe(cod)] with DPPEPM gives species of the type [MR(DPPEPM-PPP)]Cl (6-8), in which one of the internal P atoms is uncoordinated. Reactions of [PtR2(DPPEPM-PP)] with [PtR2′(cod)] or [MCl2(cod)] (M = Pd, Pt), or of [PtR(DPPEPM-PPP)]Cl with [MCl2(cod)], lead to unsymmetrical bimetallic complexes. [PtMe2(μ-DPPEPM)PdCl2] (11) and [PtClPh(μ-DPPEPM)PdCl2] (14) have been characterized crystallographically. Trimetallic complexes of the form [{PtR 2(μ-DPPEPM)}2M][MCl4] (M = Pd, Pt, 15-17) are produced by reaction of [PtR2(DPPEPM-PP)] with [MCl 2(cod)].

Reaction of the thiosemicarbazone ligands, [4-(p-bromophenyl)thiosemicarbazone of salicylaldehyde (H2L1), 4-(p-X-phenyl)thiosemicarbazone of o-vanillin {X = F (H2L2), X = Cl (H2L3) and X = OMe (H2L4)}, 4-(p-bromophenyl)thiosemicarbazone of 5-bromosalicylaldehyde (H2L5), and 4-(p-chlorophenyl)thiosemicarbazone of o-hydroxynaphthaldehyde (H2L6)] with [MoO2(acac)2] afforded a series of new oxidomolybdenum(VI) complexes [Mo(VI)O2L1–6(solv)] (1–6) {where solv (solvent) = DMSO (1, 3, 5 & 6) and H2O (2 & 4)}. The molecular structures of 2 and 3 were determined by X-ray crystallography, demonstrating the dibasic tridentate behavior of ligands. The cyclic voltammogram pattern is similar for 1–6, which includes two irreversible reduction processes within the potential window −0.71 to −0.66 V and −0.92 to −0.85 V corresponding to the metal centered reduction from Mo(VI)/Mo(V) and Mo(V)/Mo(IV) respectively. Catalytic potential of 1–6 was tested for the oxidation of styrene and cyclohexene. The effect of various parameters such as the amount of catalyst, oxidant, NaHCO3, and solvent was checked to optimize the conditions for the best performance of the catalyst. 100% product selectivity for the formation of cyclohexene oxide from cyclohexene and ∼98–99% product selectivity for the oxidation of styrene to styrene oxide was observed.