The solid state, hydrothermal and flux methods were used for the investigation of alkaline earth and transition metal borophosphate compounds. The products and the phase relations were investigated by XRD, IR, DTA, and EDX methods. The solid state reactions of several boron compounds with different phosphating agents have been studied in the temperature range of 400-1200 oC. Hydrothermal and flux techniques were performed at 150 oC and 1200 oC, respectively. On the other hand, an attempt has been made to prepare a novel borophosphate compound MIIMIV[BPO7] (where MIV= Zr4+, Si4+, and MII= Sr2+, Ca2+) by solid state reactions and to investigate intermediate and final products. (NH4)2HPO4 and NH4H2PO4 were used as a phosphating agent. For the synthesis of these new compounds, the following reaction was predicted using the stoichiometric amount of the reactants: 2MIVO2 + 2MIICO3 + B2O3 + 2(NH4)2HPO4 &amp / #8594 / 2MIIO.MIVO2.B2O3.P2O5 + 4NH3 + 3H2O + 2CO2 (According to IUPAC formulation for the compounds composed of oxides) In the case of MIV=Zr4+ and MII=Sr2+, the formation of ZrSr[BPO7] was observed together with ZrO2 and SrBPO5. The formation of a new phase was proved by indexing the XRD pattern of the product after separating ZrO2 and SrBPO5 lines. Its crystal system was found to be orthorhombic and the unit cell parameters are a=11.85&Aring / , b=12.99 &Aring / , c=17.32 &Aring / . IR analysis shows that there is [BPO7]6- bands in the spectrum. At higher temperatures, Sr7Zr(PO4)6 was obtained. In the case of MIV=Si4+, SrBPO5 was the main product together with unreacted SiO2. At 1100 oC, Si4+ entered SrBPO5 structure and the product was indexed in orthorhombic system with a=8.9243 &Aring / , b=13.1548 &Aring / , and c=5.4036 &Aring / . Several other M:B:P ratios were tried for solid state systems. For compositions with different cations (such as Al3+, Ca2+, Na+), reactions generally pass through metal phosphates and BPO4. The X-ray diffraction powder pattern and infrared spectrum of several intermediate products obtained at different temperatures were presented and the several phase relations were investigated. The DTA and EDX analyses of some products were also reported.

In this study some of the first row transition metal oxides were transformed to metal sulfides by new solid gas reaction system. Transition metal sulfides have wide application area in industry and technology. Several techniques are known for the production of metal sulfides. Such as reactions between metal or metal oxide with H2S, precipitation in several liquid medium, reaction between metal and sulfur in closed vessel, chemical vapor deposition (CVD) technique. These techniques will have some disadvantages / for example, reactants are rarely available or expensive materials, their production systems are complicated and hard to set up these systems, products contain oxygen or hydrogen or corresponding metal sulfate as impurities. In our new sulfidizing system the reactants are metal oxides, carbon and SO2. These materials can be found easily. Especially, SO2 usage in this system is a big advantage of giving possibility of usage the hazardous waste product of SO2 in industry. The sulfidizing gas mixture was obtained by passing SO2 over activated carbon at 750 OC in a vertical tubular furnace. The obtained gas contains, mainly, CS2, CO and COS. The sulfidizing reactions took place in the horizontal tubular furnace at 450OC-1250 OC. The duration of the reaction, (three hours), and flow rate (60ml/min) of the SO2 gas were kept constant. The products were examined by X-ray powder diffraction and Raman scattering spectroscopy. All examined metal oxides were transformed to metal sulfides by sulfidizing gas mixture successfully. Ti3S5 was obtained from TiO2. Cr2S3 was obtained from Cr2O3. MnS (Alabandite) was obtained from MnO2. FeS and Fe1-xS (Pyrrhotite) were obtained from Fe2O3. Co9S8 (Cobaltpentlandite) and CoS (Jaipurite) were obtained from Co3O4. NiS was obtained from NiO. Cu7.2S, Cu1.6S (Calcocite-Q), Cu1.81S, Cu7S4 (Anilite) Cu9S5 (Digenite), Cu8S5 (Geerite) were obtained from CuO, ZnS was obtained from ZnO. The electrical conductivity character of each product obtained by sulfidizing reaction was analyzed in the temperature range of 77 K-300 K. Titanium sulfide, cobalt sulfide and nickel sulfide showed metallic conductivity, cupper sulfide and iron sulfide showed semiconductor behavior in this temperature range.

Orientador: Prof. Dr. Fabio Furlan Ferreira / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2017. / Atualmente, o câncer é um dos problemas de saúde pública mais complexos que o sistema de saúde brasileiro enfrenta, dada a sua magnitude epidemiológica, social e econômica. É bem sabido que a combretastatina A4 (CA-4), que é isolada a partir das cascas da árvore sul-africana, cujo nome científico é Combrettum caffrum, é utilizada para inibir a angiogênese, que consiste no crescimento de novos vasos sanguíneos a partir dos já existentes. No entanto, dependendo da dose administrada ao paciente, a CA-4 pode causar alguns efeitos colaterais. Aqui, será apresentada a caracterização físico-química de um novo derivado N-acilidrazônico - LASSBio-1735 - um análogo da CA-4. O LASSBio-1735 foi avaliado quanto a seus efeitos citotóxicos, por ensaios de MTT, frente às linhagens tumorais HL-60 (leucemia humana), SF-295 (glioblastoma humano), MDA-MB435 (melanoma) e HCT-8 (carcinoma ileocecal ¿ cólon), apresentando resultados promissores. Pudemos determinar com êxito as estruturas cristalinas - utilizando dados de difração de raios X por policristais e um procedimento de simulated annealing - das formas anidra e di-hidratada do composto sintetizado. Foi observado que os compostos cristalizaram em sistemas cristalinos ortorrômbicos, porém em distintos grupos espaciais. A forma anidra cristalizou no grupo espacial Pna21 e a forma hidratada no grupo espacial P212121. Os efeitos sobre a viabilidade celular das formas anidra e di-hidratada do LASSBio-1735 foram comparativamente avaliados em diferentes linhagens tumorais e a forma di-hidratada exibiu maior citotoxicidade frente a linhagem tumoral K562 (leucemia mieloide crônica). Os resultados de velocidade de dissolução intrínseca levaram-nos a classificar o LASSBio-1735 em suas diferentes formas como um fármaco de baixa solubilidade, tendo sido observado um ligeiro aumento da solubilidade da forma anidra quando comparada a forma di-hidratada. / Currently, cancer is one of the most complex public health problems faced by the Brazilian health system, given its epidemiological, social and economic magnitudes. It is well known that combretastatin A4 (CA-4), which is isolated from Combretum caffrum, is used to inhibit angiogenesis, which is related to the growth of new blood vessels from the existing ones. However, depending on the dose administered to the patient, it can cause some side-effects. Herein, we present the physicochemical characterization of a novel N-acylhydrazone derivative ¿ LASSBio-1735 ¿ a CA-4 analogue. LASSBio-1735 was evaluated for its cytotoxic effects, using MTT assays, against HL-60 (human leukemia), SF-295 (human glioblastoma), MDA-MB435 (melanoma) and HCT-8 (ileocecal adenocarcinoma) tumor cells, showing promising results. We could successfully determine the crystal structures ¿ by using X-ray powder diffraction data and a simulated annealing procedure ¿ of the anhydrous and hydrated forms of the as-synthesized compound. Both compounds crystallized in orthorhombic crystal systems but under different space groups. The anhydrous form crystallized in the Pna21 while the hydrated one in the P212121 space groups. The effects on cell viability of anhydrous and dihydrated forms of LASSBio-1735 were comparatively evaluated in different tumor cell lines, and the dihydrated form exhibited higher cytotoxicity against the K562 (human chronic myeloid leukemia) tumor cell line. The results of intrinsic dissolution rate lead us to classify LASSBio-1735 in its different forms as a pharmaceutical candidate with low solubility; however, a slight solubility increase of the anhydrous form when compared to the dihydrated one was found.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-07-11T20:01:58Z No. of bitstreams: 1 webertonreisdocarmo.pdf: 7569925 bytes, checksum: d21c1add8559c40e497cf970e0833679 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-07-13T16:38:18Z (GMT) No. of bitstreams: 1 webertonreisdocarmo.pdf: 7569925 bytes, checksum: d21c1add8559c40e497cf970e0833679 (MD5) / Made available in DSpace on 2016-07-13T16:38:18Z (GMT). No. of bitstreams: 1 webertonreisdocarmo.pdf: 7569925 bytes, checksum: d21c1add8559c40e497cf970e0833679 (MD5) Previous issue date: 2012-02-27 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A hipertensão arterial é uma doença que acomete milhões de pessoas no mundo todo, por esse motivo a classe de médicos cardiologistas na publicação da V Diretrizes Brasileiras de Hipertensão Arterial ressaltou a importância de não se obter medicamentos anti-hipertensivos via farmácias de manipulação. De acordo com o que foi discutido, isso se deve a inexistência de informações adequadas de controle de qualidade, bioequivalência e/ou interação química dos compostos. Os fármacos utilizados no tratamento da hipertensão são administrados oralmente na forma sólida, podendo, portanto, cristalizar-se em diversas formas cristalinas, fenômeno este conhecido como polimorfismo. O polimorfismo em fármacos é um tema de grande interesse para a comunidade cientifica e apresenta um grande desafio para as indústrias farmacêuticas, uma vez que alterações no arranjo cristalino podem alterar as propriedades físico-químicas dos fármacos, e consequentemente afetar o desenvolvimento, a segurança e a eficácia de um medicamento. A principal técnica de caracterização do polimorfismo é a difração de raios X, cuja principal vantagem em relação às outras técnicas consiste na habilidade de diferenciar de maneira inequívoca uma fase cristalina da outra, mesmo que essa possua a mesma composição. Devido a todos os pontos levantados, nesse trabalho realizou-se a identificação e a quantificação de fases cristalinas dos fármacos anti-hipertensivos, Losartana, Clortalidona e Hidroclorotiazida que são disponibilizados às farmácias de manipulação da cidade de Juiz de Fora, denominadas de A e B. Realizou-se também a quantificação de fases em associações dos mesmos. Para esses propósitos as técnicas utilizadas foram espectroscopia vibracional Raman, análise termogravimétrica (TG) e calorimetria exploratória diferencial (DSC), análise elementar de carbono, hidrogênio, nitrogênio e a difração de raios X por policristais. Os resultados mostraram que para os diuréticos (Clortalidona e Hidroclorotiazida) apenas uma fase cristalina foi encontrada nas amostras, porém para a Losartana foram observadas as fases ortorrômbica e monoclínica. A análise de fases indicou que a técnica pode ser utilizada na quantificação de associação de medicamentos. / Hypertension is one of the most prevalent diseases worldwide affecting millions of people, for this reason the cardiologists in the publication of the V Brazilian Guidelines on Hypertension emphasized the importance of not buying antihypertensive medications through manipulation pharmacies. According to what was discussed, this is due to a lack of adequate information quality control, bioequivalence and / or chemical interaction of the compounds. The drugs used to treat hypertension are administered orally in solid form and therefore can crystallize in different crystalline forms, a phenomenon known as polymorphism. Polymorphism in drugs is a topic of great interest to the scientific community and presents a great challenge for the pharmaceutical industry, since changes in the crystalline arrangement can change the physicochemical properties of drugs, and consequently affect the development, security and effectiveness of a drug. The main technique for polymorphism characterization is the X-ray diffraction, whose main advantage over other techniques is the ability to differentiate unequivocally one of the other crystalline phases, even though this has the same composition. Based on aforementioned points, in this work was carried out the identification and quantification of crystalline phases of antihypertensive drugs, Losartan, Hydrochlorothiazide and Chlorthalidone that are available to manipulation pharmacies in Juiz de Fora city, named A and B. There was also the quantification of phases in the same associations. For these purposes the techniques used were Raman vibrational spectroscopy, thermogravimetric analysis (TG) and differential scanning calorimetry (DSC), elemental analysis of carbon, hydrogen and nitrogen, and X-ray powder diffraction. The results showed that for diuretics (Hydrochlorothiazide and Chlorthalidone) only one crystalline phase was found in the samples, but for Losartan were observed orthorhombic and monoclinic phases. The phase analysis indicated that this technique can be used in quantifying drug combination.

Contents of major, minor and trace elements in clinopyroxenes and clinoamphiboles of basanites, volcanoclastics, essexites, sodalitic syenites, and monzodiorites of the České středohoří Mts. has been determined using an electrone microprobe and LA-ICP-MS techniques. Composition of clinopyroxenes corresponds to either diopside or augite and clinoamphiboles can be classified as kaersutite or pargasite. Some pyroxenes display pronounced sector zoning showing increased contents of Mg and Si in pyramidal sectors whereas prismatic sectors show Fe, Ti and Al enrichment. Chemical composition of both sectors corresponds to diopside. Growth zoning has been found in the samples from basanites and volcanoclastics. Grain cores display the chemistry of augite and towards the rim the chemical composition changes to diopside. Samples have also been analyzed by powder and single crystal X-ray diffraction techniques. Samples of pyroxenes appear to be either pure or they contain negligible admixtures of phlogopite. Samples of amphiboles are also either without any admixtures or they show contamination by low amounts of diopside or augite, or phlogopite may rarely be encountered. Mutual relationship between the size of the unit cell parameters b and and substitutions in M1,2,3 and A sites has been observed. Longer mean T-O...

Micas from České středohoří mts. have been studied by X-ray difractometry, ICP-MS and electron microprobe. The measurements of trace elements and REEs revealed very low tendency by normalization of chondrite reservoir and primitive mantle. The micas classifications were determined by Tischendorf (2007) and Rieder (1998) as Fe- or Fe-Ti phlogopites. The abundances of Ti are very high up to 0,46 (a.p.f.u.). X-ray powder diffraction revealed double layered polytype 2M1 with space group C/2c.

Six methods have been used to study micas from České středohoří mts.: X-ray difractometry (transmission and reflection), ICP MS, electron microprobe, Mössbauer spectroscopy and termogravimetry. The measurements of trace elements and REE's revealed very low tendency by normalization on chondrite reservoir and primitive mantle. Micas show high contents of TiO2 (9,47 wt.%) and BaO (up to 2,1 wt.%) in separated grains from rock. The micas classifications were determined by Tischendorf (2007) and Rieder (1998) as Fe-phlogopites. X-ray powder diffraction revealed cell dimensions and a common polytype 1M with space group C2/m. By Mössbauer spectroscopy have been studied the rates of Fe2+ /Fe3+ and they were 1,08 - 1,86 (except rock sample, which were 9:1). Termogravimetrical measurement until 1450řC revealed weight jump from 1120řC to 1270řC.

This thesis is focused on study of the vibron state in Ce intermetallics. The presence of a vibron state is a consequence of an enhanced magneto-elastic interaction, between phonons and 4f electrons of the Ce ion. The magneto-elastic interaction is usually weak and can be neglected, but here in CeAl2, CePd2Al2, CeCuAl3 and CeAuAl3 is considered to be strong enough, which leads to a bound state called the vibron state. A well determined crystal structure of these compounds is a necessary prerequisite to discuss this unique behaviour. Therefore our investigation is performed on the following levels: A crystal structure study of (Ce,La)Pd2Al2-xGax and CePt2Al2, by low temperature and high temperature X-ray powder diffraction; Investigation of bulk and transport properties of a CePt2Al2 single crystal using the specific heat, magnetisation and electrical resistivity measurements; Symmetry analysis of phonon modes and angular momentum operators in the model Hamiltonian, based on group theory; And finally the study of phonon dispersion curves in CePd2Al2 and LaPd2Al2 single crystals using inelastic X-ray scattering. All these results and preformed analyses lead to the following conclusions: The CePd2Al2 and LaPd2Al2 are incongruently melting phases. We found and described the way which has allowed us to...

The production of stable solid crystalline material is an important issue in the pharmaceutical industry and the challenge to control the desired active pharmaceutical ingredient (API) with the specific chemical and physical properties has led to more development in the drug industry. Increasing the solubility and the dissolution of the drug will increase its bioavailability; therefore the solubility can be improved with the change in the preparation method. The formation of co-crystals has emerged as a new alternate to the salts, hydrates and solvate methods since the molecules that cannot be formed by the usual methods might crystallise in the form of co-crystals. Co-crystals are multicomponent crystals which can be known as supramolecules and are constructed by the non covalent bonds between the desired former and co-former. Therefore the synthon approach was utilised to design co-crystals with the specific properties, this involves the understanding of the intermolecular interactions between these synthons. These interaction forces can be directed to control the crystal packing in the design of the new crystalline solid with the desired chemical and physical properties. The most familiar synthon was the amide group with its complementary carboxylic group, in this work isonicotinamide and benzoic acid were chosen to design co-crystal and much literature exist that introduce the determination of co-crystal growth from these two compounds. The growth of co-crystals was carried out in water, ethanol and ethanol / water mixed solvent (30 - 90 % ethanol) by utilising the Cryo-Compact circulator. Co-crystals (1:1) and (2:1) were grown in ethanol and water respectively and a mixture of both phases were grown in the mixed solvent. All the phases were examined by powder X-ray diffraction (PXRD), Raman, Infrared and 1H-NMR spectroscopy. The solubility of isonicotinamide, benzoic acid, co-crystals (1:1) and (2:1) in water, ethanol and ethanol/water mixed solvent (30 - 90 % ethanol) were determined at 25 °C, 35 °C and 40 °C by utilising the React-Array Microvate. It was important to understand some of the thermodynamic factors which control the formation of these polymorphs such as the change in the enthalpy and the change in the entropy. Also it was important to study the pH behaviour during dissolution of the former, co-former and co-crystals in water, ethanol and ethanol/water mixed solvent (30 - 90 % ethanol) in-order to examine the affect of the solvent composition on the solubility and to identify if some ions were formed during the dissociation and how this could affects the formation of co-crystals. A discussion has been introduced in this research of how similar solubility of the compounds maps the formation of the typical ternary phase diagram of the mixture of 1:1 while compounds with different solubility maps the formation of skewed phase diagram as shown in section 1.6.2.3. In this project an isotherm ternary phase diagram at 20 °C and 40 °C was constructed to map the behaviour of benzoic acid and isonicotinamide and to show all possible phases formed and the regions where all phases are represented in the ternary phase diagram were determined by the slurry method. The ternary phase diagram was used to design a drawn out and cooling crystallisation at 100 cm3 solution of 50 % ethanol / water mixed solvent and a study of the impact of seeds of co-crystals 1:1 on the cooling crystallisation method.

No description available.