Documentação química de espécies do gênero Casearia (Salicaceae) de importância ecológica, econômica e medicinal

The Casearia genus (Salicaceae) is well known because of the medicinal use of its species. Among them, a noteworthy one is the C. sylvestris specie because it already has studies concerning its antiproliferative and/or cytotoxic activity in tumor cells. Furthermore, this specie is popularly used against snake bites, in gastric ulcers treatment and as anti-inflammatory. As well as this, there are other species from this same genus which have been poorly studied, such as the following species: C. decandra, C. grandiflora, C. javitensis, C. arborea, C. lasiophylla and C. ulmifolia. However, several biological activities have been reported for them. In this context, the aim of this project, besides of contributing to the Casearia genus studies, is to study those six species through the analysis and documentation of their leaves' chemical composition (aqueous, ethanolic and hexanic extracts), using analytical separation techniques coupled with spectroscopic techniques, such as UHPLC-DAD, GC-MS and NMR 1H, which will assist the identification of new secondary metabolites in this genus. Moreover, another goal of this present work is aiming the bioprospection of substances with medicinal and economical potential and finally promote the systematic study of some biological activities, such as antimicrobial and cytotoxicity bioassays. A wide variety of metabolites was identified in those three types of extracts, being most of them detected for the first time in Casearia genus, highlighting C. lasiophylla and C. decandra for featuring antimicrobial activity against Staphylococcus aureus.

Nanopartículas de Pd suportadas em compósitos óxido-carbono: influência das interações metal-suporte na oxidação de etanol em meio básico

Fuel cells powered directly with ethanol (Direct Ethanol Fuel Cell-DEFC) are very attractive for the possibility of using a renewable fuel in the generation of clean energy. However, it is still necessary to deepen the understanding of catalytic processes and their dependence on the catalytic properties. This work proposes to study the catalytic activity of ethanol oxidation in an alkaline medium of Pd nanoparticles supported in carbon oxide hybrids using various transition metal oxides (MoO3, TiO2, WO3 and ZrO2). The materials prepared were characterized by techniques such as X-ray diffraction, transmission electron microscopy (TEM) and X-ray dispersive spectroscopy (EDX) to verify the structure, the distribution of particles in the supports and the presence of Pd on particles oxide. Experiments of X-rays absorption spectroscopy were carried out using soft X-rays (SXS) to evaluate the changes in the electronic properties of the Pd particles caused by interactions with different oxides. Measurements of cyclic voltammetry and potential sweeps of adsorbed CO oxidation allowed evaluating general aspects of the catalysts' electrochemical behavior and determining the electrochemically active area thereof. The catalytic performances of ethanol oxidation in alkaline medium were evaluated by electrochemical techniques (potential scan and chronoamperometry), and showed an improvement in activity with the addition of oxides in material containing only carbon, which was most pronounced for the catalyst containing TiO2. This improvement was predominantly associated with the electronic effects caused by the interaction of Pd on the support, causing a vacancy in the 4d band of Pd which, in turn, produces variations in adsorption energies of the species...

Estudo químico dos escapos de Paepalanthus geniculatus Kunth

Eriocaulaceae species are popularly known as sempre-vivas. This family comprising approximately 1.200 species divided into 10 genera, with high endemic levels. Paepalanthus genus has high incidence in the Espinhaço Range region and the report of biological activities. Despite the large number of previous studies with Eriocaulaceae species, Paepalanthus geniculatus has no studies about their scapes, which demonstrates the need for new research to identify their chemical and biological composition. The aim of this work was to study the chemical composition of P. geniculatus ethanolic extract seeking the isolation and identification of metabolites and evaluate the radical scavenging activity of the extract and isolated substances. P. geniculatus were collected in Serra do Cipó-MG in 2013 (Voucher: SANO 3193) and the scapes were dried, crushed and the powder was percolated with ethanol. With the etanolic extract it is carried out a fractionation by gel permeation chromatography, yielding fractions analyzed by TLC assay. The fraction J89 (45,6 mg) was purified by semipreparative HPLC-PDA, resulting in the isolation of substance S1. The fractionation was also performed by medium pressure liquid chromatography, yielding fractions analyzed by TLC assay. The fraction number 4 (92,6 mg) were purified by semipreparative HPLC-PDA resulting in the isolation of substances S2 and S3. The substances S1 and S3 were analyzed by mono and twodimensional NMR, resulting in the identification of 3,4-dihydroxybenzoic acid (protocatechuic acid) and the flavonoid 6-hydroxyquercetin-7-O-β-Dglucopyranoside. The substance S2 were identified by comparison with standards, were it was possible to determine the presence of the flavonoid 6-hydroxy-7- methoxyquercetin-3-O-β-D-glucopyranoside. The evaluation of radical scavenging activity for the extract and the isolated substances using DPPH, showed consistent activity to S1...

Estrutura e algumas propriedades ópticas de difenilfosfinatos de terras-raras

Coordination compounds of trivalent lanthanides cations with diphenylphosphinate are originated from direct reaction between a lanthanide salt and diphenylphosphinic acid. These complexes have peculiar and intriguing features, as (i) quickly obtainment through wet process precipitation, (ii) appreciable thermal stability, similar to inorganic phosphates, (iii) polymeric structure, and consequently, (iv) low solubility in both polar and non-polar solvents. Nowadays, coordination polymers are classified as coordination networks or, in case of porous materials, as metal-organic frameworks (MOFs). By this study, we aim to determine some optical properties of rare-earth diphenylphosphinate (RE = La3+, Eu3+, Gd3+, Lu3+) and conduct an updated classification of these compounds, bringing more details of its structure and the possible proposal of new materials with applications in lighting, detection of ionizing radiation and magnetism. The complexes of trivalent rare-earth cation with diphenylphosphinate were prepared by direct mixture of diphenylphosphinic acid with rare-earth metal chloride, both in ethanolic solution. The solution of diphenylphosphinic acid was kept in a beaker under constant stirring with pH measurements of the solution and gadolinium chloride solution was then dripped slowly with the aid of a burette until its complete addition; the following metal:ligand molar ratios were tested: 1:1, 1:2, 1:3, 2:1 e 3:1. The compounds were characterized by spectroscopic and structural techniques. By Fourier Transform Infrared Spectroscopy (FT-IR), it was possible to check the total ionization of diphenylphosphinic acid in synthesized complexes, confirmed by the absence of the band type A, B, C related to ѵ(O-H) of the acid (2663 cm-1, 2168 cm-1, 1684 cm-1), as well as the disappearance of ѵ(P-OH)=961 cm-1. Furthermore, the occurrence of bands shifts of ѵ(POO-) [symmetrical and asymmetrical] of...

Propriedades estruturais e espectroscópicas de WO3 e WO3:Eu3+

Used as catalysts even in organic and inorganic molecules, as additives on catalysts, electrochromic films on smart windows the tungsten trioxide have been largely studied on the lasts decades, but there is just a few about it's luminescence. Using as precursors nitric acid and sodium tungstate the tungsten trioxide were been prepared thru wet process then treating on thermic and hydrothermal treatments. Where been evaluated the effects of methodology, nitric acid concentration, duration and temperature of treatments. The samples were characterized by X-ray diffraction (XRD), Raman scattering spectroscopy (RSS), Fourier transformed infrared spectroscopy, photoluminescence spectroscopy (PLS) and X-ray excited optical luminescence (XEOL). Hydrated phases of tungsten trioxide were obtained through hydrothermal treatments and the non-hydrated phases occur with thermic treatments. The acid concentration has the ability to determine the major phase formed as well the temperature determine the hydratation of the product. With lower temperatures dihydrate phase were preferable formed and with the rise of temperature, the water molecules were lost up to the fractionary hydratation and then the non-hydrated phase with higher temperatures depending on the atmosphere used on the thermal treatment. Doping the system with europium ions even substituting tungsten or in the interstices of the matrix were not been successful, as well the XEOL spectroscopy intensity were null and quite low for ultraviolet and visible excitation photoluminescence because of oxygen defect levels localized into the prohibited band.

Citotoxicidade de membranas à base de ácido polilático e poli-ε-caprolactona com a incorporação de fosfato de lantânio e oxiapatita dopada com lantânio

Desde a antiguidade, enxertos e membranas são estudados para promoverem um reparo ósseo otimizado. O reparo ósseo consiste na reabsorção do tecido necrosado e de seu coágulo, juntamente com um processo inflamatório que libera fatores de crescimento que irão reparar o osso danificado. Em algumas situações, o osso lesionado não tem a capacidade de se auto reparar, portanto, são necessárias intervenções cirúrgicas para inserir um enxerto ósseo. Entretanto, há uma grande dificuldade em se encontrar um material que forneça os fatores necessários para o crescimento ósseo. Para isso, foram confeccionadas membranas à base de ácido polilático e poli-ε-caprolactona (PLC) (Purasorb: PLC 7015 - Purac, Holanda), com a incorporação de fosfato de lantânio (PLC/LaPO4) e oxiapatita dopada com 20% de lantânio (PLC/La20OAP) pelo Instituto de Química de Araraquara, UNESP. Assim, o objetivo do presente estudo foi avaliar a citotoxicidade desses materiais por meio dos testes XTT e sobrevivência clonogênica. Os eluatos foram preparados com as membranas citadas de acordo com a ISO 10993-12. O cloridrato de doxorrubicina foi utilizado como controle positivo para ambos os testes. Como Controle Negativo (CN) foram utilizadas somente as células CHO-K1 (sem a ação de qualquer tratamento) por 24 horas. Os eluatos foram mantidos em contato com células CHO-K1 por 24 horas. Como os dados apresentaram aderência à curva normal, foi aplicada a análise de variância (ANOVA) one-way, seguido dos testes de Tukey e Dunnett (p<0,05). Verificou-se que os materiais testados não demonstraram absorbância estatisticamente diferente em relação ao CN (p>0,05; Dunnett - XTT) e também não causaram comprometimento na capacidade proliferativa das células (p>0,05; Dunnett - Sobrevivência clonogênica). Assim, pode-se concluir que as amostras de PLC, PLC/LaPO4 e PLC/La20OAP não apresentaram citotoxicidade em células CHO-K1.

Modificação da superfície de óxidos de ferro por dextrana derivatizada para aplicações em liberação de fármaco

Pós-graduação em Química - IQ