Sílica gel organofuncionalizada com 4-amino-5-(4-piridil) 4H-1,2,4-triazol-3-tiol (aptt): Propriedades adsortivas e eletroanalíticas

Pós-graduação em Ciência dos Materiais - FEIS

Efeito da infiltração de sílica pelo método sol-gel na resistência à flexão de bicamadas de porcelana e Y-TZP

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Propriedades elétricas de materiais híbridos de Sílica/orgânico à base de GPTS/TEOS preparados pelo método sol-gel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Mechanical properties and structure of gel systems

Understanding the origins of the mechanical properties and its correlation withrnthe microstructure of gel systems is of great scientific and industrial interest. Inrngeneral, colloidal gels can be classified into chemical and physical gels, accordingrnto the life time of the network bonds. The characteristic di↵erences in gelationrndynamics can be observed with rheological measurements.rnAs a model system, a mixture of sodium silicate and low concentration sulfuric acidrnwas used. Nano-sized silica particles grow and aggregate to a system-spanning gelrnnetwork. The influence of the finite solubility of silica at high pH on the gelationrnwas studied with classical and piezo rheometer. The storage modulus of therngel grew logarithmically with time with two distinct growth laws. A relaxationrnat low frequency was observed in the frequency dependent measurements. I attributernthese two behaviors as a sign of structural rearrangements due to the finiternsolubility of silica at high pH. The reaction equilibrium between formation andrndissolution of bonds leads to a finite life time of the bonds and behavior similar tornphysical gel. The frequency dependence was more pronounced for lower water concentrations,rnhigher temperatures and shorter reaction times. With two relaxationrnmodels, I deduced characteristic relaxation times from the experimental data. Besidesrnrheology, the evolution of silica gels at high pH on di↵erent length scales wasrnstudied by NMR and dynamic light scattering. The results revealed that the primaryrnparticles existed already in sodium silicate and aggregated after the mixingrnof reactants due to a chemical reaction. Throughout the aggregation process thernsystem was in its chemical reaction equilibrium. Applying large oscillatory shearrnstrain to the gel allowed for modifying the gel modulus. The e↵ect of shear andrnshear history on the rheological properties of the gel were investigated. The storagernmodulus of the final gel increased with increasing strain. This behavior can be explained with (i) shear-induced aggregate compaction and (ii) combination ofrnbreakage and new formation of bonds.rnIn comparison with the physical gel-like behavior of the silica gel at high pH, typicalrnchemical gel features were exhibited by other gels formed from various chemicalrnreactions. Influences of the chemical structure modification on the gelation wererninvestigated with the piezo-rheometer. The external stimuli can be applied to tunernthe mechanical properties of the gel systems.

Aza-Michael addition of amines to activated alkenes catalyzed by Silica supported perchloric acid under a solvent-free condition

An efficient aza-Michael addition of amines to a series of ,-unsaturated ketones, carboxylic esters, nitriles and chalcones has been carried out using perchloric acid supported over silica gel (HClO4-SiO2) at room temperature in high yields under solvent-free reaction conditions.

A relevante potencialidade dos centros básicos nitrogenados disponíveis em polímeros inorgânicos e biopolímeros na remoção catiônica

This review reports the application of inorganic and organic polymeric materials for cation removal by using nitrogenated basic centers. The data demonstrate the importance of the desired groups when free or immobilized on natural or synthesized inorganic polymers through silanol groups. Thus, the most studied silica gel is followed by natural crysotile and talc polymers, and the synthesized mesopore silicas, talc-like, silicic acids, phosphates and phyllosilicates. The organic natural biopolymeric chitin and cellulose were chemically modified to improve the availability of the amine groups or the reactivity with desirable molecules to enlarge the content of basic centers. The cation removal takes place at the solid/liquid interface and some interactive effects have their thermodynamic data determined.

The syntheses of the marine metabolites 3-bromoverongiaquinol and 5-monobromocavernicolin

An efficient synthesis of the marine metabolite 3-bromoverongiaquinol (1) and the first total synthesis of 5-monobromocavernicolin (2), both isolated from the marine sponge Aplysina cavernicola, have been described based on the 1,2 addition of the lithium enolate of N,O-bistrimethylsilylacetamide (BSA, 4) to 1,4-benzoquinone (3). Bromination and purification of the crude product on silica gel chromatography provided 3-bromoverongiaquinol (1) in 50% overall yield. Under alkaline conditions, the crude product of the bromination reaction was converted to 5-monobromocavernicolin (2) in 20% yield which was also obtained in 13% yield (25% yield based on recovered starting material) from 3-bromoverongiaquinol (1).

Hidrocarbonetos aromáticos policíclicos em margarina, creme vegetal e maionese

Polycyclic aromatic hydrocarbons (PAHs) are a group of compounds that have been the subject of much concern due to their toxic potential. In this study, margarine?s, vegetable cream and mayonnaise available on the Brazilian market were analyzed for pyrene, chrysene, benzo(a)pyrene, benzo(b)fluoranthene and dibenzo(a,h)anthracene. The analytical methodology involved liquid-liquid extraction, clean-up on silica gel column and determination by high performance liquid chromatography using fluorescence detector. Variable levels of contamination were found within differents brands of the same product and within differents batches of the same brand. The total PAH content was in the range of 4.1 to 7.1mug/kg in vegetable cream, 1.7 to 3.9mug/kg in margarine and 1.0 to 21.7mug/kg in mayonnaise. In general the products which according to the label contain corn oil showed the highest levels of contamination. Based on these results and on the importance of fat, oils and derived products for the intake of PAHs, it is recommended that producers of margarine, vegetable creams and mayonnaise start to control the contamination of the vegetable oils used in the elaboration of these products, in order to reduce the exposure of consumers to excessive amounts of potentially carcinogenic compounds.

Chemical composition, acetylcholinesterase inhibitory and antifungal activities of Pera glabrata (Schott) Baill. (Euphorbiaceae)

Pera glabrata (Schott) Baill. was selected for this study after showing a preliminary positive result in a screening of Atlantic Forest plant species in the search for acetylcholinesterase inhibitors and antifungal compounds. The bioassays were conducted with crude ethanol extract of the leaves using direct bioautography method for acetylcholinesterase and antifungal activities. This extract was partitioned with hexane, chloroform and ethyl acetate solvents. The active chloroform fraction was submitted to silica gel chromatography column affording 12 groups. Caffeine, an alkaloid, which showed detection limits of 0.1 and 1.0 µg for anticholinesterasic and antifungal activities, respectively, was isolated from group nine. After microplate analyses, only groups four, nine, 10, 11 and 12 showed acetylcholinesterase inhibitory activity of 40% or higher. The group 12 was purified by preparative layer chromatography affording four sub-fractions. Two sub-fractions from this group were analyzed by gas chromatography-mass spectrometry and gas chromatography-flame ionization detector. The first sub-fraction showed anticholinesterasic activity and contained two major compounds: 9-hydroxy-4-megastigmen-3-one (84%) and caffeine (6%). The second sub-fraction presented five major compounds identified as 9-hydroxy-4-megastigmen-3-one, isololiolide, (-) loliolide, palmitic acid and lupeol and did not show activity.

Cytotoxic activity of a dichloromethane extract and fractions obtained from Eudistoma vannamei (Tunicata: Ascidiacea)

This study consists of the bioassay-guided fractionation of the dichloromethane extract from Eudistoma vannamei and the pharmacological characterization of the active fractions. The dried hydromethanolic extract dissolved in aqueous methanol was partitioned with dichloromethane and chromatographed on a silica gel flash column. The anti-proliferative effect was monitored by the MTT assay. Four of the latest fractions, numbered 14 to 17, which held many chemical similarities amongst each other, were found to be the most active. The selected fractions were tested for viability, proliferation and death induction on cultures of HL-60 promycloblastic leukemia cells. The results suggested that the observed cytotoxicity is related to apoptosis induction. (C) 2007 Elsevier Inc. All rights reserved.

Detection of lead(II) and silver(I) in aqueous solution using a piezoelectric device

The gold surface of a quartz crystal microbalance was modified by the attachment of silica particles derivatised with N-[(3-trimethoxysilyl)propyl] ethylenediaminetriacetic acid. The device was employed to study the kinetics of the interaction of aqueous solutions of lead(II) nitrate and silver(I) nitrate with the surface and for the selective separation of the metal ions.

Synthesis of anatase TiO2 supported on porous solids by chemical vapor deposition

Coating anatase TiO2 onto three different particle supports, activated carbon (AC), gamma -alumina (Al2O3) and silica gel (SiO2), by chemical vapor deposition (CVD) was studied. The effect of the CVD synthesis conditions on the loading rate of anatase TiO2 was investigated. It was found that introducing water vapor during CVD or adsorbing water before CVD was crucial to obtain anatase TiO2 on the surface of the particle supports. The evaporation temperature of precursor, deposition temperature in the reactor, flow rate of carrier gas, and the length of coating time were also important parameters to obtain more uniform and repeatable TiO2 coating. High inflow precursor concentration, high CVD reactor temperature and long coating time tended to cause block problem. Coating TiO2 onto small particles by CVD involved both chemical vapor deposition and particle deposition. It was believed that the latter was the reason for the block problem. In addition, the mechanism of CVD process in this study included two parts, pyrolysis and hydrolysis, and one of them was dominant in the CVD process under different synthesis route. Among the three types of materials, silica gel, with higher surface hydroxyl groups and macropore surface area, was found to be the most efficient support in terms of both anatase TiO2 coating and photocatalytic reaction. (C) 2001 Elsevier Science B.V. All rights reserved.

Preparation, characterization and catalytic studies of V2O5-SiO2 xerogel composite

In this work, we report the synthesis, characterization and catalytic properties of a vanadium oxide-silicon oxide composite xerogel prepared by a soft chemistry approach. In order to obtain such material, we submitted a vanadium pentoxide gel previously synthesized via protonation of metavanadate species to an ""in situ"" progressive polycondensation into silica gel. The material has been characterized by X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. Further, the catalytic activity of this material was evaluated for the epoxidation of styrene and cyclooctene using iodosylbenzene, hydrogen peroxide and m-chloroperbenzoic acid as the oxidizing agent.

Comprehensive study of surface chemistry of MCM-41 using Si-29 CP/MAS NMR, FTIR, pyridine-TPD, and TGA

A comprehensive study was conducted on mesoporous MCM-41. Spectroscopic examinations demonstrated that three types of silanol groups, i.e., single, (SiO)(3)Si-OH, hydrogen-bonded, (SiO)(3)Si-OH-OH-Si(SiO)(3), and geminal, (SiO)(2)Si(OH)(2), can be observed. The number of silanol groups/nm(2), alpha(OH), as determined by NMR, varies between 2.5 and 3.0 depending on the template-removal methods. All these silanol groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol(-1), respectively. However, only free silanol groups (involving single and geminal silanols) are highly accessible to the silylating agent, chlorotrimethylsilane. Silylation can modify both the physical and chemical properties of MCM-41.