Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved.

Optimization and validation of organochlorine compounds in adipose tissue by SPE-gas chromatography

Scientific evidence has shown an association between organochlorine compounds (OCC) exposure and human health hazards. Concerning this, OCC detection in human adipose samples has to be considered a public health priority. This study evaluated the efficacy of various solid-phase extraction (SPE) and cleanup methods for OCC determination in human adipose tissue. Octadecylsilyl endcapped (C18-E), benzenesulfonic acid modified silica cation exchanger (SA), poly (styrene-divinylbenzene (EN) and EN/RP18 SPE sorbents were evaluated. The relative sample cleanup provided by these SPE columns was evaluated using gas chromatography with electron capture detection (GC–ECD). The C18-E columns with strong homogenization were found to provide the most effective cleanup, removing the greatest amount of interfering substance, and simultaneously ensuring good analyte recoveries higher than 70%. Recoveries>70% with standard deviations (SD)<15% were obtained for all compounds under the selected conditions. Method detection limits were in the 0.003–0.009 mg/kg range. The positive samples were confirmed by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). The highest percentage found of the OCC in real samples corresponded to HCB, o,p′-DDT and methoxychlor, which were detected in 80 and 95% of samples analyzed respectively. Copyright © 2012 John Wiley & Sons, Ltd.

Mecanismos de Separação em Eletroforese Capilar

Since its inception in the 80's, capillary electrophoresis has matured into a well established technique for the separation and analysis of complex samples. One of its strongest aspects is the ability to handle materials from a diversity of chemical classes, ranging from few to millions of Daltons. This is only possible because several modes of electrophoresis can be performed in a single capillary format. In this work, relevant aspects of capillary zone electrophoresis in its three modes (free solution, micellar and gel), capillary isoelectric focusing and capillary isotachophoresis are discussed and many representative applications are presented.

Adsorção do complexo H[Ru(III)Cl2(H2EDTA)] sobre a superfície da sílica gel modificada com [3-(2-aminoetil) aminopropil]trimetoxissilano em soluções etanólicas

Silica gel was functionalized with [3-(2-aminoethyl)aminopropyl]trimethoxysilane group (SF-AEATS) and the characterization by chemical analysis (N) and infrared spectroscopy confirmed the functionalization. The capacity of the modified silica to adsorb the complex Ru(III)-EDTA from ethanolic solution was studied. The selectivity coefficients of the complex formed on the support obtained was (Gñ), 2,07 x 10(4) L/mol and the average number of ligand bonded by one metal ion on the support (ñ) was ~ 1.

Fases estacionárias monolíticas para separações cromatográficas

Monolithic stationary phases represent a new generation of chromatographic separation media. These phases consist of a continuous separation bed prepared by in situ polymerization or consolidation inside the column tubing. In recent years, their simple preparation procedure, unique properties and excellent performance have attracted quite remarkable attention in liquid chromatography and capillary electrochromatography. This review summarizes the preparation, characterization and applications of monolithic stationary phases. The analytical potential of these columns is demonstrated with separations involving various families of compounds in different separation modes.

Fenilsilicato dopado com Eu III obtido pelo método sol-gel

In this work, we report the synthesis and the photoluminescence features of a Eu(III)-doped modified silica matrix obtained by the sol-gel method. The matrix was prepared by reaction between tetraethylorthosilicate and phenyltriethoxysilane alkoxide. The hydrolysis occurred using basic catalysis. The solids were treated at 100, 200 and 300 ºC during 4 h and the structure was determined by thermogravimetric analysis (TG/DTG), nuclear magnetic resonance (NMR 29Si and 13C), infrared spectroscopy (IR) and photoluminescence (PL). The PL spectra display the Eu(III) lines characteristic of the ion, 5D0 -> 7F J (J=0, 1, 2, 3, 4), the blue emission as ascribed in the silica matrix. The NMR and TG showed the stability of hybrid silica.

Eletrocromatografia capilar: contextualização, estado da arte e perspectivas

Capillary electrochromatography (CEC) is a separation technique in which the mobile phase flow is based on the application of a voltage across a packed capillary, which generates an electroosmotic flow that transports the analytes along the capillary toward the detector. As it combines the separation mechanisms of high-performance liquid chromatography (HPLC) and of capillary electrophoresis (CE), CEC can be considered a hybrid of HPLC and CE. This review presents some fundamental aspects of CEC and is focused on the instrumental advances of the technique, such as column technology, operation modes and detection systems, presenting recent papers on these topics and some applications and perspectives about CEC.

Optimization of the carrot leaf dehydration aiming at the preservation of omega-3 fatty acids

The carrot leaf dehydration conditions in air circulation oven were optimized through response surface methodology (RSM) for minimizing the degradation of polyunsaturated fatty acids, particularly alpha-linolenic (LNA, 18:3n-3). The optimized leaf drying time and temperature were 43 h and 70 ºC, respectively. The fatty acids (FA) were investigated using gas chromatography equipped with a flame ionization detector and fused silica capillary column; FA were identified with standards and based on equivalent-chain-length. LNA and other FA were quantified against C21:0 internal standard. After dehydration, the amount of LNA, quantified in mg/100 g dry matter of dehydrated carrot leaves, were 984 mg.

Determination of cetirizine in tablets and compounded capsules: comparative study between CE and HPLC

A capillary electrophoresis (CE) method was developed and validated for determination of cetirizine dihydrochloride in tablets and compounded capsules. The electrophoretic separation was performed in an uncoated fused-silica capillary (40 cm x 50 μm i.d.) using 20 mmol L-1 sodium tetraborate buffer (pH 9.3) as background electrolyte, a hydrodinamic sample injection at 50 mBar for 5 s, 20 KV applied voltage at 25 °C, and detection at 232 nm. The proposed method was compared with the high performance liquid chromatographic (HPLC) method previously validated for this drug, and statistical analysis showed no significant difference between the techniques.

Materiais híbridos orgânico-inorgânicos (ormosil) obtidos por sol-gel com potencial uso como filtro solar

This work aimed at the synthesis and characterization of particles of modified silica containing the organic filter dibenzoylmethane (DBM) by the hydrolytic sol-gel method, with modifications to the Stöber route. The structures of the resulting Xerogels were characterized by diffuse reflectance UV-VIS spectroscopy in the solid state, infrared absorption spectroscopy, Scanning Electron Microscopy (SEM) and 29Si Nuclear Magnetic Resonance (29Si NRM). The results showed favorable formation of hybrid organic-inorganic nanoparticles with efficient absorption/reflectance of radiation in the UV / VIS range, which enables their potential use as sunscreen.

Stability-indicating comparative methods using mekc and lc for determination of olmesartan medoxomil

A stability-indicating method using MEKC was validated for the analysis of olmesartan medoxomil in tablets. Successful separation was achieved using a fused silica capillary (40 cm x 50 µm i.d.); background electrolyte consisted of a combination of 10 mmol L-1 borate buffer and 5 mmol L-1 anionic detergent sodium dodecyl sulfate (95:5; v/v) pH 6.5; hydrodynamic mode at 50 mBar for 5 s; 25 kV separation voltage at 25 ºC; and column temperature 25 ºC with detection at 257 nm. The proposed method, validated following ICH guidelines, was applied to the determination of this antihypertensive with good results compared with an LC method.

USO DE SÍLICAS MODIFICADAS PARA IMOBILIZAÇÃO DE LIPASES

Enzyme-support strategies are increasingly replacing conventional chemical methods in both laboratories and industries with attributes including efficiency, higher performance and multifarious use, where silica surfaces show potential due to the chemical bonds based on the presence of hydroxyl groups which can be modified with different additives. Surface-modified silica is a novel class of materials capable of improving enzyme stability and reusability that can be applied to support several immobilization techniques. This review describes the use of innovative modified supports to improve the state of enzyme immobilization and provide the industrial sector with new perspectives.

A platform for anti-biofilm assays combining viability, biomass and matrix quantifications in susceptibility assessments of antimicrobials against Staphylococcus aureus biofilms

Bacteria can exist as planktonic, the lifestyle in which single cells exist in suspension, and as biofilms, which are surface-attached bacterial communities embedded in a selfproduced matrix. Most of the antibiotics and the methods for antimicrobial work have been developed for planktonic bacteria. However, the majority of the bacteria in natural habitats live as biofilms. Biofilms develop dauntingly fast high resistance towards conventional antibacterial treatments and thus, there is a great need to meet the demands of effective anti-biofilm therapy. In this thesis project it was attempted to fill the void of anti-biofilm screening methods by developing a platform of assays that evaluate the effect that screened compounds have on the total biomass, viability and the extracellular polysaccharide (EPS) layer of the biofilms. Additionally, a new method for studying biofilms and their interactions with compounds in a continuous flow system was developed using capillary electrochromatography (CEC). The screening platform was utilized with a screening campaign using a small library of cinchona alkaloids. The assays were optimized to be statistically robust enough for screening. The first assay, based on crystal violet staining, measures total biofilm biomass, and it was automated using a liquid handling workstation to decrease the manual workload and signal variation. The second assay, based on resazurin staining, measures viability of the biofilm, and it was thoroughly optimized for the strain used, but was then a very simple and fast method to be used for primary screening. The fluorescent resazurin probe is not toxic to the biofilms. In fact, it was also shown in this project that staining the biofilms with resazurin prior to staining with crystal violet had no effect on the latter and they can be used in sequence on the same screening plate. This sequential addition step was indeed a major improvement on the use of reagents and consumables and also shortened the work time. As a third assay in the platform a wheat germ agglutinin based assay was added to evaluate the effect a compound has on the EPS layer. Using this assay it was found that even if compounds might have clear effect on both biomass and viability, the EPS layer can be left untouched or even be increased. This is a clear implication of the importance of using several assays to be able to find “true hits” in a screening setting. In the pilot study of screening for antimicrobial and anti-biofilm effects using a cinchona alkaloid library, one compound was found to have antimicrobial effect against planktonic bacteria and prevent biofilm formation at low micromolar concentration. To eradicate biofilms, a higher concentration was needed. It was also shown that the chemical space occupied by the active compound was slightly different than the rest of the cinchona alkaloids as well as the rest of the compounds used for validatory screening during the optimization processes of the separate assays.

Modification of Polypropylene and Polystyrene Using Nanosilica

The present work focuses on the modification of the commonly used thermoplastics, polypropylene and polystyrene using nanosilica preparcd from a cheap source of sodium silicate. Melt compounding technique has been used for nanocomposite preparation as it is simple and suited to injection moulding. Nanosilica in a polymer matrix provide significant enhancement in strength, stiffness and impact strength. Incorporation of silica particles in a polymer also improves its thennal stability. To achieve better dispersion of fillers in polymer matrices the mixing was done at different shear rates. The enhancement in material properties indicates that at higher shear rates there is greater interaction between particles and the matrix and it depends on filler concentration and type of polymer used. N anosilica is a useful filler in thennoplastic polymers and has been applied in automotive applications, electronic appliances and consumer goods.This thesis is divided into six chapters. General introduction to the topic is described in chapter 1. Salient features of polymer nanocomposites, their synthesis, properties and applications are presented. A review of relevant literature and the scope and objectives are also mentioned in this chapter.The materials used and the vanous experimental method and techniques employed in the study are described in chapter 2. Preparation of nanocomposites by melt blending using Thenno Haake Rheocord, preparation of samples, evaluation of mechanical and thennal properties using UTM, Impact testing and characterization using DMA, TGA and DSC and morphology by SEM are described.The preparation of nanosilica from a laboratory scale to a pilot plant scale is described in chapter 3. Generation of surface modified silica, evaluation of kinetic parameters of the synthesis reaction, scale up of the reactor and modeling of the reactor are also dealt with in this chapter.The modification of the commodity thennoplastic, Polypropylene using nanosilica is described in chapter 4. Preparation of PP/silica nanocomposites, evaluation of mechanical properties, thermal and crystallization characteristics, water absorption and ageing resistance studies are also presented.The modification of Polystyrene using synthesized nanosilica IS described in chapter 5. The method of preparation of PS/silica nanocomposites, evaluation of mechanical properties (static and dynamic), thermal properties melt flow characteristics using Haake Rheocord, water absorption and ageing resistance of these nanocomposites are studied.

Interactions between Bacteriophage DNA and Cationic Biomimetic Particles

The interaction between giant bacteriophage DNA and cationic biomimetic particles was characterized from sizing by dynamic light-scattering, zeta-potential analysis, turbidimetry, determination of colloid stability, visualization from atomic force microscopy (AFM), and determination of cytotoxicity against E. coli from colony forming unities counting. First, polystyrene sulfate (PSS) particles with different sizes were covered by a dioctadecyldimethylammonium bromide (DODAB) bilayer yielding the so-called cationic biomimetic particles (PSS/DODAB). These cationic particles are highly organized, present a narrow size distribution and were obtained over a range of particle sizes. Thereafter, upon adding lambda, T5 or T2-DNA to PSS/DODAB particles, supramolecular assemblies PSS/DODAB/DNA were obtained and characterized over a range of DNA concentrations and particle sizes (80-700 nm). Over the low DNA concentration range, PSS/DODAB/DNA assemblies were cationic, colloidally stable with moderate polydispersity and highly cytotoxic against E. coli. From DNA concentration corresponding to charge neutralization, neutral or anionic supramolecular assemblies PSS/DODAB/DNA exhibited low colloid stability, high polydispersity and moderate cytotoxicity. Some nucleosome mimetic assemblies were observed by AFM at charge neutralization (zeta-potential equal to zero).