Extração líquido-líquido de ferro(III) e titânio(IV) pelo ácido bis-(2-etil-hexil) fosfórico (D2EHPA) em meio de ácido sulfúrico

This work presents a study on the separation of Fe(III) and Ti(IV) from sulfuric acid leaching solutions of ilmenite (FeTiO3) using liquid-liquid extraction with D2EHPA in n-dodecane as extracting agent. The distribution coefficients (K D) of the elements related to free acidity and concentration of Fe(III) and Ti(IV) were determined. Free acidity was changed from 3x10-2 to 11.88 mol L-1 and D2EHPA concentration was fixed at 1.5 mol L-1. Recovery of final products as well as recycling of wastes generated in the process were also investigated. The LLE process as a feasible alternative to obtain high-purity TiO2.

Singlet oxygen reactivity in water-rich solvent mixtures

The 3-methylindole (3MI) oxygenation sensitized by psoralen (PSO) has been investigated in 100%, 20% and 5% O2-saturated water/dioxane (H2O/Dx) mixtures. The lowering of the ¹O2* chemical rate when water (k chem∆3MI = 1.4 × 109 M-1 s-1) is replaced by deuterated water (k chem∆3MI = 1.9 × 108 M-1 s-1) suggests that hydrogen abstraction is involved in the rate determining step. A high dependence of the chemical rate constant on water concentration in H2O/Dx mixtures was found showing that water molecules are absolutely essential for the success of the 3MI substrate oxidation by ¹O2* in water-rich solvent mixtures.

Validação de métodos para determinação de fluoxetina em cápsulas

A UV spectrophotometric method was developed and validated and a chromatographic method was adapted from the American Pharmacopeia for the analysis of Fluoxetine Hydrochloride capsules. Ethanol was used as solvent for the spectrophotometric method, with detection and determination at 276 nm. The separation for the chromatographic method was carried out using the reversed-phase column LC-8, triethylamine buffer, stabilizer free tetrahydrofuran and methanol (5:3.5:1.5), pH 6.0 as mobile phase and detection at 227 nm. The results obtained for both methods showed to be accurate, precise, robust and linear over the concentration range 100.00 - 300.00 µg/mL and 40.00 - 80.00 µg/mL of fluoxetine hydrochloride for the spectrophotometric and chromatographic methods, respectively. The accuracy of the methods was evaluated by a recovery test and showed results between 98.89 and 101.10%.

Determination of free urinary cortisol in cushing's syndrome using reversed-phase high performance liquid chromatography

Determination of free urinary cortisol is a test of choice in the diagnosis of Cushing's syndrome. In this study, cortisol was quantified using reversed-phase high-performance liquid chromatography (RP-HPLC) in urine samples previously extracted with ether and using triamcinolone acetonide as internal standard (IS). A BDS-Hypersil-C18® column, water-acetonitrile (72:28; v/v), with a flow rate of 1.0 mL/min and detection at 243 nm were used. This method showed to be both effective and efficient, with sensitivity and linearity ranging from 2.50 to 150 μg/L, and can be used in substitution to the radioimmunoassay technique within this concentration range.

Antimycobacterial and cytotoxicity activities of free and liposome-encapsulated 3-(4'-bromo[1,1'-biphenyl-4-yl)-3-(4-bromo-phenyl)-N,N-dimethyl-2-propen-1-amine

The antimycobacterial activity of 3-(4'-bromo[1,1'-biphenyl-4-yl)-3-(4-bromo-phenyl)-N,N-dimethyl-2-propen-1-amine (BBAP), free or incorporated in preformed liposomes, on extracellular M. tuberculosis H37Rv was 8 and 25 μM (MIC), respectively. Extracellular antimycobacterial activity was not significantly improved by entrapment of BBAP in liposomes, but there was a 6.1-fold reduction of BBAP cytotoxicity on J774 macrophages. Liposomal BBAP or its free form showed IC50 values of 165 and 27 μM, resulting in a selectivity index (SI=IC50/MIC) of 3.4 and 6.6, respectively. Free BBAP in concentrations from 10 to 80 μM were quite effective in eliminating intracellular M. tuberculosis while liposomal formulation was less effective at these concentrations.

Spectrophotometric determination of famotidine using sulphonphthalein dyes

Four new extraction-free spectrophotometric methods have been established for the quantitation of famotidine (FMT). The methods are based on the formation of yellow ion-pair complexes between FMT and four sulphonphthalein dyes viz., bromothymol blue (method A), bromophenol blue (method B), bromocresol purple (method C) and bromocresol green (method D) in dioxane or acetone medium. The experimental variables such as reagent concentration, solvent medium and reaction time have been carefully optimized to achieve the highest sensitivity. The proposed methods were applied successfully to the determination of famotidine in tablets with good accuracy and precision and without interferences from common excipients. The results obtained by the proposed methods were compared favorably with those of the reference method.

Characterization and in vitro release of cyclosporine-A from poly(D,L-lactide-co-glycolide implants obtained by solvent/extraction evaporation

Cyclosporine-A-loaded PLGA implants were developed intended for ocular route. Implants were prepared using solvent extraction/evaporation technique followed by casting of the cake into rods in a heated surface. XRD patterns showed that cyclosporine-A was completely incorporated into PLGA. FTIR and DSC results indicated alterations on drug molecular conformation aiming to reach the most stable thermodynamic conformation at polymer/drug interface. Implants provided controlled/sustained in vitro release of the drug. During the first 7 weeks, the drug release was controlled by the diffusion of the cyclosporine-A; and between 7-23 week period, the drug diffusion and degradation of PLGA controlled the drug release.

Validação de método analítico livre de acetonitrila para análise de microcistinas por cromatografia líquida de alta eficiência

Blooms of cyanobacteria represent a public health risk due to their cyanotoxins such as microcystins. Liquid chromatography techniques to separate and quantify microcystins invariably use acetonitrile as the organic component of the mobile phase. The price and availability of acetonitrile together with its elevated toxicity encourage the validation of acetonitrile-free methods of microcystin analysis. In this work, methanol was employed as the organic solvent of the mobile phase and the validation method was performed with different environmental water samples. The method showed limits of detection between 0.17 and 0.25 µg/L and of quantification between 0.55 and 0.82 µg/L for the microcystin variants: -RR, -YR, -LR, -LA.

Optimization of solvent mixtures for extraction from bark of Schinus terebinthifolius by a statistical mixture-design technique and development of a UV-Vis spectrophotometric method for analysis of total polyphenols in the extract

A statistical mixture-design technique was used to study the effects of different solvents and their mixtures on the yield, total polyphenol content, and antioxidant capacity of the crude extracts from the bark of Schinus terebinthifolius Raddi (Anacardiaceae). The experimental results and their response-surface models showed that ternary mixtures with equal portions of all the three solvents (water, ethanol and acetone) were better than the binary mixtures in generating crude extracts with the highest yield (22.04 ± 0.48%), total polyphenol content (29.39 ± 0.39%), and antioxidant capacity (6.38 ± 0.21). An analytical method was developed and validated for the determination of total polyphenols in the extracts. Optimal conditions for the various parameters in this analytical method, namely, the time for the chromophoric reaction to stabilize, wavelength of the absorption maxima to be monitored, the reference standard and the concentration of sodium carbonate were determined to be 5 min, 780 nm, pyrogallol, and 14.06% w v-1, respectively. UV-Vis spectrophotometric monitoring of the reaction under these conditions proved the method to be linear, specific, precise, accurate, reproducible, robust, and easy to perform.

CHEMICAL CONSTITUENTS, ANTI-INFLAMMATORY, AND FREE-RADICAL SCAVENGING ACTIVITIES OF Guettarda viburnoides CHAM. & SCHLTDL. (RUBIACEAE)

Chemical investigation of Guettarda viburnoides (leaves) led to the isolation of ursolic acid, uncaric acid, secoxyloganin, and grandifloroside, along with a mixture of quercetin-3-O-β-D-galactopyranoside and quercetin-3-O-β-D-glucopyranoside, and of β-sitosterol and stigmasterol. The structures of the isolated compounds were elucidated on the basis of their NMR data. The crude extract, ethyl acetate fraction, aqueous-methanol fraction, and grandifloroside showed significant DPPH free-radical scavenging activities with IC50 ranging from 18.92 to 26.47 µg mL-1. The topical administration of the crude extract and fractions markedly reduced the croton oil-induced mice ear edema in 67.0%-99.0%. Inhibition of tissue MPO activity was also observed, which demonstrated an anti-inflammatory effect of the G. viburnoides species.

USE OF A LOW-COST TEMPLATE-FREE ZSM-5 FOR ATMOSPHERIC PETROLEUM RESIDUE PYROLYSIS

To understand the physicochemical properties and catalytic activity during the pyrolysis of atmospheric petroleum residue, a template-free ZSM-5 zeolite was synthesized using a direct method without additional seeds or an organic structure director and compared with conventionally synthesized ZSM-5. The crystallinities of the two zeolites were evaluated by XRD and FTIR and were quite similar; however, structural analyses using SEM and argon physisorption revealed that the zeolites diverged in particle diameter and in the external surface area of the micropores. The synthesis procedure without a template incorporated additional aluminum into the crystalline network, according to ICP-AES and TPD NH3 experiments. The catalytic pyrolysis performed over the template-free ZSM-5 generated results comparable to those for pyrolysis performed over the conventional ZSM-5 according to its hydrocarbon distribution. The selectivity to aromatics compounds was exactly the same for both ZSM-5 zeolites, and these values stand out compared to thermal pyrolysis. The template-free ZSM-5 produced 20% of light hydrocarbons (C4-C6), where such compounds are olefins and paraffins of great interest to the petrochemical industry. Therefore, template-free ZSM-5 is promising for industrial use due to its lowered synthesis time, low-cost and significant distribution to light hydrocarbons.

A model for specific interactions of manganese-phthalocyanine in protic media

Extinction coefficients (e) changes of manganese phthalocyanine (Mn-Pc) were studied in different organic solvents and related to solvent polarity scales; (Kosower's values (Z), Dimroth's values (E T), donor numbers (DN) and linear solvation energy relationships (LSER) or linear free energy relationships (LFER));, theoretical molecular orbital calculations and ligand/solvent coordination processes in order to predict molecular interaction with the medium and identification of predominant intermolecular forces.

Effect of magnesium addition on the vacancy-Mg binding free enthalpy in Al-Cr alloys

The Mg-vacancy binding free enthalpy of Al-Cr solid solution alloys with Mg addition was calculated by electrical resistivity measurements. The obtained value is lower than that obtained for dilute Al-Mg alloys with almost the same Mg content and may be attributed to the diffusion of Mg.

Macrophomina phaseolina: density and longevity of microsclerotia in soybean root tissues and free on the soil, and competitive saprophytic ability

In field experiments, the density of Macrophomina phaseolina microsclerotia in root tissues of naturally colonized soybean cultivars was quantified. The density of free sclerotia on the soil was determined for plots of crop rotation (soybean-corn) and soybean monoculture soon after soybean harvest. M. phaseolina natural infection was also determined for the roots of weeds grown in the experimental area. To verify the ability of M. phaseolina to colonize dead substrates, senesced stem segments from the main plant species representing the agricultural system of southern Brazil were exposed on naturally infested soil for 30 and 60 days. To quantify the sclerotia, the methodology of Cloud and Rupe (1991) and Mengistu et al. (2007) was employed. Sclerotium density, assessed based on colony forming units (CFU), ranged from 156 to 1,108/g root tissue. Sclerotium longevity, also assessed according to CFU, was 157 days for the rotation and 163 days for the monoculture system. M. phaseolina did not colonize saprophytically any dead stem segment of Avena strigosa,Avena sativa,Hordeum vulgare,Brassica napus,Gossypium hirsutum,Secale cereale,Helianthus annus,Triticosecalerimpaui, and Triticum aestivum. Mp was isolated from infected root tissues of Amaranthus viridis,Bidens pilosa,Cardiospermum halicacabum,Euphorbia heterophylla,Ipomoea sp., and Richardia brasiliensis. The survival mechanisms of M. phaseolina studied in this paper met the microsclerotium longevity in soybean root tissues, free on the soil, as well as asymptomatic colonization of weeds.