A técnica da reflectância difusa aplicada ao estudo da fluorescência de 2,3-naftalimidas n-substituídas com grupos alquila incluídas em b-ciclodextrina e adsorvidas em celulose microcristalina

The solution fluorescence of N-alkyl-2,3-naphthalimides (1-4) in polar protic and aprotic solvents was compared to the emission from solid samples resulting from the imide complexation with b-cyclodextrin or adsorption on the surface of microcrystalline cellulose. Solid samples of the inclusion complex 2,3-naphthalimides/b-cyclodextrin show maximum for fluorescence emission significantly different to the observed in methanolic solution. Beside this, a clear effect on the alkyl chain length could be observed for these samples which is probably due to differences in probe location inside the cyclodextrin cavity. The constancy for fluorescence quantum yield and fluorescence lifetime for the imides 1 - 4 adsorbed on microcrystalline cellulose suggests that, independently of the polarity of the solvent used for sample preparation, the probe is preferentially located on the cellulose surface. An increase of fluorescence quantum yield and fluorescence lifetime for solid samples, when compared to the values obtained in solution for the different solvents employed in this study (acetonitrile, methanol and water), is fully in accordance with a decrease of the probe mobility due to inclusion in b-cyclodextrin or to adsorption on cellulose.

Uso de espectrometria de massas em medidas eletroquímicas - a técnica de DEMS

The combination of cyclic voltammetry and on line mass spectrometry, called differential electrochemical mass spectrometry (DEMS), is already a well established method for on line identification and quantitative detection of the products and intermediates of electrochemical reactions. This article aims to show the principles of the method and how this technique have been used to study electrochemical problems such the electrocatalytic oxidation of organic molecules, as methanol and ethanol, at noble metal electrodes.

Tecnologia de células a combustível

The fuel cell principle was discovered by Sir Grove 150 years ago. However material problems prohibited its commercialization for a long time. A change has been occurring during the last 30 years, so two types of fuel cell technologies can be distinguished: low and high temperature operation cells. Nowadays, only phosphoric acid cells are commercially offered as 200 kWel power plants. Membrane cells are more suitable for automobile electrotraction with a very low (or no) environmental impact. The fuel continues, however, to play a very particular role, since hydrogen is not easy to store and to transport. The more promising target is the utilization of liquid methanol. The Brazilian scenario concerning this kind of technology is discussed.

A síntese do aduto binuclear [Fe(CNBu t)(CO)4(HgSO4 )]

The binuclear [Fe(CNBu t)(CO)4(HgSO4 )] adduct was obtained in the reaction of HgSO4 with [Fe(CNBu t)(CO)4] in methanol. This adduct, without a similar in the homoleptic pentacarbonyliron, was characterized by analytical and spectroscopic data. Further Mössbauer and molar conductivity studies have confirmed it's adduct nature.

Extração por fluido supercrítico de alguns inseticidas carbamatos em amostras de batata, com determinação por HPLC/fluorescência e confirmação por HPLC/espectrometria de massas

Six supercritical fluid extraction (SFE) methods were tested, by varying the following operational parameters: CO2 pressure, time and temperature of extraction, type and proportion of static modifier, and Hydromatrix®/sample rate into cell. Firstly, insecticide carbamates were extracted from spiked potatoes samples (fortification level of 0,5 mg.Kg-1) by using SPE procedures, and then final extracts were analyzed HPLC/fluorescence. Good performance was observed with SFE methods that operated with values of temperature and CO2 pressure of 50 ºC and 350 bar, respectively. Best efficiency was obtained when it was used acetonitrile as a modifier (3% on the cell volume), and Hydromatrix®/sample rate of 2:1. Static time was of 1 min; total extraction time was of 35 min; dynamic extraction was performed with 15 mL of CO2, and it was used methanol (2 mL) for the dissolution of the final residue. In such conditions, pesticide recoveries varied from 72 to 94%, depending on the analyzed compound. In higher extraction temperatures, a rapid degradation was observed for some compounds, such as aldicarb and carbaryl; presence of their metabolites was further confirmed by HPLC-APCI/MS in positive mode. Detection limits for chromatographic analysis varied from 0,2 to 1,3 ng.

Método colorimétrico para determinação de dióxido de nitrogênio atmosférico com preconcentração em coluna de c-18

An alternative analytical method for nitrogen dioxide (NO2) in atmosphere was developed. The collection of NO2 is performed by a Sep-Pack C-18 cartridge impregnated with 11% (v/v) of triethanolamine plus 3,6 % (v/v) of ethylene glycol plus 25 % (v/v) of acetone combined solution. When the impregnating is used, NO2 is collected with good repeatibility (CV = 3,3 %). The NO2 absorbed in the sampler was stripped from the sorbent with a methanol 5% (v/v) aqueous solution and was determined by colorimetry as nitrite by using the Griess-Saltzman reagent. The detection limit of 1,4 ppb for 60 min sampling at 0,5 L min-1 flow rate was obtained. Preparation and conditioning procedures for TEA-C-18 cartridge, sampling flow rate, absorption capacity and interference of other species are discussed.

Comportamento térmico da caulinita hidratada

Well-ordered kaolinite from the Brazilian Amazon Region (State of Pará) was initially reacted at 60 °C with a water dimethylsulfoxide mixture. After washing and characterisation, the resulting material was washed several times with methanol and in the final step with water. The water molecules displace the previously dimethylsulfoxide intercalated molecules and two different hydrated kaolinites were obtained. An unstable phase characterized by an interplanar basal distance of 0,996 nm that after drying collapse to the stable 0,844 nm hydrated kaolinite. The dehydration of the sample to disordered kaolinite was accompanied by Powder X-ray Diffractometry, thermal analysis (simultaneous TG and DSC) and FTIR spectroscopy.

Estudo fitoquímico e avaliação da atividade moluscicida da Kielmeyera variabilis Mart (Clusiaceae)

Methanol extract obtained from Kielmeyera variabilis stems showed significant molluscicidal activity against Biomphalaria glabrata. The phytochemical studies of the plants stem to the isolation of three xanthones (assiguxanthone-B, kielcorin and 1,3,5,6-tetrahtydroxy-2-prenylxanthone) and a organic acid (2,5-dihydroxy benzoic acid). The structures of these compounds were identified by IR, MS, ¹H and 13C NMR spectral analysis and comparison with literature data.

Influência do material do destilador na composição química das aguardentes de cana: parte II

The quantitative chemical analysis of the Brazilian sugar cane spirit distilled from glass column packaged with copper, stainless steel, aluminum sponge, or porcelain balls is described. The main chemical compounds determined by gas chromatography coupled with flame ionization (FID) and flame photometric (FPD) detectors and liquid chromatography coupled with diode array detector are aldehydes, ketones, carboxylic acids, alcohols, esters and dimethylsulfite (DMS). The spirits produced either in columns filled with copper or aluminum pot still exhibits the lowest DMS contents but the higher sulfate and methanol contents, whereas spirits produced in stainless steel or porcelain showed higher DMS concentration and lower teors of sulfate ion and methanol. These observations are coherent with DMS oxidation to sulfate, with methanol as by product, in the presence of either copper or aluminum.

Fotocromismo em filmes finos de óxidos de tungstênio de diferentes composições

Tungsten oxide thin films with three different compositions were deposited by reactive sputtering in an oxygen-argon plasma. In a system composed of a home made photochemical reactor coupled with an optic fiber spectrophotometer, the photochromic effect was studied in these oxide films as function of UV irradiation time, in ethanol, methanol and formaldehyde atmospheres. It was observed that the photochromic efficiency depends on the vapor chemical nature where the film is irradiated as well as the film composition. Kinetic analysis suggest that two kinds of optical absorption centers should respond by the photochromic effect in these films, one generated at film surface and other inside it, which one presenting a different time constant.

Transferência de energia entre corantes catiônicos em sistemas homogêneos

In this work, the energy transfer by dipole-dipole interaction between cationic dyes in n-alcohols (methanol, ethanol, 1-propanol and 1-butanol) is studied by time resolved and steady state fluorescence measurements. The critical radii of energy transfer were determined by three independent methods; the spectral overlap, fluorescence decay profiles, and relative intensity measurements. In all solvents, R0 values of the dye pairs obtained from spectral overlap were between 40 to 90 Å. Steady state and time resolved fluorescence measurements resulted in values of R0 in the range of 50 - 80 Å, with good correlation of values.

Gerenciamento de resíduos químicos e águas servidas no laboratório de isótopos estáveis do CENA/USP

A system for disposal and recovery of the main effluents and chemical waist from isotope separation plants and enriched compounds-15N and 34S production has been carried out at the Stable Isotope Laboratory (LIE) of the CENA/USP. Around four hundred thousand liters of effluents has been recovered yearly. Among the recovered chemical wastes, the more relevant are: ammonia; brome; ammonium and sodium sulfate; sodium hydroxide; sulfur dioxide; and hydrochloric acid. Chemical wastes containg recoverable heavy metals (Ag, Cr and Cu) and solvents (methanol, ethanol and acetone) are processed and recovered. Gaseous emissions, mainly H2S are used for recovery of heavy metals solutions. The minimization of the residues waters, as well the reduction of electric energy consume was established using a water deionization system. A cost/effect balance of the process is reported.

Aplicação da CLAE para determinação do ácido 10-Hidróxi-2-decenóico (10-HDA) em geléia real pura e adicionada a mel brasileiro

The aim of this paper was to determine the 10-HDA in pure royal jelly and products containing royal jelly, using HPLC methodology. 10-HDA is the natural indicator of the presence of royal jelly in products and also gives the authenticity of pure royal jelly. The chromatographic conditions used were: isocratic system, C18-H column, auto sampler, diode array UV-VIS detector (225 nm), mobile phase with methanol/water (45:55), pH= 2.5 and a-naphtol as internal standard. The results obtained using laboratory samples for pure royal jelly were 2.37%, varying from 0.15% for honey with 10% of royal jelly to 2.10% for honey with 90% of royal jelly respectivelly. For commercial products, the 10-HDA content varied from no detectable to 0.026%. The recovery test presented a minumum of 100.44% The detection limit was 45.92 ng/mL and the quantification limit was 76.53 ng/mL.

Análise de ácidos graxos por eletroforese capilar utilizando detecção condutométrica sem contato

This article describes a novel approach to the separation of fatty acids ranging from 8 to 20 carbons using capillary electrophoresis with contactless conductivity detection. Complete separation of nine linear chain fatty acids (from C8:0 to C20:0) was achieved in 15 min under normal polarity operation. Limits of detection ranged from 35 to 319 µmol L-1 for C20:0 to C8:0, respectively. The optimized running electrolyte composition was 5.0 mmol L-1 phosphate buffer at pH 7, 4.0 mmol L-1 dimethyl-b-cyclodextrin, 2.0 mmol L-1 trimethyl-b-cyclodextrin, acetonitrile 50% (v/v), and methanol 20% (v/v). The applicability of the separation system was demonstrated by the analysis of coconut vegetable oil.

Efecto de solvente sobre la descomposición térmica de trans-3,6-dimetil-3,6-difenil-1,2,4,5-tetraoxaciclohexano en solución

The thermal decomposition reaction of trans-3,6-dimethyl-3,6-diphenyl-1,2,4,5-tetraoxacyclohexane (acetophenone cyclic diperoxide, DPAF), in different solvents (methanol, 1,4-dioxane, acetonitrile and 2-propanol/benzene mixtures) in the initial concentration and temperature ranges of (4.2-10.5) x 10-3 M and 140.0 to 185.0 ºC, respectively, follows a pseudo first order kinetic law up to at least 70% DPAF conversion. An important solvent effect on the rate constant values, activation parameters (DH# and DS#) and reaction products obtained in different solvents is detected, showing that the reaction is accelerated in alcohols.