Transferência de elétron inversa na quimiexcitação da reação peróxi-oxalato usando ativadores facilmente redutíveis

Chemiluminescence properties of the peroxyoxalate reaction in the presence of activators bearing electron withdrawing substituents were studied, to evaluate the possible occurrence of an inverse electron transfer, from the peroxide intermediate to the activator, in its chemiexcitation step. Relative catalytic rate constants and singlet quantum yields were obtained for the peroxyoxalate reaction, using 9-chloro, 9,10-dichloro, 9-cyano and 9,10-dicyanoanthracenes as activators. The linear free-energy correlation of the relative rate constants with the activators' reduction potentials and the dependence of the quantum yields on the released energy confirm, for the first time, the occurrence of this inverse electron transfer.

Hidrólise Enzimática de Biomassa

Production of ethanol from biomass fermentation has gained much attention recently. Biomass cellulosic material is first converted into glucose either by chemical or by enzymatic process, and then glucose is fermented to ethanol. Considering the current scenario, where many efforts are devoted for the search of green routes to obtaining ethanol from renewable sources, this review presents the relationship between structure and properties of cellulosic material, pre-treatments and hydrolysis of cellulosic material, and structure and function of cellulase enzyme complex.

Determinação de As, Cd e Pb em amêndoas e mesocarpo de babaçu, sapucaia, xixá e castanha-do-pará por espectrometria de absorção atômica

This work describes methods for the simultaneous determination of Cd and Pb by graphite furnace atomic absorption spectrometry and As by hydride generation atomic absorption spectrometry in Brazilian nuts. The samples (~ 0.300 g) were digested to clear solutions in a closed vessel microwave oven. The pyrolysis and atomization temperatures for simultaneous determinations of Cd and Pb were 1100 and 2100 °C, respectively, using 0.5% (w v-1) NH4H2PO4 + 0.03% (w v-1) Mg(NO3)2 as chemical modifier. The limits of detection (3Δ) were 3.8 μg kg-1 for As, 0.86 μg kg-1 for Cd and 13 μg kg-1 for Pb. The reliability of the entire procedures was confirmed by peach leaves (No. 1547 - NIST) certified reference material analysis and addition and recovery tests. The found concentrations presented no statistical differences at the 95% confidence level.

Trypanocidal activity of Piper arboreum and Piper tuberculatum (Piperaceae)

In the scope of our ongoing research on bioactive agents from Brazilian flora, twenty-four extracts and fractions obtained from Piper arboreum Aub. and Piper tuberculatum Jacq. (Piperaceae) were screened for trypanocidal activity by using MTT colorimetric assay. The strongest activity was found in hexane fractions from the leaves of P. arboreum (IC50= 13.3 µg/ mL) and P. tuberculatum (IC50 = 17.2 µg/mL). Hexane fractions of the fruits of P. tuberculatum and P. arboreum showed potent toxic effects on epimastigote forms of Trypanosoma cruzi, with values of IC50 (µg/mL) of 32.2 and 31.3, respectively. Additionally, the phytochemical study of the hexane fraction of P. arboreum leaves furnished two pyrrolidine amides, piperyline (1) and 4,5-dihydropiperyline (2), which could be responsible, at least in part for the observed antiprotozoal activity.

Análise direta de sólidos por espectrometria de absorção atômica com atomização em forno de grafite: uma revisão

This is a review of direct analysis using solid sampling graphite furnace atomic absorption spectrometry. Greater emphasis is dedicated to sample preparation, sample homogeneity, calibration and its application to microanalysis and micro-homogeneity studies. The main advantages and some difficulties related to the applicability of this technique are discussed. A literature search on the application of solid sampling graphite furnace atomic absorption spectrometry in trace element determination in many kinds of samples, including biological, clinical, technological and environmental ones, is also presented.

Low temperature synthesis of CdSiO3 nanostructures

We report the synthesis of single-phase, crystalline CdSiO3 nanostructures at 580ºC; to the best of our knowledge, this is the lowest temperature at which this material is reported to form. The desired phase does not form below 580ºC, since the diffraction peaks are shifted to lower angles in the material treated at 570ºC when compared to JDPDS Card No. 85-0310. The source of silicon has strong influence on the product morphology: Na2SiO3 yields single-phase CdSiO3 in needle-shaped nanostructures, while high surface area mesostructured SiO2 yields coralloid-shaped particles. Low angle X-ray diffractometry reveals that the mesostructured nature of the silica precursor is not maintained in the resulting CdSiO3. Scanning electron microscopy suggests that in this case a transition occurs between the spherical morphology of the precursor and the needle-shape morphology of the material prepared from Na2SiO3. The surface area of the silica precursor has a strong influence in the reaction, since the use of commercial silica with a lower surface area does not yield the desired product.

Development and validation of a simple and rapid capillary zone electrophoresis method for determination of nnrti nevirapine in pharmaceutical formulations

A simple and fast capillary zone electrophoresis (CZE) method has been developed and validated for quantification of a non-nucleoside reverse transcriptase inhibitor (NNRTI) nevirapine, in pharmaceuticals. The analysis was optimized using 10 mmol L-1 sodium phosphate buffer pH 2.5, +25 kV applied voltage, hydrodynamic injection 0.5 psi for 5 s and direct UV detection at 200 µm. Diazepam (50.0 µg mL-1) was used as internal standard. Under these conditions, nevirapine was analyzed in approximately less than 2.5 min. The analytical curve presented a coefficient of correlation of 0.9994. Limits of detection and quantification were 1.4 µg mL-1 and 4.3 µg mL-1, respectively. Intra- and inter-day precision expressed as relative standard deviations were 1.4% and 1.3%, respectively and the mean recovery was 100.81%. The active pharmaceutical ingredient was subjected to hydrolysis (acid, basic and neutral) and oxidative stress conditions. No interference of degradation products and tablet excipients were observed. This method showed to be rapid, simple, precise, accurate and economical for determination of nevirapine in pharmaceuticals and it is suitable for routine quality control analysis since CE offers benefits in terms of quicker method development and significantly reduced operating costs.

Determination of picloram in waters by sequential injection chromatography with UV detection

This paper describes a sequential injection chromatography procedure for determination of picloram in waters exploring the low backpressure of a 2.5 cm long monolithic C18 column. Separation of the analyte from the matrix was achieved in less than 60 s using a mobile phase composed by 20:80 (v v-1) acetonitrile:5.0 mmol L-1 H3PO4 and flow rate of 30 μL s-1. Detection was made at 223 nm with a 40 mm optical path length cell. The limits of detection and quantification were 33 and 137 μg L-1, respectively. The proposed method is sensitive enough to monitor the maximum concentration level for picloram in drinking water (500 μg L-1). The sampling frequency is 60 analyses per hour, consuming only 300 μL of acetonitrile per analysis. The proposed methodology was applied to spiked river water samples and no statistically significant differences were observed in comparison to a conventional HPLC-UV method.

Estudo eletroquímico comparativo do aço ISO 5832-9 em diferentes meios de interesse biológico

Foi estudado o comportamento eletroquímico a 37°C do aço inoxidável ISO 5832-9, em meios de NaCl 0,9 %, de Ringer Lactato e meio mínimo de Eagle (MEM), por voltametria linear e análises da superfície por microscopia eletrônica de varredura (MEV) e por espectroscopia por dispersão de energia (EDS). Foram feitos ensaios mecânicos e testes de toxicidade. O aço ISO 5832-9 se encontra passivado no potencial de corrosão e não apresenta corrosão por pite nos três meios estudados em toda faixa de potencial investigada, desde o potencial de corrosão até 50 mV acima do potencial de transpassivação. Em meio de MEM, no entanto, as análises por MEV e EDS mostraram que o referido aço, nesse valor mais elevado de potencial, apresentou um comportamento diferente, com perda das inclusões de óxido de manganês. Os potenciais de corrosão, Ecorr (potencial de circuito aberto estacionário) bem como os valores de densidade de corrente de passivação, variaram na seguinte ordem: Ecorr, RL < Ecorr, NaCl < Ecorr, MEM. e jMEM << jRL ≅ jNaCl. No ensaio de citotoxicidade, o aço foi caracterizado como não-tóxico.

Oxidative DNA damage induced by S(IV) in the presence of Cu(II) and Cu(I) complexes

The DNA damage induced by S(IV) in the presence of some Cu(II) complexes in air saturated solution was investigated. The addition of S(IV) to an air saturated solution containing CuII GGA (GGA = glycylglycyl-L-alanine), CuII G3 (G3 = triglycine) or CuII G4 (G4 = tetraglycine) and Ni(II) traces, causes rapid formation of the respective Cu(III) complex, with simultaneous O2 uptake and S(IV) oxidation. SO3•- and HO• were detected by EPR-spin trapping experiments. The DNA strand breaks were attributed to the oxysulfur radicals formed. In the reduction of Cu(II)/BCA (BCA = 4,4' dicarboxy-2-2'-biquinoline) by S(IV), with CuI BCA complex formation, there is the possible formation of carbon centered radical of BCA or peroxyl radical (ROO•) capable of oxidizing DNA bases. The intensity of DNA damage in the presence of these Cu(II) complexes and S(IV) (10-300 µmol L-1) followed the order: CuII BCA ∼ CuII G4 ∼ Cu(II) (added as Cu(NO3)2) > CuII G3 ∼ CuII GGA. Specifically for CuII BCA the damage occurred even at lower S(IV) concentration (0.1 µmol L-1). For the Cu(II) complexes with glycylglycylhistidine, glycylhistidylglycine, glycylhistidyllysine and glycylglycyltyrosylarginine the Cu(III) formation and the DNA damage was not observed.

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

A novel disposable electrochemical microcell: construction and characterization

An alternative technique for the fabrication of disposable electrochemical microcells containing working, reference and auxiliary electrodes on a single device is reported. The procedure is based on thermal-transfer of toner masks onto CD-R (recordable compact discs) gold surfaces to define the layout of the electrodes (contour). In a subsequent step, the layout is manually painted with a permanent marker pen. The unprotected gold surface is conveniently etched (chemical corrosion) and the ink is then easily removed with ethanol, generating gold surfaces without contamination. The final and reproducible area of the electrodes is defined by heat transference of a second toner mask. Silver epoxy is deposited on one of the gold bands which is the satisfactorily used as reference electrode. These microcells were electrochemically characterized by cyclic, linear, and square wave voltammetry, and several electroactive species were used as model systems. The area reproducibility of the electrodes for different microcells was studied and a relative standard deviation better than 1,0% (n = 10) was obtained. Disposable electrochemical microcells were successfully used in analysis of liquid samples with volumes lower than 200 µL and good stability and reproducibility (RSD less than 2.0%) were achieved. These microcells were also evaluated for quantification of paracetamol and dipyrone in pharmaceutical formulations.

A biosensor based on immobilization of lactate oxidase in a PB-CTAB film for FIA determination of lactate in beer samples

An amperometric lactate biosensor with lactate oxidase immobilized into a Prussian Blue (PB) modified electrode was fabricated. The advantage of using cetyltrimethylammonium bromide (CTAB) in the electrodeposition step of PB films onto glassy carbon surfaces was confirmed taking into account both the stability and sensitivity of the measurements. The biosensor was used in the development of a FIA amperometric method for the determination of lactate. Under optimal operating conditions (pH = 6.9, E = -0.1 V), the linear response of the method was extended up to 0.28 µmol L-1 lactate with a limit of detection of 0.84 mmol L-1. The repeatability of the method for injections of a 0.28 mmol L-1 lactate solution was 2.2 % (n = 18). The usefulness of the method was demonstrated by determining lactate in beer samples and the results were in good agreement with those obtained by using a reference spectrophotometric enzyme method.

Caracterização de cálculos renais por análise térmica

Dez amostras de cálculos renais foram estudadas por Análise Elementar de CHN (EA), Espectroscopia de Absorção no Infravermelho (IV) e Difração de raios X pelo método de Pó (XRD). O comportamento térmico das amostras foi estudado por Termogravimetria/Termogravimetria Derivada (TG/DTG) e por Calorimetria Exploratória Diferencial (DSC). Os resultados de EA, Espectroscopia de Absorção IV e XRD mostraram a presença de estruvita [NH4Mg(PO4).6H2O], apatita, oxalato de cálcio monohidratado e oxalato de cálcio dihidratado. As curvas TG e DSC permitiram classificar as amostras em dois grupos diferentes: Grupo I mostrando comportamento térmico típico de estruvita e Grupo II apresentando um perfil termoanalítico característico de mistura de oxalatos.

Effect of experimental heat treatment on mechanical properties of resin composites

The aim of this study was to verify the influence of an experimental heat treatment (170ºC/10 min) using a casting furnace on the mechanical properties (hardness and flexural strength) of 2 commercial direct resin composites (TPH Spectrum and Filtek P60) compared to a commercial indirect resin system (BelleGlass). Heat treatment temperature was determined after thermal characterization by thermogravimetry (TG) and differential scanning calorimetry (DSC). Data was analyzed by ANOVA and Tukey's test at 5% significance level. There was statistical significance for the main factor heat treatment (p=0.03) and composite (p=0.02), for flexural strength. For Knoop hardness, only the main factor composite was statistically significant (p=0.00). P60 presented higher hardness than TPH. No statistically significant correlation between mechanical properties tested was detected. Based on these results, it was possible to conclude that heat treatment influenced flexural strength of direct composites, while it was not observed for hardness. The association of direct composites with a simple post-cure heat treatment may be an alternative for current indirect composite systems, although more studies are needed to verify other properties of the composites for this application.