Biblioteca Digital

O efeito Raman ressonante do complexo (NH4)4Mo2Cl8.NH4Cl.H2O, contendo o íon Mo2Cl84-, foi estudado tanto na temperatura ambiente como na de nitrogênio líquido. Com base nos resultados obtidos mostra-se que a explicação previamente oferecida por outros autores para o aparecimento de ressonância com excitação em 568,2 nm não é correta. É sugerida uma explicação diferente para este comportamento baseada nos espectros Raman e de absorção. A transferência de elétron fotoestimulada no íon complexo (NH3)5RuII-pz-CuII foi comprovada através do estudo do efeito Raman ressonante. Com base nos espectros Raman obtidos em condições de ressonância e também nas medidas de polarização, o estado eletrônico excitado envolvido foi caraterizado. Os perfis de excitação para v1 e 2vl do íon RuO42- em solução aquosa foram obtidos usando diversas radiações excitantes. Os perfis mostraram uma desintensificação das intensidades Raman pré-ressonantes na região da transição interna do íon. O efeito foi interpretado usando o tratamento proposto por Stein e col. para o efeito Raman anti-ressonante.; The Raman resonance effect of the complex (NH4)4Mo2Cl8.NH4Cl.H2O, containing the Mo2Cl84- ion, was investigated at both room and liquid nitrogen temperatures. On basis of the obtained results it is shown that the previous explanation given by others authors for the resonance observed with 568.2 nm excitation is not a correct one. A different explanation for this behaviour is suggested...

A grande diversidade de métodos para a determinação de manganês a nível de traços em diferentes matrizes, reflete a importância deste elemento. Um dos métodos mais usados é a espectrofotometria de absorção atômica, geralmente precedida por uma etapa de pré-concentração. Entre os vários métodos para pré-concentração de metais-traços, a adsorção de reagentes orgânicos em suportes sólidos tem sido bastante usada. Nestes casos a determinação é feita após a eluição do metal com um solvente adequado. Neste trabalho é desenvolvido um sistema para pre-concentração de traços de manganês, utilizando 1-(2-Piridilazo)-2 -Naftol (PAN) adsorvido em naftaleno microcristalino numa proporção 3% (massa/massa). A mistura complexante (200 mg) é colocada numa coluna de vidro (15 cm x 0,4 cm d.i.) e condicionada com solução tampão NH4Cl/NH4OH (pH 9,5). A solução aquosa, contendo o manganês, é tratada com tartarato de sódio e potássio, para evitar a hidrólise de outros íons, hidroxilamina para evitar a oxidação do Mn(II) para Mn(III) e em seguida tamponada em pH 9,5. Esta solução é eluída através da coluna onde o Mn(II) é retido. O conteúdo da coluna (Mn(II)-PAN/naftaleno) é lavado com água desionizada e dissolvido em 10...

Structural and morphological characteristics of the electrodeposited Cr and Ni-Cr-P coatings and their corresponding electrochemical behaviors in chloride aqueous medium were investigated here. All coatings were electrodeposited on copper. Cr coatings were obtained from an industrial plating solution and amorphous Ni-Cr-P coatings were successfully obtained at 60ºC in the range of 100 to 400 mA cm-2, using a plating solution at pH 2 containing 40 g L-1 NiCl2.6H2O; 102 g L-1 CrCl3; 14 g L-1 NaPH2O2; 30 g L-1 H3BO3; 15 g L-1 NaBr; 50 g L-1 NH4Cl, 80 g L-1 Na3C6H5O7 .2H2O and 40 mL L-1 HCOOH. The coatings were obtained using constant charges of 500 and 1600 Coulombs. The characterization of the coatings was carried out by Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC) and Energy Dispersive X-ray Analysis (EDX) techniques. The electrochemical behavior of both coatings was evaluated by potentiodynamic polarization curves, at room temperature, in 0.1 mol L-1 NaCl aqueous solution. It was not observed cracks on the electrodeposited Ni-Cr-P coatings and the surface morphology was characterized by the presence of spherical nodules. The crystallization of these coatings occurred at 325 °C with the formation of Ni and Ni3P phases. All the annealed Cr coatings showed cracked surfaces. The presence of cracks impairs the mechanical and corrosion resistance properties of Cr coatings. The hardness of the Ni-Cr-P was increased with the increase of the annealing temperature. Spherical noodles were absent in the surface of as-annealed Ni-Cr-P coating which it was associated with the diffusion of Cr to the surface and cracks were not observed in any annealing temperature. Among the various electrodeposited Ni-Cr-P coatings studied here...

Aluminum-doped zinc oxide (AZO) films were prepared on glass substrate by mid-frequency direct current reactive magnetron sputtering (MF-DC-MS). The influence of surface texture by NH4Cl aqueous solution on the surface morphology, electrical and optical properties of the AZO films was systematically investigated by scanning electron microscope, four-point probe and ultraviolet-visible-near infrared spectrophotometer, respectively. The results indicate that textured AZO film obtains a better texture surface for light trapping. The reflectivity for textured AZO film decreases drastically in visible light region and the electrical resistivity increases, which can be explained by the textured surface morphology of AZO film. The results above prove that NH4Cl aqueous solution is an appropriate candidate for AZO wet etching because of its easy control and relatively low cost.

Catalase in extracts of the extreme halophile Halobacterium cutirubrum exhibits up to threefold stimulation by 0.5 to 1.5 m monovalent salts and by 0.1 m divalent salts. Above these concentrations, inhibition of enzyme activity is observed. The inhibitory effect, and to some extent the stimulation, is salt-specific; the effectiveness of a salt in inhibiting enzyme activity depends on both cation and anion. Thus, the order of effectiveness is MgCl2 > LiCl > NaCl > KCl > NH4Cl, and LiCl > LiNO3 > Li2SO4. The magnitude of enzyme inhibition for the salts tested is positively correlated with their molar vapor pressure depression in aqueous solution. Stimulation of enzyme activity was observed when one salt was added at its optimal concentration in the presence of inhibiting concentrations of another salt, indicating that the effect on the enzyme is not due to changing water activity but probably to enzyme-salt interaction. Aqueous solutions of ethylene glycol, glycerol, and dimethyl sulfoxide containing no ions influence enzyme activity in the same manner as do salts.

An enzymic electric cell was constructed in which the anode was composed of a zinc plate inserted in aqueous NH4Cl solution and the cathode was composed of an electrode made of a glassy carbon stick inserted in a reaction mixture containing cytochrome c3 hydrogenase (H2:ferricytochrome c3 oxidoreductase, EC 1.12.2.1) and methylviologen under an atmosphere of N2. When the circuit was closed, the electric cell formulated as [Formula: see text] was composed, and hydrogenase-catalyzed H2-evolution was observed in the cathode of the cell with concomitant flow of an electric current. Thus, the hydrogenase-catalyzed reaction and the electron-donating reaction proceeded at different parts of the cell. This enables us to protect the hydrogenase from the byproducts of the electron-donating system, which might be hazardous to the enzyme.

It was found that the absorbance and fluorescence of green fluorescent protein (GFP) mutants are strongly pH dependent in aqueous solutions and intracellular compartments in living cells. pH titrations of purified recombinant GFP mutants indicated >10-fold reversible changes in absorbance and fluorescence with pKa values of 6.0 (GFP-F64L/S65T), 5.9 (S65T), 6.1 (Y66H), and 4.8 (T203I) with apparent Hill coefficients of 0.7 for Y66H and approximately 1 for the other proteins. For GFP-S65T in aqueous solution in the pH range 5-8, the fluorescence spectral shape, lifetime (2.8 ns), and circular dichroic spectra were pH independent, and fluorescence responded reversibly to a pH change in <1 ms. At lower pH, the fluorescence response was slowed and not completely reversed. These findings suggest that GFP pH sensitivity involves simple protonation events at a pH of >5, but both protonation and conformational changes at lower pH. To evaluate GFP as an intracellular pH indicator, CHO and LLC-PK1 cells were transfected with cDNAs that targeted GFP-F64L/S65T to cytoplasm, mitochondria, Golgi, and endoplasmic reticulum. Calibration procedures were developed to determine the pH dependence of intracellular GFP fluorescence utilizing ionophore combinations (nigericin and CCCP) or digitonin. The pH sensitivity of GFP-F64L/S65T in cytoplasm and organelles was similar to that of purified GFP-F64L/S65T in saline. NH4Cl pulse experiments indicated that intracellular GFP fluorescence responds very rapidly to a pH change. Applications of intracellular GFP were demonstrated...

The experiments with the NH4Cl are similar to, and corroborate micro injection experiments performed in connection with some work on mustard gas in which the writer collaborated. Eggs immersed in sea water containing decomposed mustard gas, at a certain low concentration are not affected. If, however, the solution be injected, the egg quickly cytolyzes owing to the free HCl present. A similar impermeability of the protoplasmic surface film to certain substances was also encountered in injection work on Amœba. Amœbœ immersed in an aqueous solution of eosin will not take the stain till after death. On the other hand, the eosin, when injected into the Amœba, quickly permeates the protoplasm, to be arrested only at the surface. The semipermeability of a living cell appears primarily to be a function of its surface film. It is immaterial whether this film be that of the original cortex of the cell, a film newly formed over a cut surface, or a film that surrounds an artificially induced vacuole within the cell. As long as such a surface film exists neither the acid group of the NH4Cl nor the alkaline group of the NaHCO3 can, within certain concentration limits, penetrate the protoplasm. These solutions, if injected beneath the surface film...

An automated system to perform liquid-liquid extraction in monosegmented flow analysis is described. The system is controlled by a microcomputer that can track the localization of the aqueous monosegmented sample in the manifold. Optical switches are employed to sense the gas-liquid interface of the air bubbles that define the monosegment. The logical level changes, generated by the switches, are flagged by the computer through a home-made interface that also contains the analogue-to-digital converter for signal acquisition. The sequence of operations, necessary for a single extraction or for concentration of the analyte in the organic phase, is triggered by these logical transitions. The system was evaluated for extraction of Cd(II), Cu(II) and Zn(II) and concentration of Cd(II) from aqueous solutions at pH 9.9 (NH3/NH4Cl buffer) into chloroform containing PAN (1-(2-pyridylazo)-2-naphthol) . The results show a mean repeatability of 3% (rsd) for a 2.0 mg l-1 Cd(II) solution and a linear increase of the concentration factor for a 0.5mg l-1 Cd(II) solution observed for up to nine extraction cycles.

Pressure solution creep rates and interface structures have been measured by two methods on calcite single crystals. In the first kind of experiments, calcite monocrystals were indented at 40 degrees C for six weeks using ceramic indenters under stresses in the 50-200 MPa range in a saturated solution of calcite and in a calcite-saturated aqueous solution of NH4Cl. The deformation (depth of the hole below the indenter) is measured ex-situ at the end of the experiment. In the second type of experiment, calcite monocrystals were indented by spherical glass indenters for 200 hours under stresses in the 0-100 MPa range at room temperature in a saturated aqueous solution of calcite. The displacement of the indenter was continuously recorded using a specially constructed differential dilatometer. The experiments conducted in a calcite-saturated aqueous solution of NH4Cl show an enhanced indentation rate owing to the fairly high solubility of calcite in this solution. In contrast, the experiments conducted in a calcite-saturated aqueous solution show moderate indentation rate and the dry control experiments did not show any measurable deformation. The rate of calcite indentation is found to be inversely proportional to the indenter diameter...