Kinetics of Hydrogen Peroxide Decomposition in Guaiacol Solution, Catalyzed by Hexacyanoferrate(II)

The kinetics of hydrogen peroxide decomposition in a guaiacol solution, catalyzed by potassium hexacyanoferrate(II), were studied. The reaction mainly follows the pathway of guaiacol hydroxylation. The reaction order is 1 with respect to H₂O₂, 0.5 with respect to hexacyanoferrate, and from 0.4 to 0 with respect to guaiacol (the latter parameter decreases with increasing guaiacol concentration). The apparent activation energy is 105 kJ mol^{- 1}. A kinetic scheme of the process was proposed. An expression consistent with the experiment was obtained for the rate of hydrogen peroxide decomposition in the presence of guaiacol, catalyzed by hexacyanoferrate(II).     

Spin dynamics investigated by EPR in the paramagnetic regime of La2/3Ca1/3Mn1−x Me x O3 (Me = Al, In) manganites

We report an electron paramagnetic resonance (EPR) investigation of the spin dynamics in the paramagnetic regime of the colossal magnetoresistive manganites La_2/3Ca_1/3Mn_1?x Me _x O₃ (Me=Al, In;x≤0.05). The temperature dependences of the EPR linewidth and integral intensity have been analyzed in terms of the bottleneck spin relaxation and small-polaron hopping models. The exchange coupling integral between Mn³⁺ and Mn⁴⁺ ions and the polaron activation energy decrease with increasing doping level. A discussion is given concerning the factors which could explain the observed changes.     

Intermolecular interactions of p-nitrophenol with butyl acetate,according to IR spectroscopic data

Infrared difference spectroscopy has been used to study the association of p-nitrophenol (NP) with butyl acetate (BA) in CCl₄ and in undiluted BA. It has been shown that in CCl₄, an associate is formed, [NP·BA] ·BA (Ia), in which one molecule of BA is linked to the NP by a hydrogen bond, and the second BA molecule is linked to the H-complex NP·BA by outer-sphere (dipole-dipole) interaction. In undiluted BA with low concentrations of NP, (Ia) is formed; with high concentrations of NP, an associate [(NP)₂BA] ·mBA is formed, in which two molecules of NP are bonded successively to each other and with a BA molecule; and the number of outer-sphere BA molecules may depend on the concentration of free BA molecules in the solutions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 593–599, March, 1991.     

Anodic stripping coulometry with collection for absolute trace analysis of lead, using flow-through electrochemical cells with porous working electrodes

Summary Flow-through electrochemical cells with porous working electrodes made of crushed reticulated vitreous carbon and plated with mercury were used for absolute analysis of trace amounts of lead by anodic stripping coulometry with collection (ASCWC) in a flow system. The role of mercury coating, flow rate and pH were investigated. The coulombic content of the collection peak corresponded to the theoretical values calculated by Faraday's law in a concentration range from about 10^–9 to 10^–6 mol/l. The relative error and the relative standard deviation was +0.15% and 0.8%, respectively for 2×10^–6 mol/l analyte concentration. The absolute detection limit (3 s) was 0.1 ng of Pb, the linear response range 7×10⁴. One leave from: Department of Analytical Chemistry, Slovak Technical University, CS-812 37 Bratislava, Czechoslovakia     

Immobilized pH gradients (IPG) simulator--an additional step in pH gradient engineering: II. Nonlinear pH gradients

While in the companion paper (Tonani, C. & Righetti, P. G., Electrophoresis 1991, 12, 1011-1021) we gave the general outline of our new computer program, immobilized pH gradients (IPG) simulator, able to simulate and optimize linear pH gradients for isoelectric focusing in immobilized pH gradients, in the present report we extend the application of such a program to: (i) convex exponential gradients, (ii) logarithmic and (iii) polynomial gradients. Such gradients are meant to give equal space to protein spots in complex protein mixtures (e.g., cell lysates, biological fluids) and follow the statistical distribution of protein pI values along the pH axis. They will prove of fundamental importance in two-dimensional maps, both because they optimize the spreading of spots in the two-dimensional plane and because of the excellent reproducibility of immobilized pH gradients. The following concave exponential recipes are given: pH 3-8, pH 3-9, pH 3-10, pH 3-11, pH 4-7, pH 4-8, pH 4-9, pH 4-10, pH 4-11, pH 5-8, pH 5-9, and pH 5-10, as well as the most extended pH 2.5-11 interval. Two interesting logarithmic gradients are described: pH 3-6 and pH 3-7 and one sigmoidal (derived with a polynomial of 5th degree): pH 3-11.     

The effect of the external lateral electric field on the luminescence intensity of InAs/GaAs quantum dots

We report on low-temperature microphotoluminescence (μ-PL) measurements of InAs/GaAs quantum dots (QDs) exposed to a lateral external electric field. It is demonstrated that the QDs’ PL signal could be increased severalfold by altering the external and/or the internal electric field, which could be changed by an additional infrared laser. A model which accounts for a substantially faster lateral transport of the photoexcited carriers achieved in an external electric field is employed to explain the observed effects. The results obtained suggest that the lateral electric fields play a major role for the dot luminescence intensity measured in our experiment—a finding which could be used to tailor the properties of QD-based optoelectronic applications. The text was submitted by the authors in English.