Hydrogen sulphide doping of GaAs and AlxGa1−xAs grown by molecular beam epitaxy (MBE)

H₂S gas has been used during molecular beam epitaxy (MBE) growth of GaAs and Al _x Ga_1–x As as sulphur vector forn-type doping. Doping efficiencies are less than 10^–3 at usual growth temperatures, and are limited by an incorporation competitive surface process, probably 2Ga+H₂SGa₂S+H₂. In Al_xGa_1–x As forx0.2 the doping efficiency is further reduced by carrier freeze-out at deep levels. Measured thermal activation energies depend on growth conditions and remain relatively low even up to the direct-indirect bandgap crossover for substrate temperatures in the 585–645 C range.     

On the mechanism of electroluminescence emission by porous silicon layers

The analytical treatment of a model considering the electrooxidation of p-porous silicon layers under galvanostatic conditions is able to give account of experimental facts such as the shape and location of the electroluminescence peak as well as of the spectral shift of the electroluminescence peak produced by oxidation. The proposed model considers electroluminescence to be the result of electron injection into the conduction band by an adsorbed intermediate produced by electrooxidation of the surface coverage with hydrogen or siloxene of the silicon nanocrystallites. The access of holes to the surface is made possible by low accumulation layer conditions and is the rate determining step in the electroluminescence mechanism. In this way it is possible to give a satisfactory explanation to the shift towards the blue experimented by the electroluminiscence emission maximum as a consequence of electrooxidation.     

Alkylation of β-diketones through their co(II), co(III) and zn(II) complexes. 1-Bromoadamantane as alkylating agent.

α-(1-adamantyl)-β-diketones are now accessible by the alkylation of Co(II) complexes of β-diketones with 1-bromoadamantane. The intermediacy of adamantyl cation is proposed. Co(II), Co(III) and Zn(II) complexes of pentane-2,4-dione react with alkyl halides precursors of stabilized carbenium ions, to give 3-alkylpentane-2,4-diones.     

Stereochemical analysis of N-cyclohexylidene-N-(1-phenylethyl)amine derivatives

The configurational properties of a series of cyclohexylidene imines are discussed on the basis of their 1H, 13C and 15N NMR spectral data.     

Determination of formation constants of hydroxo and carbonate complexes of Pr(3+) in 2 M NaCl at 303 K

The hydrolysis of praseodymium III in 2 M sodium chloride at 303 K was studied. Two methods were used: pH titration followed by a computational refinement and solvent extraction in the presence of a competitive ligand. The hydrolysis constants obtained by pH titration were: logbeta(1,H)=-7.68+/-0.07, logbeta(1,2H)=-15.10+/-0.03, and beta(1,3H)=-23.80+/-0.04. The stability constants of praseodymium carbonate complexes were determined by pH titration as well and were: logbeta(1,CO(2-)(3))=5.94+/-0.08 and logbeta(1,2CO(2-)(3))=11.15+/-0.15. Praseodymium carbonate species were taken into consideration for calculating the first hydrolysis constants by the solvent extraction method and the value obtained was: logbeta(1,H)=-7.69+/-0.27. The values for logbeta(1,H) attained by both methods are the same. The species-distribution diagram was obtained from the stability constants of praseodymium carbonate complexes and hydrolysis products in the conditions of the present work.     

Electrocatalytic effect of iron sulfates on oxygen reduction. Influence of the solvation sphere of the mediator

The redox catalysis of oxygen reduction was performed on a platinum rotating disk electrode. The Fe(III)/Fe(II)/H₂SO₄ system at different pH's was used as a MEDIATOR. The catalytic effect of mediator was directly related to the solvation sphere of Fe(III) and Fe(II). Only the redox couple FeHSO ₄ ²⁺ /FeHSO ₄ ⁺ (pH<0) showed a catalytic effect on oxygen reduction.     

The reaction of β-aminoenones with substituted acetonitriles. Regiospecific synthesis of 2(1H)-pyridones

Unsymmetrically substituted β-aminoenones react with malononitrile, cyanomethylphenylsulfone, benzoyl-acetonitrile and ethyl cyanoacetate, in very mild conditions, to yield regiospecifically 3-functionalized 2(1H)-pyridones in high yields.     

New physically adsorbed polymer coating for reproducible separations of basic and acidic proteins by capillary electrophoresis

In this work, a new physically adsorbed coating for capillary electrophoresis (CE) is presented. The coating is based on a N,N-dimethylacrylamide-ethylpyrrolidine methacrylate (DMA-EPyM) copolymer synthesized in our laboratory. The capillary coating is simple and easy to obtain as only requires flushing the capillary with a polymer aqueous solution for 2 min. It is shown that by using these coated capillaries the electrostatic adsorption of a group of basic proteins onto the capillary wall is significantly reduced allowing their analysis by CE. Moreover, the DMA-EPyM coating provides reproducible separations of the basic proteins with RSD values for migration times lower than 0.75% for the same day (n = 5) and lower than 3.90% for three different days (n = 15). Interestingly, the electrical charge of the coated capillary wall can be modulated by varying the pH of the running buffer which makes possible the analysis of basic and acidic proteins in the same capillary. The usefulness of this coating is further demonstrated via the reproducible separation of whey (i.e. acidic) proteins from raw milk. The coating protocol should be compatible with both CE in microchips and CE-MS of different types of proteins.     

Ferrocenyl and permethylferrocenyl cyclic and polyhedral siloxane polymers as mediators in amperometric biosensors

Cyclosiloxane and silsesquioxane-based ferrocenyl and permethylferrocenyl polymers have been used as mediators in amperometric enzyme electrodes for the detection of glucose. Biosensors have been prepared by electrostatically immobilizing the enzyme glucose oxidase (GOx) on electrodes modified with the polymers. The steady-state amperometric response of the sensors is investigated as a function of the applied potential and substrate concentration. The dependence of the sensors response on the structure of the siloxane-framework and on the presence or not of methyl groups on the ferrocenyl units is discussed.