A strong law of large numbers for generalized random sets from the viewpoint of empirical processes

In this article we prove a strong law of large numbers for Borel measurable nonseparably valued random elements in the case of generalized random sets.

     

Differential pulse polarographic determination of trace amounts of vanadium and molybdenum in various standard alloys and environmental samples after preconcentration of their morpholine-4-carbodithioates on microcrystalline naphthalene or morpholine-4-dithiocarbamate cetyltrimethyl-ammonium bromide-naphthalene adsorbent

A highly selective, sensitive, and fairly rapid and economical differential pulse polarographic (DPP) method has been reported for the determination of trace amounts of vanadium and molybdenum in standard alloys and various environmental samples. The morpholine-4-carbodithioates of these metals were retained (>99% recovery) quantitatively on microcrystalline naphthalene in the pH range 4.5-6.9 for vanadium and 1.5-4.5 for molybdenum. These metals were determined by DPP after desorption with 10 ml of 1 M HCl. Vanadium and molybdenum may also be preconcentrated by passing their aqueous solutions under similar conditions on morpholine-4-dithiocarbamate CTMAB-naphthalene adsorbent packed in a column at a flow rate of 1-5 ml min(-1) and determined similarly. The detection limits are 0.20 ppm for vanadium and 0.04 ppm for molybdenum at minimum instrumental settings (signal to noise ratio=2). The linearity is maintained in the following concentration ranges, vanadium 0.50-10.0 and molybdenum 0.10-9.0 ppm, with a correlation factor of 0.9996 (confidence interval of 95%, slopes 0.0196 and 0.01497 muA mug(-1), intercepts 3.65x10(-3) and -1.92x10(-3) respectively) and relative standard deviation of 1.1% in the microcrystalline method, while in the column method, the linearity is maintained in the concentration ranges, 0.50-6.5 for vanadium and 0.10-5.5 ppm for molybdenum with correlation factor of 0.9994 (with confidence interval of 95%, slopes 0.0194, 0.015 muA mug(-1), intercepts 3.60x10(-3) and -1.90x10(-3) respectively) and relative standard deviation of 1.4%. Various parameters such as the effect of pH, reagent, naphthalene and CTMAB concentrations, volume of aqueous phase and interference of a large number of metal ions on the estimation of vanadium and molybdenum have been studied in detail to optimize the conditions for their voltammetric determination at trace level in various standard alloys and environmental samples.     

Column preconcentration of trace manganese with the ion pair of 2-nitroso-1-naphthol-4-sulfonic acid tetradecyldimethylbenzyl-ammonium chloride supported on naphthalene and determination by derivative spectrophotometry

A column preconcentration method has been developed for the determination of trace amounts of manganese by preconcentration on 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S)-tetradecyldimethylbenzylammonium (TDBA) naphthalene as an adsorbent using a simple funnel tipped glass tube. Manganese reacts with nitroso-S to form a water soluble brown colored chelate anion. The chelate anion forms a water insoluble Mn-Nitroso-S-TDBA ion pair on naphthalene packed in a column in the pH range 9.6-10.5 at a flow rate of 1-2 ml/min. The solid mass consisting of manganese complex and naphthalene is dissolved in 5 ml of dimethylformamide (DMF) and the metal determined by second derivative spectrophotometry. The calibration curve is linear in the concentration range 0.25-35.0 micrograms of Mn in 5 ml of the final DMF solution. Eight replicate determinations of 25 micrograms of standard manganese solution give a mean peak height of 4.0 with a correlation coefficient of 0.9995 and relative standard deviation of +/- 1.1%. The sensitivity was calculated to be 0.502(d2 A/d lambda 2)/microgram ml-1 from the slope of the calibration curve. The detection limit was 0.020 microgram ml-1 for manganese at the minimum instrumental settings (signal to noise ratio = 2). Various parameters effecting the method such as the effect of pH, volume of aqueous phase and interference of a number of metal ions on the determination of manganese have been evaluated to optimize the conditions for its determination in standard alloys and biological samples.     

Simultaneous determination of lead and cadmium in various environmental and biological samples by differential pulse polarography after adsorption of their morpholine-4-carbodithioates onto microcrystalline naphthalene or morpholine-4-dithiocarbamate-CTMAB-naphthalene adsorbent

A highly selective, sensitive and rapid differential pulse polarographic method (DPP) has been developed for the simultaneous estimation of trace amounts of lead and cadmium in standard alloys, biological and environmental samples. The morpholine-4-carbodithioates of the samples were absorbed on microcrystalline naphthalene in the pH range of 5-10 for lead and 3.4-11 for cadmium. The metal complexes were desorbed with 10 ml of 1M HCl and determined simultaneously with a differential pulse polarograph. These metals can alternatively be quantitatively adsorbed on morpholine-4-dithiocarbamate-cetyltrimethylammonium bromide-naphthalene adsorbent packed in a column and determined similarly. The detection limits are 0.14 ppm for Pb and 0.014 ppm for Cd at minimum instrumental settings (signal-to-noise ratio = 2). The linearity is maintained in the concentration ranges of Pb, 0.7-15 ppm and Cd, 0.07-10 ppm with a correlation factor of 0.9997 and relative standard deviations of 0.95 and 0.81%, respectively. Various parameters such as the effect of pH, volume of aqueous phase, and interference of a number of metal ions on the estimation of lead and cadmium have been studied in detail to optimize the conditions for their simultaneous estimation in various biological and environmental samples.     

N-Methylethylxanthocarbamate as an Analytical Reagent: Differential Pulse Polarographic Determination of Cadmium in Standard Alloys, Biological and Environmental Samples after Adsorption of its Complex on Microcrystalline Naphthalene

N-methylethylxanthocarbamate has been used as an analytical reagent for the determination of trace amounts of cadmium in standard alloys, biological, and environmental samples. The reagent has been found to form a water insoluble complex with cadmium. It is quantitatively adsorbed over microcrystalline naphthalene in the pH range 2.5 to 12.0. The metal complex is desorbed with HCl and cadmium determined with a differential pulse polarograph. The detection limit is 0.05 ppm (signal-to-noise ratio = 2) and the linearity is maintained in the concentration range 0.2–25 g/ml, with correlation coefficient of 0.9995 and a relative standard deviation of ±0.81%. Characterization of the electroactive process includes an examination of the degree of reversibility. Various parameters, such as the effect of pH, reagent concentration, amount of naphthalene, volume of aqueous phase, and the interference of a large number of metal ions on the determination of cadmium, have been studied in detail to optimize the conditions for its determination in various complex materials.     

Preconcentration of trace cobalt with the ion pair of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and tetraphenylborate onto microcrystalline naphthalene or column method and its determination by derivative spectrophotometry

Cobalt-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)-tetraphenylborate ion associated complex is quantitatively adsorbed on microcrystalline naphthalene in the pH range 3.5-9.5 from a fairly large volume of the aqueous samples (preconcentration factor ~30). After filtration, the solid mass consisting of the cobalt complex and naphthalene was dissolved with 5 ml of dimethylformamide (DMF) and the metal determined by first-derivative spectrophotometry. The cobalt-5-Br-PADAP complex can alternatively be quantitatively retained on ammonium tetraphenylborate-naphthalene adsorbent filled in a column (preconcentration factor 120) in the same pH range and determined similarly. The detection limit is 30 ppb (signal-to-noise ratio=2) and the calibration curve is linear over 0.3-8.0 mug of cobalt in 5 ml of the final DMF solution. Eight replicate determinations of 1.0 mug of cobalt gave a mean peak height of 0.208 (at 611.5 nm) with a relative standard deviation of 1.2%. The sensitivity of the method is 1.04 (dA/dnm) ml mug(-1) found from the slope of the calibration curve. The interference of a large number of anions and cations on the determination of cobalt has been studied and the optimized conditions developed were utilized for its trace determination in various standard alloys and biological samples.     

A simple and reliable semipreparative high-performance liquid chromatography technique for the isolation of marker-grade hyperforin from Hypericum perforatum L extract

The present work describes isolation of bioactive lipophilic constituent [namely, hyperforin from St. John's wort (Hypericum perforatum L.)], of approximately 98% purity by semipreparative high-performance liquid chromatography (LC). The extraction, isolation, and analysis of the collected compound is performed without the use of antioxidants and inert gas atmospheres at all the stages. Hyperforin, separated isocratically on a 12microm semiprep column, is obtained in high purity, lyophilized after the removal of the organic phase, and preserved at a low temperature. The purity of the collected marker compound is estimated by the use of LC-mass spectrometry and spectroscopic techniques.     

1,1,1,1-Tetrakis(o-fluorophenylamino)silane tris[titanium(IV) chloride]. Evidence for a new titanium cation [Ti2Cl7]+

Si(NHC₆H₄F-o)₄ · 3TiCl₄ (1) has been obtained from the disproportionation of (CF₃CH₂O)₃SiNHC₆H₄F-o and TiCl₄ in petroleum ether (40–60 °C) at –10 °C. The analytical (elemental analysis, molar conductance) and spectral (i.r., ¹H- and ¹⁹F-n.m.r.) data suggested that (1) behaves as [Si(NHC₆H₄F-o)₄ · Ti₂Cl₇]⁺ [TiCl₅]^–. The presence of these ions has been confirmed by characterising the products of metathetical reactions of (1) with R₄NX (R = Bu and Et; X = I and Br) and with AgNO₃. The data suggest the presence of a new titanium cation [Ti₂Cl₇]⁺.     

Ammonium tetraphenylborate-naphthalene adsorbent for the preconcentration and trace determination of uranium in standard alloys and synthetic samples using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol by fourth-derivative spectrophotometry

A solid ion-pair material produced from ammonium tetraphenylborate (ATPB) and naphthalene has been used for the preconcentration of uranium from the large volume of its aqueous complex samples. Uranium reacts with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) to form a water insoluble, coloured complex. This complex is quantitatively retained on the ATPB-naphthalene adsorbent filled in a column in the pH range 7.0–9.5 and at a flow rate of 2 ml/min. The solid mass from the column is dissolved with 5 ml of dimethylformamide (DMF) and uranium is determined by fourth-derivative spectrophotometry. The calibration curve is linear over the concentration range of 0.13–15.0 g of uranium in 5 ml of the final DMF solution. Seven replicate determinations of 6 g of uranium gave a mean peak height (peak-to-peak signal between 592 nm and 582 nm) of 1.02 with a relative standard deviation of 0.95%. The sensitivity is 0.8419 (d⁴A/d⁴)/(g ml^–1) found from the slope of the calibration curve. The interference of a large number of anions and cations on the estimation of uranium has been studied and the method applied for the determination of uranium in coal fly ash, Zr-base alloy and some synthetic samples corresponding to standard alloys.