Optimization of experimental parameters in single-drop microextraction-gas chromatography-mass spectrometry for the determination of periodate by the Malaprade reaction, and its application to ethylene glycol

The aim of present work was to optimize the experimental parameters in single drop microextraction under solution immersion (SDME) and headspace (HS-SDME) extraction modes for the determination of periodate using guaifenesine [3-(2′-methoxyphenoxy)-1,2-propane diol] and norephedrine (phenylpropanolamine) as new and alternative reagents for the Malaprade reaction. The reactions were complete within 5 min resulting in the formation of 2-(2′-methoxyphenoxy)-acetaldehyde and benzaldehyde, respectively. SDME/HS-SDME of oxidation products with 2 μl of anisole or 1 μl of toluene, respectively, has permitted the determination of periodate at μg l⁻¹ concentration levels. The results indicated that HS-SDME (range 0.01-10 mg l⁻¹, r² = 0.9990; limit of detection 1.55 μg l⁻¹) was more sensitive than SDME (range 0.05-50 mg l⁻¹, r² = 0.9984; limit of detection 3.42 μg l⁻¹), and was inexpensive, rapid and convenient. Tolerance of excess of iodate has permitted the application of this method in the determination of ethylene glycol in motor oil; the average recovery on spiked sample was 98.6% with R.S.D. of 4.2%.     

High-performance thin layer chromatography method for quantitative determination of four major anthraquinone derivatives in Rheum emodi

A high-performance thin layer chromatographic (HPTLC) method for the rapid and simple quantification of the four major anthraquinone derivatives i.e. physcion, chrysophanol, emodin and chrysophanol glycoside in Rheum emodi is described. HPTLC of anthraquinone derivatives was performed on pre-coated RP-18 F254S HPTLC plates. For achieving good separation, the mobile phase of methanol-water-formic acid (80:19:1, v/v/v) was used. The densitometric determination of anthraquinone derivatives was carried out at 445 nm in reflection/absorption mode. The calibration curves were linear in the range of 20-100 ng for physcion, 80-400 ng for chrysophanol and emodin, and 200-1000 ng for chrysophanol glycoside. The method was found to be reproducible and convenient for quantitative analysis of anthraquinone derivatives in the methanolic extract of rhizomes of R. emodi collected from three different locations of Western Himalaya, India.     

2,5-Dihydroxyacetophenone oxime as an analytical reagent for the amperometric determination of copper,palladium, and nickel

Summary Copper, palladium and nickel can be titrated amperometrically with 2,5-dihydroxyacetophenone oxime at –0.15, –0.4 and, –1.2 V vs. S. C. E. respectively, the optimum p_H values being 4.6, 4.0, and 9.0. Alkali and alkaline earth metals, Al, Bi, Cd, Co, Cr. Fe(II), Hg, Mn, Ni, Pb, Th, Zn, UO, W, and Zr do not interfere with the estimation of copper and palladium. The interferences due to the presence of silver and iron(III) can be eliminated by adding excess of KCl and KF respectively. Most heavy metals interfere with the estimation of nickel and should be eliminated before titration.

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Zusammenfassung Kupfer, Palladium und Nickel können mit 2,5-Dihydroxyaeetophenonoxim bei –0,15, –0,4 bzw. –1,2 V gegen eine gesättigte Kalomelelektrode amperometrisch titriert werden, wobei man das p_H am besten auf 4,6, 4,0 bzw. 9,0 hält. Alkalimetalle, Erdalkalien, Al, Bi, Cd, Co, Cr, Fe(II), Hg, Mn, Ni, Pb, Th, Zn, UO₂, W und Zr stören die Bestimmung des Kupfers und des Palladiums. Silber und Eisen können mit Kaliumchlorid gefällt bzw. mit Kaliumfluorid maskiert werden. Die meisten Schwermetalle stören die Nickelbestimmung und müssen daher vor der Titration entfernt werden.

     

Valence fluctuation in some Yb intermetallics by X-ray photoemission and X-ray absorption

The valence state of Yb in some of its intermetallics, YbNi₂Ge₂, YbCu₂Si₂ and YbPd₂Si₂ has been investigated by L_III(Yb) absorption edges and X-ray pnotoelectron spectra in the 4f and 4d regions. These studies establish the presence of mixed valence in all three systems and illustrate the utility of 4f and 4d spectra in the study of mixed valence in Yb compounds.     

Substituted sulphoxide ligands in piperidinium based ionic liquid: novel solvent systems for the extraction of Pu<Superscript>4+</Superscript> and PuO<Subscript>2</Subscript><Superscript>2+</Superscript>

Sulphoxide ligands in piperidinium based ionic liquid were demonstrated as highly efficient, selective and environmentally benign systems for the extraction of plutonium from acidic aqueous solution. The extraction followed ‘cation-exchange mechanism’ via [Pu(NO₃)·L]³⁺ and [PuO₂(NO₃)·L]⁺ species. The extraction efficiency followed the trend: APSO > BPSO > BMSO. The phenyl substituted sulphoxides showed higher affinity for plutonium due to a combination of steric as well as electronic factors. Extraction process was thermodynamically spontaneous for all three solvent systems. Oxalic acid and sodium carbonate were suitable for quantitative stripping of Pu⁴⁺ and PuO₂ ²⁺, respectively. APSO in ionic liquid showed good radiolytic stability.     

CdSe quantum dot-dispersed DOBAMBC: an electro-optical study

Cadmium selenide quantum dot (CdSe QD) has been used as a dopant in ferroelectric liquid crystal (FLC) 2-methylbutyl 4-(4-decyloxybenzylideneamino) cinnamate (DOBAMBC). Effect of CdSe QD in DOBAMBC on its different electro-optical (E-O) properties has been studied in the SmC* phase. The optical micrographs recorded for the pure and composite material are showing good dispersion of QDs in the FLC matrix. Micrographs of unaligned sample cell revealed that CdSe QDs induce homeotropic alignment of FLC molecules. An appreciable change in the value of E-O parameters like tilt angle, spontaneous polarisation and response time with shifting of SmA–SmC* phase transition temperature has been observed for CdSe QD–DOBAMBC composite. The observed properties of composite system have been discussed on the basis of surface properties of QDs in FLC system.     

One-Pot Synthesis and Fungicidal Activity of Pyrimidinylidenamido- and Thiazolinylidenamidomonothiophosphoric Esters

A novel one-pot synthesis of four new classes of amidothiophosphoric esters and trisamidothiophosphoric esters is developed. (1-Alkyl-2-pyrimidinylidenamido)bis(diethylamido)thiophosphates, (1-alkyl-2-pyrimidinylidenamido)bis (O-2/4-methylphenyl)thiophosphates, (3-alkyl-2-thiazolinylidenamido)bis (diethylamido)thiophosphate and (3-alkyl-2-thiazolinylidenamido)bis(O-2/4-methylphenyl)thiophosphates are obtained from the nucleophilic substitution and oxidation of N-alkyl-2-cycloiminylidenaminodichlorophosphines generated in situ from the reaction of the corresponding N-alkyl-2-aminocycloiminium halide with phosphorus trichloride and triethylamine. The synthesized thiophosphoric esters have been investigated for fungicidal properties.     

Convergence of Szász-Beta operators

In the present article we find the hypergeometric representation of the Szász-Beta operators and obtain the moments using confluent hypergeometric functions, which can be related to generalized Laguerre polynomials. Then we estimate a convergence result for functions having bounded derivatives.     

Synthesis,physicochemical characterization and biological activity of nano complexes of iron(III) of 3(2'‐hydroxyphenyl)‐5‐(4′‐substituted phenyl) pyrazolines and aspartic acid

Mixed ligand complexes of Iron(III) with aspartic acid and 3(2′‐hydroxy phenyl)‐5‐(4′‐substituted phenyl) pyrazolines of type [Fe(C₄O₄NH₆)₂(C₁₅H₁₂N₂OX)] and [Fe(C₄O₄NH₆)(C₁₅H₁₂N₂OX)₂], where (C₄O₄NH₆) = aspartate, (C₁₅H₁₂N₂OX) = deprotonated 3(2′‐hydroxyphenyl)‐5‐(4′‐substituted phenyl) pyrazolines (X = H, CH₃, OCH₃, Cl), have been synthesized. These newly synthesized derivatives have been physicochemically characterized by elemental analysis (C, H, N, Cl and Fe), magnetic moment data, thermogravimetric analysis, molar conductance, cyclic voltammetry, spectral analysis (UV–visible, IR, far IR and fast atom bombardment mass spectrometry). Scanning electron microscopy, transmission electron microscopy and X‐ray powder diffraction studies have been carried out for powdered samples, which show nanometric particles of these derivatives. Antibacterial and antifungal potential of free pyrazoline and some iron(III) complexes have been evaluated. Copyright © 2012 John Wiley & Sons, Ltd.