Optical sensor for sulfur dioxide based on fluorescence quenching

A series of potential indicator dyes is evaluated for use in the development of optical sensors for measuring sulfur dioxide in gaseous samples. Rhodamine B isothiocyanate is selected on the basis of relative sensitivity to dynamic quenching by sulfur dioxide and oxygen. A solid-state fluorometer is described for monitoring the sulfur dioxide induced fluorescence quenching of sensing membranes composed of silicone and rhodamine B isothiocyanate. A modulated blue LED is coupled with the lock-in detection of a photodiode detector to provide high signal-to-noise ratios. The limit of detection is 0.114+/-0.009% for sulfur dioxide in a carrier stream of nitrogen gas. Selectivity measurements indicate no interference from several common gases (HCl, NH(3), NO, and CO(2)). Oxygen alters the sensor response when comparing signals for sulfur dioxide in 0, 20 and 100% oxygen environments.     

Atomic absorption spectrometric and potentiometric microdetermination of the nitro and nitroso groups in organic compounds

New simple, rapid, accurate, and selective methods are described for microdetermination of the nitro and nitroso groups in organic compounds. These are based on reduction with cadmium metal and 0.05 M HCl whereby 6 and 4 equivalents of the cadmium ions are released per nitro and nitroso groups, respectively. The cadmium ions are measured by atomic absorption spectrometry at 228.8 nm, potentiometrically by titration with EDTA using the cadmium ion selective electrode, and visually by EDTA titration using Eriochrome Black T indicator. Results with an average recovery of 98% and a mean standard deviation of 1.3% are obtainable and no interferences are caused by many nitrogen, oxygen, and sulfur functional groups.     

Synthesis of 5-Substituted 1,3-Dimethylpyrazolo[4,3-<Emphasis Type="Italic">e</Emphasis>][1,2,4]triazines

Summary.  A novel method for the synthesis of a new series of 5-substituted 1,3-dimethyl pyrazolo[4,3-e][1,2,4]triazines is described. The new synthetic strategy is based on the classical Bischler 1,2,4-benzotriazine synthesis. This approach involves the preparation of 5-hydrazinopyrazole from 5-chloro-1,3-dimethyl-4-nitropyrazole followed by acylation and nitro group reduction to form the corresponding 4-amino-3-(acylhydrazino)pyrazoles. Intramolecular oxidative cyclization of the latter derivatives, using polyphosphoric acid, produced the respective target pyrazolotriazines.     

Synthesis of 5-Substituted 1,3-Dimethylpyrazolo[4,3-e][1,2,4]triazines

A novel method for the synthesis of a new series of 5-substituted 1,3-dimethyl pyrazolo[4,3-e][1,2,4]triazines is described. The new synthetic strategy is based on the classical Bischler 1,2,4-benzotriazine synthesis. This approach involves the preparation of 5-hydrazinopyrazole from 5-chloro-1,3-dimethyl-4-nitropyrazole followed by acylation and nitro group reduction to form the corresponding 4-amino-3-(acylhydrazino)pyrazoles. Intramolecular oxidative cyclization of the latter derivatives, using polyphosphoric acid, produced the respective target pyrazolotriazines.     

Isotope shift studies in the spectra of Gadolinium in UV region and term shifts of high even levels of Gd I

Isotope shift Δσ(¹⁵⁶Gd?¹⁶⁰Gd) is reported in 70 spectral lines of neutral gadolinium atom (Gd I) in the 3290- 3920 Å region providing isotope shift data in UV lines of Gd I spectrum for the first time. The measurements were carried out on a photoelectric recording Fabry-Perot Spectrometer using highly enriched isotopic samples of gadolinium. Term isotope shifts ΔT(¹⁵⁶Gd?¹⁶⁰Gd) have been evaluated for 48 high lying even parity energy levels of Gd I using this data; new ΔT values have been obtained for 24 levels. Electronic configurations 4f⁷5d6s6p, 4ff⁷5df²6p and 4f⁸5d6s assigned earlier to these even levels have been either confirmed or configuration mixing pointed out in some of these levels. Probable assignment of 4f⁸5d6s configuration to 8 even levels between 32 930 and 35 500 cm^-1 have been confirmed.     

UV-vis, IR and 1H NMR spectroscopic studies of some mono- and bis-azo-compounds based on 2,7-dihydroxynaphthalene and aniline derivatives

The absorption spectra of mono- and bis-azo-derivatives obtained by coupling the diazonium salts of aromatic amines and 2,7-dihydroxynaphthalene have been studied in six organic solvents. The different absorption bands have been assigned and the effect of solvents on the charge transfer band is also discussed. The diagnostic IR spectral bands and 1H NMR signals are assigned and discussed in relation to molecular structure. Also, semi-empirical molecular orbital calculations using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory have been performed to investigate the molecular and electronic structures of these compounds. According to these calculations, an intramolecular hydrogen bonding is essential for stabilization of such molecules.     

A simplified sampling technique for use with the Weisz ring oven: application to qualitative analysis of some gold and silver alloys

Up to 100 microg of sample can be collected from gold or silver alloys by rubbing the specimen with the ground hemispherical tip of a 4-mm Pyrex glass rod. Gold alloys are then dissolved in potassium cyanide solution containing hydrogen peroxide; silver alloys are exposed to vapours of nitric acid. Procedures for transfer, ring oven separation and identification of alloy constituents in the sample solutions are described.     

Thermal analysis of pharmaceutical compounds

Some sulphonamides are evaluated by means of thermal analysis. Use is made of their characteristic endothermic DTA peaks (melting peaks), where the area changes linearly with variations in the amount of sulphonamides. The method is suitable for the determination of 30–100 mg of sulphathiazole, sulphisomidine, sulphaguanidine, sulphacetamide sodium and sulphamethoxypyridazine with reasonable accuracy. As for sulphisoxazole, two peaks are used for its determination: an endothermic one to determine 30–100 mg, and an exothermic one to determine 6–30 mg.

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Zusammenfassung Einige Sulphonamide wurden durch thermische Analyse bestimmt, wobei von der linearen Abhängigkeit der Fläche der charakteristischen endothermen DTA-Peaks (Schmelzpeaks) von der Menge der Sulphonamide Gebrauch gemacht wurde. Mit der Methode können 30–100 mg Sulphathiazol, Sulphisoimidin, Sulphaguanidin, Natrium-Sulphacetamid und Sulphamethoxypyridazin mit ausreichender Genauigkeit bestimmt werden. Bei der Bestimmung von Sulphisooxazol wurde ein endothermer Peak für Mengen von 30–100 mg und ein exothermer für geringere Mengen von 6–30 mg herangezogen.

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Amperometric monitoring of lactate accumulation in rabbit ischemic myocardium

Fabrication and characterization of miniature, flexible, planar biosensors for monitoring l-lactate accumulation in an ischemic myocardium are described. Three configurations of Au-based electrodes were fabricated by a photolithographic technique on flexible polyimide Kapton((R)) foil. All sensors are based on an immobilized lactate oxidase with amperometric detection of the enzymatically produced hydrogen peroxide at a platinum-electroplated-gold base electrode polarized at 0.5 V versus Ag/AgCl. An inner electropolymeric layer is used to prevent electrode fouling and to reject the interference effects of easily oxidizable molecules. In addition, a diffusion controlling outer layer that greatly enhances the linear dynamic range of the sensor, is obtained by casting a polyurethane external film. The developed sensor was evaluated in vitro and proved to have high selectivity, good operational stability, good accuracy and precision (average recovery = 102.3 +/- 0.4% for control sera), fast response time (t(95) = 20 s) and high upper limit of the linear dynamic range (25-80 mM, with sensitivity of 1.7-0.4 nA mM(-1) respectively at PO(2) = 15 mmHg). Subsequently, the sensor was brought into direct contact with the surface of the rabbit papillary muscle and used for continuous quantitative monitoring of extracellular lactate accumulation during no-flow ischemia.     

Selective kinetic determination of pyridoxal-5'-phosphate with an ammonia gas-sensing electrode

The coenzyme pyridoxal-5'-phosphate (PLP) is deiermined by in situ measurement of the rate of ammonia production using a potentiometric gas-sensing membrane electrode. It is shown that the initial rate of ammonia liberation from L-tryptophan by action of tryptophanase apoenzyme and the coenzyme can be linearly related to PLP levels in the nanogram range with minimal interference from related compounds. Calibration data for the 1 × 10^-7–2.5 × 10^-6 M range for PLP yielded a least-squares equation of rate (mV min^-1) = (0.64 ± 0.01) C — 0.01 ± 0.02 with a standard error of 0.02 mV min^-1, where concentration, C, is expressed in units of 10^-7 mol l^-1.