Studies on the long-term stabilities of the background of radionuclides in inductively coupled plasma mass spectrometry (ICP-MS)

The long-term stabilities of the ICP-MS background of nine radionuclides are studied, of which the signals are partially superimposed by polyatomic interferences or affected from carry-over and memory effects. The background generated by the ICP flame, by two pure waters, and by nitric acid (2% v/v) was investigated in detail. A minimum of 50 measurement points was used for each long-term investigation. The detection limits of the radionuclides of the masses 90 amu (⁹⁰Sr: 30 Bq/mL), 99 amu (⁹⁹Tc: 4 mBq/mL), 238 amu (²³⁸U: 10 nBq/mL), and 244 amu (²⁴⁴Pu: 0.6 Bq/mL) are calculated from the mean standard deviation of the background signals. For all nine radioisotopes, the calculated detection limits are between 0.8 and 6 pg/mL. While the detection limit of the mass 90 amu is blank limited, those of the mass 99 amu and the actinides are totally uneffected by the blank solutions. The detection limits are compared with those given in literature.     

Studies on the chemistry of thieno-anellated O,N- and S,N-containing heterocycles. 2. Synthesis of thieno[2,3-b]diazepine derivatives with potential CNS activity

Thieno-anellated compounds analogous to Clobazam (1) [2] and the nootropic drugs 2 and 3 [3] were synthesized. Thus, nucleophilic substitution on halogenated nitrothiophene derivatives with aniline and reaction with ethyl malonyl chloride gave after cyclisation the thieno[2,3-b]diazepinedione derivatives 7 and 14 . These compounds were methylated to give the thieno-anellated heterocycles 8 and 9 .     

L3/L2 white-line intensity ratios in the electron energy-loss spectra of 3d transition-metal oxides

The L₃/L₂ white-line intensity ratio in transition-metal oxides deviates widely from the statistical value of 2 : 1 but shows interesting systematics. In a series of oxides of a given metal, the ratio reaches a maximum for the d⁵ configuration (e.g. MnO) and a minimum for the d⁰ configuration (e.g. KMnO₄). In a series of monoxides, sesquioxides and dioxides of different metals, the ratio is again a maximum at the d⁵ configuration and decreases as the configuration changes towards d⁰ or d¹⁰. Our results, obtained by electron energy-loss spectroscopy, carried out in an electron microscope, are interpreted on an atomic mechanism involving spin-spin coupling. According to this model, the L₂ transition probability decreases in the progression d⁰ to d⁵ whereas the L₃ transition probability decreases beyond d⁵.     

Optical and electrochemical studies of the underpotential deposition of metals Part I. Thallium deposition on single crystal silver electrodes

The underpotential deposition of thallium on single crystal silver cathodes, orientations 100, 110 and 111, was investigated optically and voltammetrically. Careful chemical polishing of the silver surfaces was necessary to reveal the fine structure on the voltammograms reproducibly. The deposition process for the first monolayer was shown to be the formation of a layer of adsorbed atoms initially, followed by a phase transformation to form a crystal plane by two-dimensional nucleation and growth. The extent of the initial adsorption was related to the number of favourable sites on each crystal face such that the adsorbed layer formed a superlattice. The influence of the substrate structure was seen on the formation of the second thallium monolayer. The formation of this layer also involved adsorption followed by transformation into a crystal plane.     

The Isolation,Structure, and Synthesis of Davana Ether,an Odoriferous Compound of the Oil of Artemisia pallens Wall.

Several stereoisomers of 2,6,10-trimethyl-2:5, 7:10-diepoxy-dodeca-3,5,11-triene ( 3 ) have been isolated from the oil of Artemisia pallens. The synthesis of the isomeric mixture is described.     

An efficient synthesis of 6-formyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid and some carbonyl derivatives of it and its 6-acetyl homologue

Starting with 1,1-dimethoxy-2-propanone ( 1 ), 6-formyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid ( 5a ) has been prepared in large quantities by a highly efficient, 4-step synthesis. This compound, along with its one carbon homologue, 6-acetyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid ( 5b ) has been reacted with several carbonyl derivative forming reagents to provide a series of side chains for β-lactams. Among these carbonyl derivatives are styrylamides which were prepared from Wittig and Horner-Emmons reagents. The preparation of the phosphonium salts and phosphonate esters is also described.     

A CONVENIENT IRRADIATION CELL FOR FERRIOXALATE ACTINOMETRY

Abstract— A calibrated volumetric optical cuvette is described which both simplifies the technique and improves the precision of potassium ferrioxalate actinometry. The cuvette is used both for irradiation of the actinometer solution and for in situ dilution and chemical developing of the irradiated aliquot. The technique permits all but one manipulation to be carried out in total darkness, thus protecting the actinometer solutions from ambient light. The method can be extended to any actinometric procedure and the volumetric cuvettes are very useful in a variety of other spectrophotometric applications.     

Stereoselective synthesis of (E)-beta-tributylstannyl-alpha,beta-unsaturated ketones: construction of a key intermediate for the total synthesis of zoanthamine

(E)-beta-Trialkylstannyl-alpha,beta-unsaturated ketones are readily available from secondary propargylic alcohols via a two-step sequence involving highly regio- and stereoselective Pd(0)-catalyzed hydrostannation followed by mild oxidation (TPAP). The methodology has been applied to the synthesis of enantiomerically pure enone 12 which is a key intermediate for the total synthesis of zoanthamine, a structurally complex marine natural product.     

HPLC of antibiotics. 1. Streptolydigin and related compounds

Two new acyltetramic acids related to streptolydigin have been isolated from fermentations of Streptomyces lydicus. The principal members of this complex were resolved by TLC on silica gel. However, the methods of detection, permanganate spray or bioautography, were not suitable for both crude fermentation broths and purified extracts. Gas chromatography is unsuitable for the detection of either underivatized or silylated streptolydigins. High performance liquid chromatography (HPLC) particularly on triethylaminoethyl cellulose is rapid and sensitive and is the method of choice for the analysis of both crude and purified samples. Using high performance liquid chromatography, two components were detected in the complex, which are not observed using any of the other chromatographic procedures.